Special Project 1 - Improvised Manufacture of Nitric Acid PDF

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Special Project 1: Improvised Manufacture of Nitric Acid
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The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid
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1. Uses of Non-Anhydrous Nitric Acid (4 replies)

2. Proper/Safest Heat Source Question (5 replies)
3. Distillation of HNO3 with OTC products (3 replies)
4. Found 2 liters of 70% nitric acid. What to do with it? (6 replies)
5. HNO3 Purification with CO2 (5 replies)
6. Nitric acid physical properties - just the facts (1 replies)
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18. Electrolysis of Ammonia (21 replies)
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20. Quantitative report on HNO3 distillation (0 replies)
21. Vacuum Distilator Schemes (13 replies)
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24. short question about hno3 - Archive File (1 replies)
25. Cleaning up after nitric distillation - Archive File (1 replies)
26. Concentrating HNO3 - Archive File (17 replies)
27. From AN to Nitric acid. - Archive File (4 replies)
28. 95% Azotic Acid without Vacuum Pump - Archive File (0 replies)
29. Some interesting reactions - Archive File (13 replies)
30. Generating Oxygen Gas for the Production of Nitric Acid - Archive File (37 replies)
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32. Some nitric acid questions - Archive File (0 replies)
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34. Nitric Acid Distillation - Archive File (1 replies)
35. Concentrating Nitric Acid - Archive File (73 replies)
36. nitric acid %? - Archive File (1 replies)
37. Why does my nitric acid not condense? (3 replies)
38. Concentrating HNO3 by decomposing HNO3 - Archive File (14 replies)
39. NA from Ca(NO3)2 - Archive File (27 replies)
40. short question about hno3 - Archive File (2 replies)
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45. Acid recovery after RDX pption - WARNING!!! (5 replies)
46. what a conc. of H2SO4 would work for HNO3 dist? - Archive file (0 replies)
47. Nitric Acid - Archive Thread (0 replies)
48. Distilling Nitric Acid (150 replies)
49. Distilling HNO3 and fire hazards (6 replies)
50. HNO3 (83 replies)
51. HNO3 the easy way (89 replies)
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53. HNO3 purification via decanting with acetone, and the runaway nitration which ensued (1 replies)
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55. Nitric Acid Purification (21 replies)
56. HNO3 byAgNO3 (2 replies)
57. Expedient Nitric Distillation (2 replies)
58. A review of ammonia preparation (25 replies)
59. Dehydrating agents(for concentrating HNO3) (16 replies)
60. HNO3 from air, using an electric arc. (92 replies)
61. Syntheses of 100% Nitric Acid HNO3 (5 replies)
62. Methylene Chloride (118 replies)
63. Purifying and concentrating sulfuric acid. (2 replies)
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67. FKT: HONO2 The inconcievable (5 replies)
68. Nitric Acid by Kno3 (47 replies)
69. concentrating nitric? (20 replies)
70. Nitric Acid Manufacture (23 replies)
71. HNO3 with NaHSO4+KNO3 (9 replies)
72. Nitric Acid manufacture (35 replies)
73. Nitric Acid Catalyst (33 replies)

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The Explosives and W eapons Forum > Chemistry for Am ateur Expe rimenters and C itizen Scientists > Special Project 1:
Improvised Manufacture of Nitric Acid > Dehydrating agents(for con centratin g HNO 3)
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rikkitikkitavi August 23rd, 2002, 12:14 PM

W ell, it is showing up in various thread s in this section. So assuming we have a way of obtaining HNO 3, how do we get it to 95+
%?
So what mea ns of dehydrating do we have? Im refering to conce ntrating

68% , aezotropic HNO 3. Trying to concentrate lower % a cid is only a waste of dehydrating agent, since a simple distillation at
atmospheric pressure can give 68 % HNO 3 from lower conc.
First idea is H2SO4, which can be reused. This is well proven and m ight n ot need distillation under vacuum , if the extraction-
route is taken. (se CH2Cl2-thread)
There is also the possibility of using solid dehydrating agents like

C a S O 4, CaCl2, Mg(NO3)2 e t c.
I h a v e e x p e r i m ented a bit with CaSO4, but gaining no success. Left was a mushy mix of HNO3-dre anced CaSO4 slowly
solidfying. To much C a S O 4 i s n e e d e d t o c o m pletely absorb all the water.
Industrially, Mg(NO 3)2 is used in parallell to the H2SO4 m e t h o d .
HNO 3 of 68 % is m ixed with 72 % Mg(NO 3)2 and feed to a distillation tower. In the bottom 68 % Mg(NO3)2 is recovered and
later reconcentrated under vacuum. At the top 100 % HNO3 is re covered.
This gives that for 100 grm HNO3 68 %, you need 544 grms 72 % solution, yielding 68 gram s 100 % HNO 3.
This is of course theo retical, losses com e in to play in real life. The density of the Mg(NO3 )2 solution is roughly 1,4 , so
translates to rougly 400m l m ixed with 70 m l HNO3.
Is this feasible to do in a labscale?
The Mg(NO3)2 solution will be thick in consistency, I have not a exact value, but a guestimate wou ld be like syrup.
A n d m o r e i m portant, ideas to dehydrate HNO3 by other means? solids dehydration, extraction or whatever..
/rick ard
vulture August 23rd, 2002, 02:53 PM

Mg(NO3)2 co uld be possible, but using MgSO4 would be easier, since it's m ore easily available. How m uch water can Mg(NO 3 ) 2
t a k e ? I k n o w t h a t o n e m o l e M g S O 4 c a n a b s o r b u p t o 1 2 m oles of water.
Also, does the Mg(NO 3)2 dissolve? I'm asking this because when using MgSO4 and if it is added carefully and in ex cess, it
won't dissolve but just fall out of the solution as the hydrate crystal. The nitric wouldn't need (as m uch) destillation then.
<sm all>[ August 23, 2002, 01:55 PM: Message edited by: vulture ]</sm all>
xoo1246 August 23rd, 2002, 05:32 PM

It occurs in n ature as nitrom agnesite( Mg(NO 3)2.6H2O ).
I'm also interested in using MgSO 4 to dehydrate HNO 3 since it's easy to get and m a y b e a g o o d r o u t e f o r t h o s e w h o d o e s n ' t
have distillation appa ratus(?)
<sm a l l > [ A u g u s t 2 3 , 2 0 0 2 , 0 4 : 4 4 P M : M e s s a g e e d i t e d b y : x o o 1 2 4 6 ] < / s m a l l >
kingspaz August 24th, 2002, 09:38 PM

wouldn't the HNO3 do nate H+ to the sulphate ion present in the MgSO4 to som e extent? i know it wouldn't very m uch since
sulphate is a m uch weaker base but it would a little resulting in a minute am ount of H2SO 4 contam i n a t i o n . . . i f t h a t m a k e s n o
sense sorry but i'm sooooo tired!
Pu239 Stuchtiger August 24th, 2002, 10:55 PM

Here's the problem .
MgSO 4 + HNO 3 ----> MgHSO4(NO3)
MgHSO4(NO3) should be fairly soluble in HNO3. Problems like this are why HNO3 prepared from Ca(NO3)2 and H2SO 4 by
filtering out the precipitate is going to be heavily contaminated with Ca++ cations.
Polverone August 25th, 2002, 02:17 AM

M a g n e s i u m n i t r a t e i s e a s i l y p r e p a r e d . B o i l a m m onium nitrate so lution with m a g n e s i u m carbonate or hydroxide. It does cling to
water very tightly (hey, otherwise it wouldn't be of much use.) I've heated the molten hydrate up to 150 C and it just sat there,
look ing at me, apparently not doing anything. I'm not sure how hot it would have to get to give up all of its water. My Lange's
h a n d b o o k s a y s t h a t t h e h y d r a te decom p o s e s a t 129 C, but I don't know if they m ean it starts giving up water at that
temperature or what. In any case it doesn't give up the water very fast.
rikkitikkitavi August 25th, 2002, 05:44 AM

I think that anhydrous Mg(NO3)2 is ha rd to pre pare, like anhydrous MgCl2, due to the fact that it has to be heated to such
high temperatures that the NO3- ions decom p o s e .
However, it is a solution of 72 % m /m that is used in the extractive distillation.

If you look u p "dehydrating agents" in Lange (and CRC) , there is a table of how effective dehydrating agents are com p a r e t o
each other.
B e s t i s P 2 O 5 , H 2 S O 4 , C a S O 4 e t c. This lead m e to believe that

C a S O 4 was efficent.
/rick ard
Madog555 August 29th, 2002, 04:54 PM

i am getting confused on this. i have read that you can boil down low con centratio ns up to 68%. can anyone confirm this? thats
what a i need to know.
rikkitikkitavi August 29th, 2002, 05:36 PM

you cant "boil down" nitric acid to 68 % like you can with sulfuric acid.
If you have a HNO3/H2O mix with less than 68 % HNO3 and it boils the vapours will be richer in H2O % than the boiling liquid.
But they still contain HNO 3.
So the liquid slowly gets enriched in HNO3 until it reaches 68 %. Then the vapour also is 6 8 %.
So to do this properly , you need a distillation setup with a fractionating coulm n. Like in a still for home ma de alcohol.
T h i s s e p a r a t e s t h e H N O 3 / H 2 O m ore efficently, so that only H2O com e s o ut at the top until the concentration in the botton
reaches 68 % .
Counterwise , above 68 % the vapour given of is richer in HNO 3 than the liquid until the concentration in the liquid has reach e d
68 %.
/rick ard
jimwig S e p t e m b e r 3 0th, 2002, 10:23 PM

i haven't tried this yet but sulphuric will suck wa ter like the tijuan a whores
will suck the chrome off a bum ber hitch. (or so I have been told)
s o u n d s r e a s o n a b l e . m i x t u r e o f "HNO a nd HSO " and distill. should be som e pretty strong

stuff. don't spill any on your b umber hitch. using vacuum wouldn't hurt. lowers distillation
temperature i figure. clean high test - rrroooooom m m !!!
rikkitikkitavi October 1st, 2002, 02:51 AM

gee, jim wig, that was some useful info ./irony
If I ever go to Tijuana...
/rick a d
simply RED October 18th , 2002, 08:15 AM

You can distil a m ixture of Pb(NO3)2 a nd H2SO 4(96%H2SO 4 5 , a n h y d r i d o u s l e a d n i t r a t e ) t o g e t 9 6 % H N O 3 g o o d e n o u g h f o r
h e x o g e n . I m a d e a d istiller using a construction sim ilar to "iodin e chrystalizer" the nitric acid condenses on the cool test tube
and leaks in a beher glass below the test tube.
i'm gonna describe the device when have tim e...
y u c a n m a k e the device with a glass ja r and polyethylene v shaped "cap' in the ja r is put another jar or beh er glass to collect
the acid
one ay i m a d e 4 0 0 m l alm ost anhydride HNO3...
<sm all>[ October 18, 2002, 07:19 AM: Messag e edited by: sim ply RED ]</sm all>
Marvin October 19th , 2 0 0 2 , 0 9 : 2 1 P M

That m ethod will certainly work, and the low solubility of lead sulphate will aid it, but to m e i t s e e m s s o m e t h i n g o f a w a s t e o f
l e a d nitrate. I'm sure I dont h ave to m ention its toxic, but it will decom p o s e t o ' n i t r o u s g a s s e s ' e s s e n t i a l l y a m i x o f N O 2 a n d
NO on heating, this would contaminate the acid but can be very useful. The temperature affects the ratio and with the right
ratio pure sodium nitrite can be produced from hydroxide or carbonate, and m ore interestingly amm onium nitrite ca n b e
p r o d u c e d . A m m onium nitrite resists most other attem pts to produce it, eg a mixture of a nitrite an d a n a m m onium com p o u n d
generally decomposes to nitrogen and water.
A dehydrating agent for nitric acid that may or m ay not have been discussed allre ady is m etaphosphoric acid, it can be m a d e
easily and its *just* possible a mixture can be obtained consisting of m o r e t h a n o n e p h a s e . P o t e n t i a l l y r e m o v i n g t h e
requirement for distillation.
I will search to see if either of these has been discussed before, and what inform ation I have on the subjects.
Polverone October 20th , 2002, 06:07 AM

</fo nt><blockquote>quote:<hr />Am m o n i u m nitrite resists m ost othe r attemp ts to produce it, eg a m ixture of a nitrite and an am m onium com p o u n d
generally decomposes to nitrogen and water.<hr /></blockquote>Truly? That's kind of disappointing. I'd always thought that if I ever wanted am monium nitrite I'd just m i x
p o t a s s i u m n i t r i t e a n d a m monium perchlorate.
vulture October 20th , 2002, 11:56 AM

J u s t a s i d e n o t e : M o s t a m m onium s a l t s w i t h n o n m e t a l o x i d e s a s t h e n e g a t i v e p o l y a t o m ic group are only stable if the non
m e t a l h a s t h e h i g h e s t v a l e n c e t o o x y g e n . E x a m p l e s : A m m onium perchlorate is ve ry stable , while chlorate is not, the s a m e
g o e s f o r b r o m ate/perbrom ate.
I think this h a s s o m e thing to do with the stronger oxidizing properties of the chlorate/brom ate versus perchlorate/perbromate.
simply RED October 21st, 2002, 10:37 AM

"Pb(NO3)2 will decom p o s e i n m y distilation system"
l e a d nitrate decomposes in very very high tem perature, at that temperatures H2SO4 boils and ecom poses too! The ditilator
works on water bath, this is 100 degrees and none of the products decom p o s e , o f c o u r s e s o m e HNO3 turns to nitrous oxides
and oxigen but the ditilator is colosed and they form hno3 again... Pb(NO3)2 is n ot poisonous if not taken very long time, o r
in very, very high dose, look in its data in the net!!!
Ca(NO3)2 - 1dolar per kilo

H2SO 4 96% 2 dolars per kilo
h e x a m ine 2 dolars per kilo
~20 kilos Ca(NO3)2 plus ~15 kilos H2SO4 will produce ~15 kilos 96% nitric acid - 50$
1 5 k i l o s H N O 3 + 2 k i l o h e x a m ine = 2 k ilo RDX
2 dolars for the silicone paste and you have 2k g PBX... for ~60$
Period of pro duction 3 days (if you work untouched)!!!
( a t t h e s a m e price everyoune can m ake 5kg plasticized PETN)
I'm g o n n a p r o v e i t i f h a v e e n o u g h t i m e
:)
<sm all>[ October 21, 2002, 09:51 AM: Messag e edited by: sim ply RED ]</sm all>
Marvin October 22nd, 2002, 01:33 AM

("Pb (NO 3)2 will decompose in my distilation system")
Dont paraphrase with quotes sim ply RED, use brackets or som ething else.
You are quite right about the decom position, I assum ed since it could be done in glass co ntainers that it was less than about
350C, its actually about 450C. If your distillatio n is at 100C then you are doing very well, when I was using sodium nitrate and
sulphuric acid my distillation e n d e d s o m ewhere over 250C. If you are willing to have lower yeilds based on sulphuric acid you
can reduce these tem perature s.
"Pb(NO3)2 is not poisonous if not taken very long tim e, or in very, very high dose"
Lead nitrate is downright toxic and the MSDS supports this. Though the a cute exp osure, LD50 is somewhat unim pressive, this
is becuase its not comm only relavent, exactly why MSDS sheets dont just rely on these values and in the case of this specific
salt often dont contain them. Lead is a cum ulative toxin with a very long biological half life, of the order of 20 years. Hydrogen
cyanide for e x a m p l e h a s a b i o l o g i c a l h alf life of about 1 hour. This expla ins why the long term e x p o s u r e v a l u e s ( e g T L V / T W A )
for lead nitra te are lower (by a factor o f 20) than cyanide salts.
T h i s d o e s n t m ean that lead nitrite is m ore toxic than cyanide, but it does m e a n s a f e l e v e l s o f e x p o s u r e i n t h e l o n g t e r m ( e v e n
if the actual exposure is acute) is lower for lead nitrate than it is for cyanides.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Nitric Acid
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stanfield July 20th, 2001, 05:17 PM

Like many guys on this site, I produce my own nitric acid by distilling sodium nitrate and sulfuric acid, the equation is : 3NaNO3+2H2SO4 ==> 3HNO3+NaSO4+NaHSO4
So, if I have 500g of NaNO3, how much sulfuric acid do I need ? (I have 95 % H2SO4)
I think i'm wrong somewhere in my calculations...
thanx...
Anthony July 20th, 2001, 08:12 PM

RAM of 1 molecule of HNO3 w ould be 1x1 1x14 3x16 = 63
For one molecule of HNO3 you'd need one molecule of NaNO3 to supply the NO3 and 0.5 molecules of H2SO4 to supply the H.
So you should need tw ice as many molecules of NaNO3 to H2SO4.
RAM of NaNO3 = 1x23 1x14 3x16 = 85

RAM of H2SO4 = 2x1 1x32 4x16 = 98
85/63 = 1.35
98/63 = 1.55
So, you need 1.74 times as much NaNO3 as H2SO4. so for 500gm you'd need 500gm/1.74 = 287gm H2SO4 and you'd get 371gm of HNO3
Lagen July 20th, 2001, 08:39 PM

stanfield: Actually there should be Na2SO4 but I see what you mean. Given that the equation is correct, and given your numbers, you w ould need 405g of the acid, the
theoretical yield w ould be 391g HNO3 containing 20g water, or roughly 95% nitric. (371g anhydrous if you manage. But you won't. This reaction proceeds at higher temps and
there w ill be lots of HNO3 decomposition.)
Anthony: I think a very high temperature would be necessary to convert NaNO3 to Na2SO4 completely (lots of decomposition again). I lean more towards stanfield's equation,
or maybe only NaHSO4 would be produced, depending on the conditions. In that case (at low er temp., 50-60C, vacuum):
NaNO3 + H2SO4 -> HNO3 + NaHSO4 and 607g H2SO4 -> 371g HNO3 anhydrous again, or 401g with all the H2O (only 92.5% this way, but more likely to succeed).
[This message has been edited by Lagen (edited July 20, 2001).]
stanfield July 21st, 2001, 03:41 AM

Anthony VS Lagen :
Tw o guys
Tw o answers
Who win ?
http://theforum.virtualave.net/ubb/smilies/smile.gif
more seriously, i found 405g like anthony...

but Lagen's calculation seems right too...
The temperature at the end of my Vigreux Column is around 70-80C so, I dont think Water can pass since, it boils at 100C !
Any reply is more than appreciated
Lagen July 21st, 2001, 08:25 AM

stanfield: 405g of which acid? Of the distillate? Or did you mean the 405g in my post? I'm confused. Anthony's reaction assumes more complete (in fact perfect) conversion and
hence you would need much less H2SO4 than 400g.
Generally the amount of distillate would be around 400g too, it doesn't depend much on which of the reactions will happen. (Only the H2SO4 consumption and resulting purity.)
In reality you shouldn't expect more than 85% from the first distillation, and should redistill with H2SO4. Some water will pass too, as the b.p. of H2O and HNO3 are too close
together and they will not boil completely separately. It's similar to distilling alcohol, you don't get 100% at 80C, but not even the 96% (azeotrope) from the first distillation.
Some H2O also results from HNO3 decomposition (if the red fumes are there then H2O will be too).
Somebody with greater experience, please give us your comments...
Anthony July 22nd, 2001, 03:20 PM

Dude, go with Lagen's answer! I haven't taken into account the various inefficiencies that will occur.
It does raise a question of my own though, Lagen you say that considerably more H2SO4 is needed than I w orked out. When doing nitrations w ith metalNO3/H2SO4 I have been
using the amount of H2SO4 worked out as above. This is obviously a problem, how much extra H2SO4 do you think should be used to counter the effects of the inefficiencies?
Lagen July 22nd, 2001, 04:08 PM

Well I'm not an organics chemist, just a chemistry hobbyist, but these are my guesses:
With plain nitric acid the nitration would look something like this:
R-H + HNO3 -> R-NO2 + H2O
H2SO4 would be added to take up the water. With a "mixed" acid it w ould look something like this:
(I know this is gross oversimplification.)
R-H + MNO3 + H2SO4 -> R-NO2 + M+ + HSO4- + H2O
R-H + MNO3 -> R-NO2 + M+ + OH-
The metal produced is basic so HSO4- -> SO4(2-)
Can be thought of as: MOH + MHSO4 -> M2SO4 + H2O
------------------------------------------------------------------------------
Overall imaginary equation: 2 R-H + 2 MNO3 + H2SO4 -> 2 R-NO2 + M2SO4 + 2 H2O
During distillation the preferred reaction is MNO3 + H2SO4 -> HNO3 + MHSO4. The "excess" H2SO4 is there to allow all the HNO3 to distill over by this mechanism. The other
process, 2 MNO3 + H2SO4 -> 2 HNO3 + M2SO4, where you have just half the amount of H2SO4, proceeds according to MNO3 + H2SO4 -> HNO3 + MHSO4 at first. At some
medium temperature (like 100C I'd say) you end up with a MNO3 + MHSO4 mix (50/50). When this is pushed harder, like with 300C or so, the MHSO4 acts as an acid: MNO3
+ MHSO4 -> HNO3 + M2SO4. So strictly speaking, the excess H2SO4 is not there just because of inefficiency, but mainly because the "perfect" two stage process cannot
proceed. I'd say that during the nitrations you have quite a different situation, you have couple of other things around, not just KNO3 + KHSO4 (at least it's in solution!), so the
reactions can make it to the M(+)2SO4(2-)...
So I think, wherever you can do the nitration with plain nitric acid, just use metalNO3 + H2SO4 in stoichiometric proportion. Use an excess H2SO4 to the same extent as it is
used in the nitric/sulfuric mix. But! I am sure that one cannot change the composition of the nitrating mix and expect to get exactly the same results. One example you all are
familiar w ith: the nitration of PE. Using a mixed acid yields a product of poor quality... Nitrating hexamine to RDX with KNO3+H2SO4 sounds ridiculous, right? Sometimes it can
work fine, sometimes it may w ork backwards, sometimes you w on't get anything at all. The background mechanisms of nitration are pretty damn complicated and one cannot
make a generalising statement, without having a particular reaction in mind.
For example, I found this info on the effects of increasing H2SO4 concentration:
In solution, nitric acid exists in the form of either NO3(-)H+ or N(O3)(-)H(+). Concentrated HNO3 on the other hand has this structure: NO2.OH or NOH.O2 (in equilibrium). This
is called pseudo-acid, and has the form of a nitric ester. The pseudo-acid is capable of nitration and esterification, while the dissociated acid is not. Addition of w ater increases
concentration of dissociated acid (NO3(-)H+). Adding H2SO4 increases the concentration of pseudo-acid. Sulfuric acid is stronger than nitric and passes its proton to the nitric
acid: NO2.OH + H2SO4 -> NO(OH)2(+) "nitracidium ion" + HSO4(-), or NO2.OH + 2 H2SO4 -> N(OH)3(2+) "hydronitracidium ion" + 2 HSO4(-). So IMHO a nitrating mix
composed of KNO3+H3SO4+HNO3 could behave differently under circumstances...
In the KNO3+ H2SO4 mix, the dissociation would look like this: KNO3 + 2 H2SO4 -> NO2(+) + 2 HSO4(-) + K+ + H2O. As you can see, there is only a nitronium ion produced
and no nitracidium or hydronitracidium, so again, this may or may not behave like genuine HNO3... I'm sorry to disappoint you, but I'd say stick to the standard, tested
procedures and always consider the substitution of a MNO3+H2SO4 mix an experiment!
stanfield July 22nd, 2001, 06:05 PM

according to you that in my vigreux column, the temperature is ~ 80C, what will be the concentration of my nitric acid (approximately) ? Do I need to re-distillate it for HE
synthesis ?
thanx !
Lagen July 22nd, 2001, 06:29 PM

That depends on w hat nitration you have in mind! If it requires something like 98%, you cannot expect that from a single step distillation. But there is a number of reactions
where you use only 65-70% HNO3.
The concentration depends mostly on the strength of the sulfuric acid (you said yours is 95%), how much the HNO3 is decomposed, and whether Na2SO4 is formed. The
maximum theoretical concentration from the numbers you gave w ould be 95%, but only if not too much nitrogen oxides appear! If you use a vacuum, you could approach that
concentration, and only if you do not use more than the 405g H2SO4 and if the amount of HNO3 produced is around 400g. The other extreme: Without a vacuum, with 600+g
H2SO4 95% it could be something like 85%. There are too many combinations and I don't know the details!
My guess is this: NaNO3+ H2SO4-> HNO3+ NaHSO4. You aren't using vacuum and 80C is a little bit too hot. You would use 600g H2SO4 and the conc. w ould be low er (like 85-
90%).
Anthony July 22nd, 2001, 08:43 PM

Thankyou for taking the time to post that information in detail Lagen. I will do some calculations with various known to work MNO3/H2SO4 nitration procedures and see what
amount (if any) of excess H2SO4 they use, to see if there's a general figure.
stanfield July 23rd, 2001, 05:31 AM

hey, Lagen,
do you think I can tell you the weight of my acid (example : 50 mL) and you, you could give me an approximate concentration ?
(for information : my acid is fuming and yellow, not red !)
thanx...
Lagen July 23rd, 2001, 08:11 AM

Sure, no problem, I've got density tables here in my spreadsheet all ready to go!
What I would recommend to you, make an improvised hydrometer (I believe PHILOU posted the instructions some time ago) or buy one with a 1.0-2.0 range. The car battery
kind you can get at gas stations etc. will not work, it's only 1.1-1.3.
I could email a decent excel table for HNO3 if you're interested (or post it here, but it's BIG).
stanfield July 25th, 2001, 05:46 AM

I weighed my acid :
I only have a 0.1 g electronic scale and the value oscillates between 75.8 and 75.7 g for 50 mL. so, what's the concentration ?
and could you send me your density table ?
thanx for all !
Demolition July 25th, 2001, 05:59 AM

It's easy to find the density.Just divide the weight of the acid by how many ml's there are.In your case
75.8 divided by 50 = 1.51
I'm not to sure but I think the concentration would be around 98-100%.
Did you distill it under vacuum?
Demolition

I'll post a picture of my distillation apparatus soon...
see ya !
John456 July 25th, 2001, 02:05 PM

Stanfield, w hat color is your acid? Mine is always a cloudy dark yellow even when its in the 98-100% range. It fumes thick white.

my acid is yellow but no dark... it fumes thick white too...
here is my distillation apparatus :

http://ww w.geocities.com/st4nfield/distillation.jpg
see ya !

damn... w hen I try to view my page it says 404 http://theforum.virtualave.net/ubb/smilies/frown.gif
I registered to geocities 5 min ago !!!
and you ?

Stanfield, pretty good job!
But! These measurements can be very tricky! The difference in density of 100% and 90% HNO3 is only 2.6%! Which means the volume must be measured very precisely! A 1%
error (0.5ml in your case) would thus lead to a 5% error in calculated concentration!
That's why I stick to the hydrometer - it affords better precision. Another good point is that you can do the measurement even on a small sample, with no decrease in precision.
If you measure the volume (& weight) you need a large sample to do it precisely enough. The improvised kind would have another good point, you can make the scale to read
in % directly w hich altogether saves a lot work if you do these measurements frequently. I am sending the density table to you (1000 rows). For everybody - here's a
condensed form of it:< CENTER>
<TABLE BORDER=0 CELLSPACING=0 CELLPADDING=0>
<CAPTION ALIGN=TOP></CAPTION><TR><td w idth="55"> w[%]</td><td width="120">d[g/ml]</td>< td width="55">w[% ]< /td> <td width= "120"> d[g/ml]</td><td
width= "55">w [% ]</td> <td width="120">d[g/ml]</td></tr>< TR><td>1</td><td>1.0036< /td>< td>42< /td> <td>1.2591</td>< td> 84< /td>< td>1.4655</td></
tr><TR><td>2< /td> <td>1.0091</td>< td> 44
</td><td> 1.2719</td><td>85
</td><td> 1.4689</td></tr><TR><td>4< /td> <td>1.0201</td>< td> 46< /td>< td> 1.2847</td><td>86</td>< td> 1.4716</td></tr><TR><td>6</td> <td>1.0312</
td><td>48</td>< td> 1.2975</td><td>87
</td><td> 1.4745</td></tr><TR><td>8< /td> <td>1.0427</td>< td> 50< /td>< td> 1.3100</td><td>88</td>< td> 1.4773</td></tr><TR><td>10</td><td>1.0543< /
td><td>52</td>< td> 1.3219</td><td>89
</td><td> 1.4796</td></tr><TR><td>12</td><td>1.0661< /td> <td>54</td><td>1.3336< /td>< td> 90< /td> <td>1.4826</td>< /tr>< TR><td> 14</td>< td> 1.0781</
td><td>56</td>< td> 1.3449</td><td>91
td><td>60</td>< td> 1.3667</td><td>93
td><td>64</td>< td> 1.3866</td><td>95
td><td>68</td>< td> 1.4048</td><td>96.5</td ><td> 1.4972</td></tr><TR><td>28
</td><td> 1.1666</td><td>70</td><td>1.4134< /td> <td>97</td><td>1.4988< /td>< /tr> < T R > < td> 30< /td> <td>1.1800</td>< td> 72< /td>< td> 1.4218</
td><td>97.5</td><td>1.5005< /td> </tr><TR> <td>32
td><td>98.5</td><td>1.5044< /td> </tr><TR> <td>36
td><td>99.5
</td><td> 1.5091</td></tr><TR><td>40</td><td>1.2463< /td> <td>82</td><td>1.4589< /td>< td> 100</td><td>1.5129< /td> </tr></table> </CENTER>
Anthony July 25th, 2001, 10:29 PM

stanfield, geoshities won't let you link directly to a file, you need to put the picture on a HTM or HTML page and then link to that.

you'll have to type manualy the URL in your browser to acess my picture...
I did a search for "hydrometer" but nothing was found... I would like more info on this stuff plz... and how to make one if possible.
thanx for all !
Lagen July 26th, 2001, 06:36 AM

The instructions for the improvised hydrometer w ere posted here by PHILOU Zrealone on April 20 on the "No nitric acid" http://theforum.virtualave.net/ubb/smilies/smile.gif
thread. It's on page 2.
For a professional hydrometer you would most probably have to go to a labware supplier. There are other kinds sold elsewhere (like the ones for car batteries, winemaking etc.)
but they're not appropriate (do not range to 1.5+ ).
Mick July 26th, 2001, 06:44 AM

yeah, geoshits sucks
for those of you who w ish to view the picture, just right click the link and select "Save Target As.."
and then save to your desktop or something and view it there

Lagen, are you sure that no hydrometer (for car battery) on the market range to 1.5+ ? I will try to phone some companies to ask them about hydrometer...
If you found one in your contry, Lagen, you could buy and send it to me then, i'll re-buy it to you...sorry for my bad englsih http://theforum.virtualave.net/ubb/smilies/smile.gif
finally, if you find a labware supplier who can sell in France and who has (good)hydrometer, tell me too...
see ya !

Now I have the guts of a car battery hydrometer in front of me, it only goes to 1.3. But obviously, one could cut the glass tube open, insert some more lead shot and re-seal it.
All that one would need then, would be some good calibration solution (of a high and exactly known density).
The prices here are as follows:

w/out thermometer they all cost cca 8$:
1.0-2.0
1.4-1.6
w/thermometer they cost about twice as much:
1.45-1.50
1.40-1.50
1.50-1.60
I will look for some more sources if you're interested, I'm not sure if any would deliver to France, but surely you can get it close to your home too.
nbk2000 July 26th, 2001, 11:07 PM

Hydgrometer is simple:
A large straw has one end heat sealed. Enough BBs to keep it floating upright about half way in the w ater are dropped in and a little wax dropped in and melted to hold the BBs
in place.
Then calibrate. First in water at (I believe) 3*C (maximum density = 1). Then in another pure liquid of know n denisty. The difference betw een the 2 is evenly divided and
extrapolated to both ends of the scale. If you have a clear straw, you can mark the scale on a piece of paper that you then have sealed inside the straw.
Cost = $0
------------------
"The know ledge that they fear is a weapon to be used against them"
Go here (http://members.nbci.com/angelo_444/dload.html) to download the NBK2000 website PDF.
Go here (http://briefcase.yahoo.com/nbk2k) to download the NBK2000 videos.
Chaos A.D August 6th, 2001, 06:07 PM

ok, I havent tried it but from my knowlege of chem this process for making nitric acid wont work...
When you mix H2SO4 and CaNO3 the Ca precipitates out the SO4. you're left with a solution of NO3- and H+.
Nitric acid is a strong acid so the equation:

HNO3 --> H+ + NO3-
is not reversable.
That means the ions w ont come together to form HNO3.
To make nitric acid, industry uses the Haber process... That uses NH3 and O2.
Lagen August 6th, 2001, 07:05 PM

http://theforum.virtualave.net/ubb/smilies/confused.gif To my best knowledge the Ca(NO3)2+H2SO4 process fails due to the CaSO4 being insoluble (even more so because of
the SO4(2-) common ion) and forming a layer on the Ca(NO3)2 preventing it from being reacted. But to make dilute HNO3 w/ some Ca(NO3)2 in it, or to concentrate HNO3,
this works pretty w ell. Please look here (http://theforum.virtualave.net/ubb/Forum1/HTML/000452.html). I have no idea w hat you meant by the equation thing. Please read in
my earlier post here on the ions occuring in HNO3 soln. Why should the ions "combine"? There is no such thing as a HNO3 compound, except at 0 Kelvin. Even 100% HNO3
undergoes autoprotolysis, so some ions form. The H2SO4+ KNO3 or H2SO4+NaNO3 rxn followed by distillation w orks well too and has been discussed to death.
[This message has been edited by Lagen (edited August 06, 2001).]
BrAiNFeVeR August 6th, 2001, 07:59 PM

Why w ould anyone want to make nitric acid ??? Isn't it less expensive to jus t buy it ? (less then 5 /liter)
Making it yourself could only make sense if you could not buy it (which country do you live in ? UK ??)
Anyway, on making nitric acid you can find tons of information on the net (as it w ould be a nice experiment) I easily could give a pile of addresses, but hey, if you're too lazy
too look for yourself ;-)
------------------
"Mess with me, and you'll end up with a .44 under your chin and your brains on the ceiling"

I'm getting it for 1.5/ltr. 65%. H owever I serious ly doubt that you can buy any more than 90% HNO3 anywhere. Even that w ould have 2 bad points about it: for HE synthesis it would
need distillation anyway, plus it w ould be a BIT more expensive than OTC H2SO4+fertilizer followed by distillation.

ok, just cause u got NO3- and H+ ions in the same solution it does not mean u have Nitric acid. If that was true you could make nitric acid out of any other acid.
What if you mix acetic acid(vinegar) and any nitrate...
CH3COOH + NaNO3 --> CH3COO- + Na+ + H+ + NO3-
Here there is H+ and NO3- in the same solution. This is not nitric acid. Nirctic acid is HNO3, not H+ and NO3-. Thats nitric after it has reacted w ith something.
Chemicaly it is not possible to produce nitric acid this was. Why would they(industries) make nitric using the costly Haber process if it was just this easy.
FadeToBlackened August 8th, 2001, 03:29 PM

HNO3 forms H+ and NO3- in solution.

I hate to repeat myself, but if you really think it's impossible, I recommend you to make a dilute solution of calcium nitrate, and add (a calculated amount of) sulfuric acid to it.
Filter out the precipitate and do some tests on the liquid, to prove it's not nitric acid. You will be surprised. It will colour your skin permanently yellow. What's that? Nitric acid. If
you still don't believe me, then I can't help you any more. You just lost an easy way of making HNO3 (dilute, of course). Yes the Haber process is cheap to do on large scale,
because there aren't any byproducts to throw aw ay.
H+ + H2O tends to form H3O+ (oxonium cation).

I have included a link to PHILOU's explanation of how this mechanism can be used for concentrating nitric acid - or producing more nitric acid in a nitric acid solution. As you just
insisted it's impossible, I'm including a copy here for your kind perusal. Sorry to everyone else for the crappy post. You can used this
process w ith a little modification to produce nitric acid more concentrated than the original one without need of a distillator:
If you have concentrated H2SO4 more than your HNO3- and only if you have it!
-Mix hot medium conc or conc HNO3 and saturate it w ith Ca(NO3)2 by strong stirring.Heat it long to be sure it is saturated. Cool it until ambiant temp some Ca(NO3)2 cristals
will come out proof of the saturation, filter them. In the clear solution can now be inserted under stirring the conc H2SO4 ( it has to be in minor quantity as compare to
Ca(NO3)2 dissolved).
Then in your solution you will have a cloud of CaSO4 pure HNO3 more concentrated and some Ca(NO3)2 leftover.

ok fine, if you actually did it and it works. I havent tried it but Im just going by w hat I learned it chem.

Double replacement w ith precipitation will be one of the most common schemes you will encounter in "preparative" chemistry. In this one you can practically get just "dilute"
HNO3 because the mass of the precipitate is comparatively large and it will take up a lot of space in the reaction mix. If you try to make more concentrated HNO3, you will end
up with an almost solid mass of CaSO4 from w hich the HNO3 is nearly impossible to separate. Most precipitated stuff has an initial density of 0.1-0.05, you can figure out w hat
that means in this case...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1:
Improvised Manufacture of Nitric Acid > HNO3 the easy way
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View Full Version : HNO3 the easy way
kingspaz January 1st, 2003, 09:09 AM

right, you are trapped in a desert and need a piss but don't want to lose the water. what do you do? you piss in a whole and
put a plastic bag over it with a stone in the centre to make a cone. the water from the piss evapourates and condenses and
can be collected with a cup underneath the bag. now try this with HNO3 :)
this was originally thought of by simplyRED. all i have done is develop this a bit.
the idea is to take the mix you would normally distill containing H2SO4, HNO3 and
xHSO4 and apply the desert survival technique.
it works because H2SO4 boils at a very high temperature compared to HNO3. this
means sulphuric acid evapouration will not be significant. i made an electric version of this principle by holding the acid
container in a kettle to act as a water bath. the original idea was just to leave the kettle on but this didn't work because the
water boiled too violently and the confinement of the main container inside the kettle created jets of boiling water <img
border="0" title="" alt="[Eek!]" src="eek.gif" />
heres the pics to explain it better.
<img src="http://www.boomspeed.com/kingspaz/distillerdiagram.JPG" alt=" - " />
<img src="http://www.boomspeed.com/kingspaz/distiller.JPG" alt=" - " />
sorry if this post comes across as a bit confused but i'm really tired!
oh almost forgot, it does work pretty well too :cool:
Mr Cool January 1st, 2003, 09:24 AM

I would be better to lift the receiving jar out of the acid mixture, to stop it from heating up as much.

yes but i don't think it would make that much difference as this unit is designed to operate for a while so no matter how good
an insulator is used between the collecting flask and the HNO3 source the heat WILL get through eventually. also it doesn't
really matter because once the HNO3 is in the collection flask it gets trapped in a cycle of evapouration, condensation and
returning to the flask.
BrAiNFeVeR January 1st, 2003, 11:04 AM

I took a shot at this too, but my results are not that good, mainly, I think, because I heated it too much. (didn't had much
time)
I got a lot of NOx due to thermal decomposition of HNO3 (for pictures, look <a href="http://www.geocities.com/brainfevert/
hno3.html" target="_blank">here</a>), a low yield and a relatively low percentage of HNO3.
I don't know how the water got in there, my NH4NO3 didn't contain much water.

the water came from decompostion of HNO3...2HNO3 ---> 2NO2 + H2O + 1/2O2
i think thats right, some one correct me if its wrong please.
[ January 01, 2003, 10:16 AM: Message edited by: kingspaz ]
simply RED January 1st, 2003, 11:12 AM

The first time the distilator was tried using Ca(NO3)2, H2SO4 mix. The Ca(NO3)2 prills were crushed and then heat to drive off
the chrystalohydrate water. Then mix with H2SO4 (the H2SO4 was 3/2 the calculated mass but i don't think it will matter if you
make it stechiometric). Some mililiters of water were added to start the reaction.
After the distilation on the bottom was left unsoluble in water CaSO4.
The nylon is good to be substituted with glass, because it can rip if you distil too long.
At the end i made 1 liter HNO3 (suitable for RDX)
(in the experiment was wasted material for 1,5 liters :) )
Still don't know what is the optimal temperature for distilation...
My source says 85 degrees C is the optimal temperature.
[ January 01, 2003, 10:38 AM: Message edited by: simply RED ]
THe_rEaL_dEaL January 1st, 2003, 12:57 PM

Here s a n idea a bit off topic but still con ce rned with acid concentration/distillation.
This apparatus could be used to concentrate Battery Acid/Dilute H2SO4
You may think wow.... Big deal. What a waste of time.....but!
It could give an easy way of calculating the approximate percentage purity of the concentrated acid.
If the percentage purity of the battery/dilute acid used is known, then by finding the volume of the distillate, (mostly
H2O) the percentage purity of the concentrated acid can be found. Assuming that the density of water is
approximately 1g/ml at 3.98o C.
This could be useful to people who d on t have precise s ca les for density testing or a precise thermometer for testing boiling
points. A measuring cylinder can be used instead.
Another idea :)
A hose connected through a hole at the bottom of the collection jar could lead distillate away to prevent water evaporating
back into the ppe jar. Sit a second collection jar on the floor and the apparatus on a table so the distillate could drain through
the hose into the second jar on the floor.
Back on topic :cool:
The hose idea could possibly be used when distilling out HNO3 from a Sulfuric, Nitric, and Sulfate solution. A
valve could be fitted to the hose somewhere close to the apparatus so that the distillate could reflux. Near the end of the
distillation, the valve could be opened to drain the distillate. The small amount of nitric, yet to be collected would then flow
straight into the second jar. This could prevent nitric being left behind in the still because the distillate nitric quickly passes
through the hot collection jar and into the second, cooler collection jar. This could prevent reflux leaving nitric in the still and
thus extracting the most nitric possible from the initial solution.
Hoses containers and valves would need to be made of a substance that can resist corrosion from concentrated nitric acid.
PTFE and lab glass comes to mind.
Comments, Criticism, Suggestions?
Mic January 9th, 2003, 10:49 PM

I am questioning myself for the sort of plastic we can use for this method for producing HNO3.
Is polythene suitable for HNO3?

:confused:
Thanks
stanfield January 10th, 2003, 03:06 AM

yes, it resists a bit, but it will be eated after several distillations...
A-BOMB January 10th, 2003, 10:50 AM

I was thinking instead to plastic why not use a glass funnel? I thing it would be work better than plastic and would allow it to
drip right in to the collector. Like in this drawing.
<a href="ftp://ewf:sd332gf@209.195.155.80/Hosted%20Images/New%20Folder/HN03.jpg" target="_blank">ftp://

ewf:sd332gf@209.195.155.80/Hosted%20Images/New%20Folder/HN03.jpg</a>
[ January 10, 2003, 09:51 AM: Message edited by: A-BOMB ]
simply RED January 10th, 2003, 04:05 PM

The smaller the anagle of the collecting cone the bigger its surface, the fastest the speed of distilation.
The smaller the collecting glass, less acid will condense on it, the faster the distilation.
The higher the temperature the faster the ditilation but 90 degrees C is the upper maximum.
mongo blongo January 10th, 2003, 04:51 PM

I would go with the glass funnel idea. I was actually thinking of the same kind of thing. I would not want the plastic being
eaten away and breaking when in use. The glass funnel would need a bit of sealing so the HNO3 wouldn't escape out of the
sides. It would need some sort of venting to release pressure though.
BrAiNFeVeR January 10th, 2003, 07:30 PM

For the venting, I just made a tiny hole in the plastic, on the flat side of my big glass container.
So whenever pressure rises, and blows up the plastic a bit, it opens up the hole, and releasing the overpressure.
Has anybody had descent yield using this method ?
knowledgehungry January 10th, 2003, 07:56 PM

I tried this method and got a very clear liquid, I am positive that it was not highly conc. nitric because it didnt smell like nitric,
fume like nitric or have the same density as nitric. I think either some ice leaked through my Al foil cone or moisture from the
air also condensed on the cone. I think that it is the former because i got a far larger amount of the mixture than one would
expect with condensation from air. I really like the idea for this method but it needs some fine tuning for me to get it to work.
nbk2000 January 10th, 2003, 08:20 PM

Use a glass funnel with the stem flame sealed, or an old martini glass with the stem cut off, and place it over the mouth of
the jar.
Rather than ice, which could leak water, use glycol and dry ice. This would be infinitely more efficient at condensing the nitric,
with no risk of water dilution.
[ January 10, 2003, 07:21 PM: Message edited by: nbk2000 ]

You might get a layer of frozen HNO3 on the funnel though and won't collect in the beaker.
nbk2000 January 10th, 2003, 11:09 PM
Anything that might freeze on it will melt when you stop adding the dry ice. Plus, the constant immersion in the nitric "steam"
will ensure that it doesn't freeze up too badly. After all, nitric doesn't freeze till about -50F, so just go light on the dry ice, eh?
<img border="0" title="" alt="[Wink]" src="wink.gif" />
Also, Ye Olde Timey distillers that used this sort of arrangement, would suspend a smaller funnel underneath the point of the
cone with a tube leading out so that the product was removed as soon as it was formed.
simply RED January 11th, 2003, 06:40 AM

It is not need to make a small hole for venting.
The pressure in the vessel is equal to the pressure of the HNO3 vapours and the pressure of the air. The HNO3 condenses so
its pressure does not matter.
BrAiNFeVeR January 12th, 2003, 06:00 AM

When you're constanlty standing near it, it wouldn't be needed to make that pinpoint hole, because then, you fill up on ice
regulary, thus keeping the condensation rate high.
If, however, you're anything like me, you'd rather distill at a lower temperature (I used 60C) and just use water instead of ice
in the cone. Now I'm just looking for a system that feeds it water when it needs it to compensate for the evaporation ...
I'm getting off track there, the point was, if the condensation rate isn't high enough for some reason, you ARE getting
overpressure, which bulges up the plastic, pouring over the water, and thus removing all means of cooling, and creating an
ever bigger overpressure !!
In this case it would be better to evacuate a bit of HNO3 vapour, then to come back in a few hours later, finding a plastic
balloon filled with HNO3 vapour ...
nbk2000 January 12th, 2003, 06:41 AM

How about feeding polyethylene tubing of the right size to just barely be forced through the stem of the funnel, and having it
wrap around the exterior of the cone (inside the jar), and the end coming back through the top rim of the funnel, to drain the
flow of cooling water out into a sink? :D
Simple, and cheap. <img border="0" title="" alt="[Wink]" src="wink.gif" />
Also, it'd be advisable to have this running outside because of the highly toxic nature of NOx fumes. You could have a very
small leak, but the extended length of exposure over the course of hours inside of a closed room could hurt you. May not kill
you, but it could cause impairment and make you susceptable to lung infections you might otherwise not have gotten.
DarkAngel January 12th, 2003, 12:33 PM

<img src="http://entersection1.virtualave.net/Pictures/nitric.JPG" alt=" - " />
I tried something similar like on the picture only my heat source wasn't good enough so it failed.
It's made from 2 coke bottles, One with only the top and the second the top and bottom cut off.
The first bottle holds the collecting jar the condenser and the chemicals and the second bottle where the top and bottom are
cut off is placed over the first bottle.One hole is punctured into the second bottle where a hose is inserted which let water flow
away when necessary.
The only problem is that water leaks out through the space between the 1st and 2nd bottle so something needs to be find to
prevent this.
[ January 12, 2003, 11:35 AM: Message edited by: DarkAngel ]
Axt August 20th, 2003, 05:27 AM

I think this method holds most merit as a vacuum setup, since the apparatus is so compact it could be easily confined inside
a larger pressure vessel.
This could simply be done by using the glass funnel in the bottle and using a glass marble (or teflon coated bearing) in it to
form some sort of check valve allowing pressure to equalise between the vessels, but sealing the pressure vessel from the
acid.
The vacuum is easily created by fixing a large syringe, and drawing the air out through a valve. You can just use common
copper pipe/valves/fittings for this as its not in contact with the acid.
Id post a picture but ive lost my motivation to do so :mad: .
Edit: Actually you can pollute your eyes at totse if you wish to view the PICTURE (http://www.totse.com/bbs/Forum19/HTML/
004163.html) . They seem to allow you to post them.
vulture August 20th, 2003, 08:30 AM

A syringe for pulling a vacuum? :rolleyes:
Use your brains for gods sake. You'll pull a tiny weeny bit of vacuum in the beginning, but as soon as the nitric starts
evaporating it will get back to 1 atm or higher.
You couldn't even use a vacuum aspirator, since this would draw all your nitric vapors out before they can condense.
That's why the vacuum connector is always connected to the distilling flask in a normal setup.
Axt August 20th, 2003, 12:16 PM
I think your wrong.
I believe it will form some sort of equilibrium at a certain heat and pressure, where the pressure will stabalise and vacuum can
be maintained. The HNO3 going through the liquid/gas cycle will for the most part be trapped within the cylinder. After all, it is
exactly the same as the methods above but working in a reduced pressure environment, even if the vacuum has to be
"topped up" now & then. Though I couldnt think of an easy way of cooling the funnel.
And for the record, I know fuck all about vacuum distillations.
vulture August 20th, 2003, 04:09 PM

You're vaporizing HNO3, if you suck away HNO3 vapor more HNO3 will evaporate to compensate.
In a glassware distillation setup the vacuum outlet is positioned behind the cooler because most HNO3 is in liquid form there,
so that you aren't simply wasting HNO3 vapor.
Axt August 21st, 2003, 11:35 PM

Acceptable loss.
If a pinhole was used through the bottle just under the funnel to allowing the pressure to equalise, which would allow you to
cool the condensor (funnel) with water the losses will be minimal. After quality, not quantity.
simply RED August 22nd, 2003, 11:26 AM

When you use this type of distiller, driving away the air will significantly faster the distilation.
Why?
The speed of distilation depends from the concentration of the HNO3 vapours. The more concentrated HNO3 vapours, the
faster the process.
immagine the next example:
You have isolated your distiller from surrounding atmosphere. In one moment the pressure inside is reduced 2 times. The
HNO3 then begins to evaporate quickly and fills the space with denser fumes. Until the mols of the evaporated HNO3 is equal
to the mols condensed HNO3.
The pressure inside will not be equal to the atmospheric pressure because the aparature will be isolated (sealed well). The
pressure inside will depend from temperature.
Axt August 22nd, 2003, 01:10 PM

Yep.. Ive convinced myself enough that itll work, and well enough to try.
Ive began on a pressure vessel (steel), 12"x18"x5mm. this assumes I can get hold of one of these (http://www.steps-to-
memories.com/Glass/fsg2643.jpg) to make use of the volume.
I was under the impression that not terribly much vacuum is needed to prevent the decomposition of HNO3, What vacuum
should it be run at. Is it a case of "the more the better" (more the faster)?
Take a look here (http://ww1.altlist.com/~52497/rogue.altlist.com/images/vacuumstill.jpg), tell me what wont work before I

get too far into it.
kingspaz August 22nd, 2003, 06:33 PM

Axt, shouldn't the vacuum pipe go into the HNO3 vessel and not the oil bath vessel?
Axt August 23rd, 2003, 02:59 AM

Originally posted by kingspaz
Axt, shouldn't the vacuum pipe go into the HNO3 vessel and not the oil bath vessel?
No, mainly because I wont be able to do it. Its so much easier working with steel. Im assuming here that the temp. difference
between the "condenser" and oil bath will be enough that the small amount of HNO3 vapor to escape through a pinhole near
the cone will be negligible.
nbk2000 August 23rd, 2003, 04:46 AM

I'd raise the receiver for the nitric up out of the oil so it's not heated as much, making it easier to keep it condensed. :)
simply RED August 24th, 2003, 06:05 AM

Which plastic is resistant from heat nitric acid (100 degrees) 98% concentrated?
It must be resisitant form mixed acids too.
PVC?
blindreeper August 24th, 2003, 07:11 AM

I think polytetrafluroethylene would hold up. But it may be hard to get. Don't quote me on this but PP (polyprypolene sp?)
may be resistant and it is available in some products such as watering cans where the PP can be around 5mm thick and you
can mould it with heat.
But the best bet would be PTFE
A wine glass could be used to bring the collecting vessel up out of the nitrate/acid mix. Not sure if it will be any cooler, but in
the very least it will stop the collecting vessel floating around.
I was thinking of using these - http://www.bestcontainers.com/drum-liners-heavy-duty--ptfe--drumright-tm--teflon-r--

liners.html for the acid/nitrate, that way you could use steel to make the correct sized jar for the glass cone to sit on, but they
are bloody expensive.
Mr Cool August 24th, 2003, 02:12 PM

Axt, while your diagram is nice, this topic is called "HNO3 the easy way"!!
Would it not be easier and more effective to buy some glassware?
simply RED August 24th, 2003, 03:55 PM

1. Never use oil bath. Sometimes the glass brakes. If hot nitric acid mixes with oil, it will be a huge blast and fireball.
2. Do not use vacuum if you distill in quantities less than 2 liters HNO3 per cycle. If the condenser is near the acid (or acid -
nitrate (tested with Ca and Pb nitrate). The speed is fast enough.at 80-100 C.
3. If you use vacuum, make the vacuum in the distilation vessel, this will speed up the process.
4. Make the condenser(the upper (wineglass) part) form a bottle, cut it from the middle and fill with ice. Use plastic cap to
secure the bottle. No matter tiny holes absolutely no HNO3 vapours escape.
5. Use medicine syringe with attached hose to drive off the k.HNO3.
No matter with vacuum or not this is easier to make and cheper than normal distiller. Plus it never needs vacuum pump to
work all the time.

1. I always use an oil bath, because otherwise you're mainly wasting energy on evaporating water.
Just heat up the oil slowly and make sure the temperature difference doesn't get too high.
You could always use synthetic non-flammable motor oil.
3. Ofcourse, in the distilling vessel the nitric is mainly in fluid form, so it won't get sucked away like the vapour. That's exactly
the problem I'm trying to point out with your setup, because there isn't enough separation between the distilling and
evaporating vessel, thus you're sucking away a great deal of nitric acid vapor.
5.Medicinal syringes will melt to goo in contact with hot nitric acid.
Glass distilling setup works perfectly for nitric even without vacuum. Looking at the construction Axt is going to make I have
my doubts about it being cheaper. I got my whole se tup for 100 .
Use teflon grease to cover your plastic. It's relatively cheap (12 /500g) and you don't ne ed much.
I found it in the automotive supplies section of a big supermarket.
nbk2000 August 24th, 2003, 11:21 PM

Using water, instead of oil, is the only sane thing to do.
RTPB "Plan for Failure".
You must assume that the flask will implode while drawing down the vacuum, and that it will happen at the worst possible
moment.
Imagine hot, concentrated nitric acid oxidizer being explosively mixed with a hot hydrocarbon fuel by a vacuum implosion. Hot
oxidizer...hot fuel...BOOM! Cooked vulture. :p
If it's water, instead of oil, worst thing that happens is a big mess and a lot of dilute acid to be cleaned up, not a flaming
fireball.
Better yet, use sand, since it's inert and a solid.

Buy glassware! .... :confused: It is much easier for me to make whats in the picture then to somehow aquire a glass
distillation setup.
Im not sure how stupid im going to sound by saying this, but is it possible to draw such a vacuum from the chamber so that
heating isnt even necessary? at what pressure? that would solve many problems.
Milamber August 25th, 2003, 04:42 AM

If you did that, the problem is that the receiving vessel would ALSO be at a pressure that low, meaning that the acid in there
would evaporate too (or, more to the point, would not condense) without being put in a cooling bath, which is sort of difficult if
using the jar-in-a-jar setup described above. It could work using a real still, but you'd need to immerse the receiving flask in a
cooling bath and you'd need a vacuum of around 20 torr (assuming a BP of 122*C for 70% nitric, and 25*C as room
temperature) - which means a good aspirator or a pump. Problem there is unless you have REALLY good cooling, there's still
gonna be a lot of vapour from the receiving flask, which would be happily sucked up by the vacuum source. The aspirator
would probably suck a lot of nitric fumes down the drain with the waste water, while a pump could suffer severely from
exposure to the fumes.

Axt, do you need so much acid? :) Without vacuum it works fast enough, try it to see.
Syringe is not even touched from cool nitric acid in any concentrations. Never tried to displace HNO3 hot.
Axt's construction is not wrong. Only the recieveing glass may not touch the hot acid. The idea here is to make the vacuum
once, and not use a vacuum pump working all time.
This of course is near(near absolutely) impossible to make at home... It needs perfect sealing.
If all the time vacuum pump is used, HNO3 vapours will escape.
HNO3 in the receving vessel will be cooler, not only that, it will be (97%) which evaporates slower than the acid in the H2SO4
mix. (with vacuum or not no matter).
Don't know for the others, but for me buying glasswere is not posiible. Thats why i make such constructions. This costs
absolutely nothing to be made and works much better than non-vacuum device.
Where do i know about the shattering glass! Yesterday the jar shattered while distilling :)
before that, i had never thought what bath to use. (i was using water when the jar shattered, and of course with water nothing
happened). (happily the distilled acid survived).
I never had any instruments to measure temperature vacuum and so on.

(now i have digital multimeter "Lamar" for 9 dolars which measures temperature with probe.)
What do you want.... 1 liter sulphuric acid 98% - 2,5 dolars. Ca(NO3)2 -5 kilos - 2 dolars. No funds or time for complicated
devices....

Im finding it hard to get my head around this, does that mean to create a vacuum of 20 torr one would have a pressure of
559 psi pressing on the outside of the vessel?
1 atm = 760 torr = 14.7 psi.

760 / 20 = 38
38 x 14.7 = 558.6
It was always assumed that the HNO3 would continue to evaporate from the collecting vessel, but once vapourised it should
condense and fall back into it so it will either be in the air, on the condensor or in the collecting vessel at any one time in the
cycle. the lower surface area of the collecting cylinder compared to the acid/nitrate will also lower its evaporation.
Mr Cool August 26th, 2003, 08:45 AM

I'm not quite sure what you mean there Axt... even with a full vaccuum in the vessel, you would only have a net pressure of
14.7 psi on the outside of the vessel. The atmosphere can't exert any more than atmospheric pressure.
(20 / 760) * 100 = 2.6% of atmospheric pressure inside, = 0.38 psi.
(14.7 psi outside) - (0.38 psi inside) = 14.32 psi net pressure on the walls of your container.
:confused:

Correct .. in that im talking crap.
If it was 1 atm inside the vessel it would be 558 outside the vessel to have the vacuum ratio im after.
I was finding it really hard to get a mental picture of how much that really is - thats the way I reasoned with it.
Meaning to create a vacuum of 0.38psi one would have to exert the force necessary to compress 558psi.
Tuatara August 26th, 2003, 09:06 PM

Axt, you still seem rather confused. The ratio is irrelevant - only the absolute pressures matter. Example: say you were using
a piston pump to create the vacuum, and that piston had an area of 1 square inch. If you had a perfect vacuum (0psi) on the
low pressure side of your piston, and atmosphere on the other side, then the force needed to hold the piston still would only
be 14.7 pounds-force. As you can see, the ratio of zero to 14.7 is infinte, yet the force is still only 14.7 lbs

I did spend last night banging my head against the head of the bed reciting how stupid I am.
Does this mean I could have just used the syringe to begin with.
bobo September 17th, 2003, 07:35 PM

In the place where I work, there is often a full 10l jerrycan of used piranha standing around because no one likes to haul the
stuff away:D This typically means about 65% sulfuric, a lot of water, some H2O2 and NaS2O3 used to neutralize it.
I want to make some nitric acid and think this source of acid is far cheaper than buying sulfuric. now I know that even weeks
old, neutralized piranha is evil (I cleaned a bathroom with it. When a liter of piranha met the fungi and shit behind the toilet it
bubbled and the trusted smell of piranha fumes became so strong I decided to open all windows). If they see me hauling the
chemical waste no one would think of theft:D
Would this be a good idea? I have no idea of the interactions of the other chemicals with fertilizer KNO3 prills let alone the
mixture CA, NH4, K + NO3.
knowledgehungry September 17th, 2003, 07:45 PM

If you boiled it down the H2O2 should decompose and the water should boil off. Im not sure about the NaS2O3 though.
bobo September 17th, 2003, 08:26 PM

If NaS2O3 is indeed what remains - this stuff SHOULD be added in far less than stoichiometric amount to neutralize piranha. If
you add much, a slab of sticky slurry will remain on the bottom. Pouring out the fluid and adding water to this slurry will lead to
'the fumes' coming at you. I cannot figure out a good reason for this.
densest September 19th, 2003, 11:50 AM

Just a thought about used piranha solution - you could do a couple of things to it:
try mixing a small amount of it with a cold solution of urea - the H2O2 should oxidize the urea (maybe even to HNO3?) In
larger quantities be sure to do this slowly and keep the mixture cool. Other organic materials would probably work as well, but
there is a danger of explosion if you add a solid or more than a little liquid at a time.
try stirring it with a stainless steel or nickel spoon - this should catalyze the breakup of H2O2 without getting much
random metal in the solution
BTW, according to some graphs (google for nitric acid synthesis or production) with any reasonable concentration of H2SO4 in
excess (say 50%) shifts the anti-azeotrope point significantly towards 90% HNO3. Thus a vacuum might not be necessary
except to get the last 10% water out.
Sodium bisulfate or aluminum sulfate powder should work as a source of H+. They're much easier to get than H2SO4.
vulture September 19th, 2003, 11:53 AM

Sodium bisulfate or aluminum sulfate powder should work as a source of H+. They're much easier to get than H2SO4.
Sodiumhydrogensulfate will react acidic, but Aluminiumsulfate will not, since the Al3+ ion is very slightly acidic and the SO4- ion
is very slightly basic.
And sodiumhydrogensulfate is not acidic enough (in solution) to produce HNO3 from a nitrate, since HNO3 is a strong acid and
HSO4- is not.
ossassin March 18th, 2004, 11:55 PM

Would anyone recommend fastening the funnel/martini glass to the beaker, or would resting it on top be enough? How much
pressure would the reaction create?
simply RED March 19th, 2004, 09:26 AM

In my last experiments i use duct taped (one layer) funnel to a 3 liters jar. The jar is cut near the top so a higher surface of
the funnel could be used as a fume reciever.
The reaction produces no pressure. The best resaults come from distilling Ca(NO3)2 fertilizer or NaNO3 + k.H2SO4. Maybe
NaNO3 is the best choice.
The acid is collected in 800ml jar inside the big one, put over another jar to insure low heat transfer.
All heat on sand bath at 100 degrees celsius.
At the end of the distilation (500-600ml acid collected(hours are needed)), after colling the system, the 800 ml jar is extracted
with "jar catcher" and put immediately in a bucket with water bath.
After this, all the acid is immediately "converted" into RDX with hexamine dinitrate.
Here lies the big problem. With no acetic anhydride the yiled is not perfect...
(the reaction produces "very low pressure" as said upper, it is done on atmospheric pressure)
al93535 April 5th, 2004, 03:20 AM

I get quite nice, very high purity clear HNO3 from very simple distillation. I use a large pickle jar, set inside it a small cup
upside down and a small mayson jar right side up on top of it. I then add about 300ml 95% H2SO4 and either appropriate
ratios KNO3 or dilute nitric. I went to the good will and bought a coffe machine for 5 bucks, disassembled it and got the hot
plate out. I set the filled pickle jar on top of the hot plate, and turn it on (gets to 55 to 60 degrees). I used no water or oil
bath, like last time. I used another hot plate last time and set to 75 and got yellow nitric from decomposition. So this way I
get no decomposition and pure clear HNO3. I then use 3 mil thick plastic sheeting from home depot to lay over the top and
make an inverted cone into the mayson jar, and fill with ice water. This plastic sheet stands up excellent for up to 5
distillations. I got about 75ml HNO3 for 9 hours running time. I can take pictures if you guys want. The coffe hot plate I think
is a great idea. What do you think? Also, with a real distillation set-up what kind of results do you get, if anyone here is using
one? Time for how many ml's? Thanks for all the great information guys. ;)
Mr Cool April 5th, 2004, 04:10 PM

Simply RED, could you tell me the width of your funnel, roughly what surface area the acid/nitrate has, and how long it takes to
collect that much acid (500-600mL)?
I've recently acquired a nice big funnel, so this method may now be practical for me to distil useful amounts of acid until I
replace my condenser.
Edit: al, I never bothered to time my distilations, but I generally distilled at the rate of about 3-4 drops a second. You can do
it faster with more vigorous heating, but then you'll probably get more decomposition. I found that when distilled at 1atm at
this rate the acid was barely yellow, and good enough for respectable yields of RDX.
Mendeleev April 5th, 2004, 11:43 PM

I found that 1 layer of saran wrap holds up just fine to hot nitric vapors for at least one 12 hour distillation. Also, about
distillation being slow, how the hell do they do it in industrial plants? I mean they have to operate on thousands of liters a day
output, so how is it that they can distill so quickly, if they have to keep the heat/vacuum at a certain point, otherwise the water
or other contaminating liquid will distill over?
simply RED April 6th, 2004, 07:22 AM

The active funnel surface is about 3-4 square decimeters. The evaporating surface is lower. It distills at a rate about 2 drops a
second. Maybe slightly slower. 4-6 hours for 400-500 ml. Maybe slightly faster.
400 ml jar is better for recieving than 800 ml.
Use the highest possible surfaces and make higher quantity at one time.
90-100 degrees is optimal if the condensed acid and the "mother liquid" are separated (no heat transfer).
With real setup you get nothing without vacuum. (the vacuum also needs dehydrating of the circulating air)
The big jar can be cut with nichrom red hot wire (in order to place the funnel inside, it cranks exactly where the wire was.
rikkitikkitavi April 10th, 2004, 04:18 AM

dont worry mendelev , that is why they have guys like me...
no , but seriously it is not easy to tell how a process behaves on larger(industrial scale) compared to the lab. How many times
havent I got in discussions with lab people about reactions that are almost impossible to scale-up?
they recyce any decompositon products, better temperature/pressure control (withint mbar and tenths of degress C) ,
controlling power input and flows e t c . It is actually not so difficult... :)
/rickard
ossassin April 10th, 2004, 02:42 PM

I like the coffee machine hotplate idea. I'm going to look into that.
simply RED April 12th, 2004, 04:00 PM

Never let the collecting vessel touch the hot mother liquid.
In one of the last tries, it accidentally happened and the yield was zero because of eveporation.
Use a jar with alluminium foil "funnel cap" letting the acid inside, not letting the fumes outside.
Centimeter April 20th, 2004, 09:02 PM

I used brainfever's method however I used a hollowed out lightbulb as the vessel for holding cool water. I can then use a slow
syphon to replnish the cold water. Using this method I collected about 7 mL of slightly yellow acid with a density of about 1.43
g/cc. I distilled at about 65-70*C for 2 hours. I used KNO3 and ROOTO Concentrated H2SO4. Why did I collect a slightly yellow
acid at such low temps? Is it good enough quality for making RDX?
Centimeter
Mendeleev April 21st, 2004, 12:43 PM

I have actually stopped using brainfevers method :) . Instead, I took two wine bottles, and joined them with piece of plastic
hose I bought at Lowes. I then inserted the plastic hose into a larger diameter plastic hose, the edges of which I heated with a
propane torch until they were very soft, at which point I ziptied them very tightly, effectively forming a water jacket and a
condenser.
I poked two holes in the top and bottom of the improvised water jacket, and inserted a length of hose in each one. The wine
bottle screw on caps were made out of some unknown metal so I just melted a thick layer of aluminum onto them, so that the
oxide coating forms and protects the rest. I am going to see if plumbing solder works just as well, as it is much easier to melt.
You could do it with a match. The holes in the wine bottle caps through which the plastic hose was put were sealed using
melted paraffin.
This rig in my opinion is much better as it allows proper cooling of condensation medium and receiving flask, plus it is vacuum
compatible, just poke another hole in the cap of the receiving wine bottle, and insert a hose connected to the vacuum source.
Make sure the condesner hose is much lower than the vacuum hose so that you don't suck away any nitric acid. I have not
tested vacuum, but I have successfully distilled water, and I just recently distilled about 100 mL of HNO3, only 100 mL though,
because it is a bit slow :mad: trying to keep the temperature no higher than 65 to prevent decomposition. I hope to soon
rectify the rate problem by constructing a vacuum aspirator. A water bath was used for the distillation. I have pictures of the
rig, but they are about 2048 x 1600, so I need to edit, so as not to kill the forum's bandwidth.
This rig cost me about 92 cents, because I took the wine bottles out of the recycling, and the rest was about 30 cents for the
smaller hose, 35 for the larger one, and about 10 or 20 cents per ziptie. And it is completely OTC. Not bad eh :D?
aikon April 21st, 2004, 02:38 PM

I collected about 7 mL of slightly yellow acid with a density of about 1.43 g/cc. I distilled at about 65-70*C for 2 hours. Is it
good enough quality for making RDX?
Centimeter
Maybe the acid will work but you'll need more than 7mL to get an acceptable yield. The color by the acid is caused by the acid
breaking down to NO2. A light yellow color is ok, but a reddish brown or pink acid shouldn't be used. You can try to add a litte
bit of urea to it. For RDX you need nitric acid with next to no water in it to avoid the nasty side reactions producing toxic fumes.
Your acid is more likely to produce these side reactions.
vulture April 21st, 2004, 03:44 PM

You could try treating your acid with O2 gas under pressure for a while. O2 produced from H2O2 would be fine, as a bit of
moisture is even beneficial in converting the NOx back to HNO3.
Slight, bright yellow color is normal for highly concentrated HNO3. My vacuum distilled stuff is a bright yellow, but you can
perfectly see through. The NOx content is very low, under vacuum it almost immediatly turns colorless by giving away a few
bubbles of yellow NOx.
Nothing like the red gas/destillate I got under atmospheric pressure.
SantasL.Helper April 29th, 2004, 06:57 AM

What would happen if you would, considdering you are using a triple or double neck distilling flask and a normal setup without
vacuum, let oxygen flow into the distilling flask (not through the solution, just into the flask) at the same time you are
distilling your nitric?
0EZ0 May 3rd, 2004, 09:52 AM

SLH, what are you hoping to achieve by doing so? Allowing atmospheric air to come into contact with the contents of the
distilling flask would completely kill the distillation unless it was forced in with a high positive pressure. Having an open
recieving flask would allow some of the HNO3 to escape as vapour unless the vessel is sufficiently cooled. The resulting
concentration of the product may also diminish with extended distillation cycles as it would pick up moisture from the air.
Just "allowing" the contents to come into contact with bottled or chemically produced oxygen would probably do little to remove
any discolouration of your nitric. The best method is probably prevention with vacuum equipment of alternatively very low
distilling temperatures over extended periods.
Mendeleev May 9th, 2004, 08:13 PM

Here are the pictures of the still. The first one is one of the earlier ones, before I made the second hose connection to the
water jacket, and in the second one, you can see the joint is pretty crude. I had expected the tubing would melt, but it burned
instead. However it got soft enough to effectively apply a zip-tie. The metal screw-on caps can be made nitric acid proof
through either melting on a layer of aluminum foil or folding several layers of saran wrap which is very resistant to nitric acid,
and melting that on. A gentle flame must be used for the saran wrap so that it doesn't decompose. The whole still is made
airtight by melting either paraffin or saran wrap around the hole through which the tubing is inserted into the cap. :)
nbk2000 May 10th, 2004, 02:25 PM

How wonderfully Lo-tec, Mendeleev! :)
Stuff like this makes the oppressors disdain of ever gaining total control over their herd of sheeple. :D
al93535 May 24th, 2004, 06:51 AM

Using brainfevers method of distillation, I aquired HNO3 with a purity just under 100% anhydrous. Pure anhydrous hno3's
density is 1.5129 and I measured mine at 1.512432 after a double distillation at 60 degrees. Quite nice I must say, thanks
brainfever for the wonderful method. I used a pickle jar, two tiny mayson jars, the corner of a gallon zip-lock bag, and the
hotplate from a coffee machine, which regulates at 60 degrees. I get pure colorless acid I love to just look at it. With a double
distillation I can produce about 200 ml in 3 days. Two days to get about 125 ml each day of 95%, then one more day to
double distill that. Also the last distillation goes much faster then the first two that produce the HNO3. :D I plan on making
some more RDX!
nbk2000 May 24th, 2004, 01:23 PM

How on earth did you measure 1.512432? That's very precise for a kitchen chemist...
al93535 May 24th, 2004, 09:33 PM

NBK: I used a grain scale for gun powder, it measures down to a tenth of a grain. One tenth of a grain = 0.00648 grams. I
used a 1ml dropper, I then added 1 ml of distilled water noted the level, and weighed it until I got exactly 1 gram. I then
weighed one ml of the acid at 20 degrees. To be sure of accuracy I also weighed 10 ml, and it only varried by .0008 grams. :D
++++++++++
Good thinking! :) NBK
PeterB2 November 30th, 2007, 11:00 PM

Ok, after a few small scale tests, I amped this one up a bit.
I used ~350 g of cruddy, black drain opener sulfuric acid. Assuming 95% purity of the acid, I started with 332.5 g H2SO4. I
used 288.2 g NaNO3. In a old steamer/frier I kept a water bath at about 80-85 C through the whole procedure. For the
condensing cone, I used a zip-lock bag corner with an aluminum cone (for safety) inside that which held the salt/ice bath
(which I replaced periodically).
After about 12 hours, I collected about 45 mL of bright yellow, see through nitric acid in my glass condesation collector cup.
Even assuming a 100% purity, I got only about 68.4 g (estimated based on pure HNO3 density; haven't measured the actual
density yet) out of a calculated theoretical yeild of 213.6 g product. Thus, the yeild is only about 32%.
Why are the yeilds so bad even with a relatively high temp and long distillation?
Emil December 1st, 2007, 08:23 PM

Sounds like quite a bad yield given the amounts of pre cursors used.
The only thing that could be your problem there is purity of your HS2O4 or your Nitrate. With drain cleaner, never assume
concentration as it could be a lot worse than you expect. There are endless amounts of different brands out there and some
are reported to be of much more use than others. May I ask what brand of drain cleaner it is??
I noticed a very sly piece of information recently with a certain drain cleaner I was looking at. Sure on the bottle it said
"Contains 96% sulphuric acid."
But then if you check the box the bottle it's in, it says >51% sulphuric acid. A further check on an internet safety sheet left me
with the knowledge that it was full of all kinds of inhibitors and other crap.
I've yet to try my first distillation, but I have all the gear ready, just waiting for some spare time. I'm really looking forward to
trying it though. Got some holidays coming up very soon so I'll be planning to try then.
Masonjar Chemist December 2nd, 2007, 12:39 AM

The bad yields are due to the design of the distillation set up. The "collector" being inside of the reaction vessle means that
the distillate will coninualy re-evaporate and condense. A band-aid fix would be to create a stand so that the collector is above
of the mixed acid as was stated earlier in this thread I believe (my apologies if you already knew this). The only true way of
getting better yeild would be useing a conventional "still".
The brand of drain cleaner that I personaly use (liquid lightning drain opener)is black and "cruddy" so I doubt this is the
problem.
PeterB2 December 2nd, 2007, 02:53 PM

Yes, I did raise the collector above the acid mix with a solid glass cylinder about 1 inch high to try to correct this problem. I
waited several hours after cutting off the heat source in an attempt to allow any vaporized acid to condense before I collected
it.
In the end, I think I'll just have to save up to get a nice distillation setup. Has anyone seen the glassware for sale on
sciencefair.com? Looked like a nice rig to me.
The brand of sulphuric acid I used this time is call "Floweasy Drain Opener" made by Jones Stephens Corporation. According to
the MSDS, it is 94.19% H2SO4 by weight.
rangegal December 4th, 2007, 11:43 PM

How does a still for under $150 sound?
I don't mean to give them free advertising or anything, but I think this is rather relevant. You should check out
www.unitednuclear.com. They have RB flasks, liebig condensers, glass tubing, corks, and stands.
You'll need to wrap the stoppers in Teflon tape to protect them from nitric acid though (I can't personally vouch for this idea
yet, but totenkov can).
I'm pretty sure you could even use their handpump vacuum filtration kit to make it a vacuum still. That is of course if it can
hold up to nitric acid vapor, which I will find out when I get one.
I'm getting a still from them soon, along with some other glassware.
I'll post about how it goes.
PeterB2 December 6th, 2007, 10:48 PM

I tried wrapping rubber stoppers in Teflon tape. Maybe I didn't do it well enough, but it tends to seep through the cracks and
get at the rubber soon enough.
If you want to use a distillation setup for nitric, you really need to go for an all glass setup.
I think it's been pretty well established that the plastic in the hand pumps will not stand up to nitric very long unless you have
several traps to neutralize the acid.
How about using an all glass apspirator instead? The additional advantage is that the fumes get instantly diluted and washed
down the drain. pelletlab.com sells a nice all glass aspirator for under $10. They also sell glass retorts.
rangegal December 7th, 2007, 09:01 PM

Thats a pretty nice website! Wish I would have found them earlier. Now that I've seen their prices, unitednuclears look pretty
bad...
I don't see the glass aspirators though... maybe they discontinued them?
PeterB2 December 8th, 2007, 12:27 AM

From the main menu, click "Filtering Kit" under "Filtration". Should be right there for $6.95. You'll also need the adaptors and
tubing.
megalomania December 8th, 2007, 12:54 AM

In my experience United Nuclear is very pricy, but at least they still sell to individuals, and based on the press they are not
fedgov affiliated. Of course they were raided once, so who can say if they won't sell you out to the gestapo thugs the next time
they get raided.
rangegal December 8th, 2007, 01:37 AM

Ohhh now I see it. I guess their search function doesn't work. Thanks PeterB2. I don't get how I would measure the vacuum
though, since if the vapors will eat a hand pump, wont they eat any sort of valve or gauge I hook up?
BTW I notice their chemicals aren't badly priced either! (from what I have to compare it to) Their nitric acid is nearly half as
much as that Trinity Lab Supply site somebody made a thread about. Not that I'm going to just go buy some nitric, because
whats the fun in that?
United nuclear also has a lot of stuff that other sites like pelletlab don't, such as their (limited) pyrotechnic chemicals,
isotopes, and aerogel (which I need for my heater/stirrer project!). And I have to give them props for their hydrogen car
conversion thing, that is if they ever release it.
Azido December 10th, 2007, 09:40 PM

I'm in the process of building my own vacuum distillation rig, primarily from Vinyl Plastics and glass.
I built an aspirator, from a bit of T joint for 10mm vinyl tubing. I filled with epoxy filler and drilled a 4mm hole right through
and a 4mm hole for the vacuum hookup.
Cost me about $6 for the aspirator and 30 NZD all together.
I'll post more pictures and maybe even a nice Documentary thread when (if) it works. :)
But yeah, the aspirator works, and for cheap. If it is a bit.. makeshift?
Emil December 29th, 2007, 04:30 PM

As far as what Nitric acid reacts with, I think it's quite hard to determine exactly. I gather that it attacks most materials, but
how harshly is the true question. With Infomation on this type of topic hard to find it doesn't make it easy. I'm not sure with
plastics how violently it attacks them, of course some more than others.
The only true safe material for use with Nitric is glass, metals are obviously a no no, so a glass aspirator is really an ideal way
to go.
Of course it all depends on your situation as to whether a water fed aspirator is any good. If you have mains water pressure at
hand then you are ok, but not everyone does.
Given my situation, I'm actually looking into electric vacuum pumps at the minute. You can get hold of some really nice ones,
but of course the main problem being that you have to find one which is not made of metal parts. Luckily I have came across
a nice range of pumps which are made of different plastics and teflon/ptfe parts, which are meant for increased chemical
resistance.
Of course this type of pump comes at a price, not hugely expensive, but I know some people are all for cheaper alternatives
and improvisation.
Besides all this, I really doubt that nitric acid attacks any plastics so tremendously that your unable to temporarily hook up a
gauge to pull off a reading.
PeterB2 December 31st, 2007, 12:56 AM

I dunno...one time I tried to put a little of my nitric acid in a plastic soda bottle (PET) to see if it would be suitable to store it
in. It's not...it turned it white within a matter of seconds, and I didn't want to find out what would happen next.
Charles Owlen Picket December 31st, 2007, 10:21 AM

Many, many "plastics" today are made to be "bio-degradable". That often means that they are designed to break down and
contain organic materials. That's a prescription for frustration. Don't forget that you are dealing with a heat issue as well.
megalomania December 31st, 2007, 07:23 PM

Acids also attack materials differently depending on concentration. I posted some links to chemical compatibility charts several
months ago... Some chemical engineering reference books should have an extensive list. A google search for "chemical
compatibility" + your material is a good way to find out.
I don't think most people go around with broad incompatibility knowledge in their heads. This is the kind of thing you have to
look up in reference works.
gaussincarnate January 2nd, 2008, 02:28 AM

Some of the best materials for nitric acid are 304, 316 stainless, bronze,
Al2O3, Teflon, Viton, and Ti. So sayeth the Cole-Palmer compatability database. They list a few more, but most of them are
not exactly what I would call common consumer products. I would also like to assume that any other metal that can be
passivated would be effective, which is more than likely why titanium is on this list.
I know that anondized aluminum has been discussed here to some extent, but it seems almost ideal. The only problem I
could think of for some of these materials is their activity with nitrogen oxides or the danger assosiated with heating materials
like Teflon.
Setharier June 24th, 2008, 05:41 PM

I saw a video making nitric acid from KNO3 and H2SO4 heating. 97.7% of you knew this, but question I would like to ask is,
do the KNO3 need to be pure or very pure, does it matter if it has some "extra fertilizers" in it? We have here plenty of KNO3
available but in most cases it has impurities like cement etc. random sh*t in it. My Chem Supplier could deliver all of these in
lab purity but price is what it is(11 for 500g, bloody heavens and quite same stuff in 25kg bags for about same price in
agristore).
I so wish we would have equal shop in EU like United Nuclear is. After hours of searching our country sites for lab stuff, ending
with empty hands, I just open UN site, click once and got EVERYTHING glassware I would probably ever need in my lab life in
front of my eyes. That's one more reason for move to USA as soon as it's phossible for me.
ChippedHammer June 24th, 2008, 08:12 PM
Its relatively easy to purify KNO3 by recrystallization, not that that's needed if you are distilling the HNO3. Straight fertilizer
grade is suitable most of the time.
I'm still collecting my lab gear, I now have a complete quickfit glass distillation setup. I just need to turn a few stoppers and
thermometer adapters out of my PTFE barstock.
Cobalt.45 July 27th, 2008, 08:46 PM

To expand on gaussincarnate's earlier post, here is a link to a page on compatibility of concentrated nitric acid (and other
chemicals) with various types of material, about 42, IIRC: http://www.coleparmer.com/techinfo/chemcompresults.asp
The following are deemed Severe Effect, not recommended for ANY use:
ABS plastic
Acetal (Delrinr)
Aluminum
Brass
Buna N (Nitrile)
Carbon graphite
Carbon Steel
Carpenter 20
Cast iron
Copper
CPVC
EPDM
Epoxy
Hypalon R
Hytrelr
Natural rubber
Neoprene
Nylon
Polyetherether Ketone (PEEK)
Polypropylene
Polyurethane
Silicone
Tygon R
Considered Good - Minor Effect, slight corrosion or discoloration, are:

ChemRaz (FFKM) (a high-temperature perfluoroelastomer)
Hastelloy-Cr
Noryl R (alloy of polyphenylene ether (PPE) and polypropylene (PP))
PVC
Said to be Excellent, are:

304 stainless steel (food service, often)
316 stainless steel
Bronze
Ceramic Al203
Fluorocarbon (FKM)
Kalrez (O-rings, seals)
Kel-Fr
PTFE
PVDF (Kynar) (tubing)
Titanium
Viton R (available as tubing in at least two different hardnesses)
Glass wasn't listed, but is obviously an "Excellent"-type material.
Various other materials are listed as "C = Fair -- Moderate Effect, not recommended for continuous use. Softening, loss of
strength, swelling may occur."

The Explos ives and W eapons Forum > Chemistry for Amateur Experimenters and Citiz en Sc ientists > Special Project 1: Improvised Manufac ture of Nitric Ac id > A review of ammonia preparation
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meg aloman ia October 4th, 2002, 03:32 AM

In my next round of nitric acid experiments I plan to use both anhydrous ammonia and highly concentrated amm onium hydroxide. After looking over m y website, I noticed I dont have any satisfac torily useful information on the preparation of ammonia. Furtherm ore, it appears that
nowhere else on the net or in books is there a thorough treatise of more than one method of ammonia preparation. As s uch I am s tarting this thread to go over the various m ethods by which amm onia can be prepared in the com fort and safety of ones own home lab, and to put them
all in one plac e.
There are basic ally two ways of going about ammonia preparation, the in s itu generation of am monia gas as it is needed, and making concentrated am monium hydroxide solutions. I am ignoring the preparation and storage of pres suriz ed or liquefied ammonia for now as I dont have
muc h on that, but I will have a write up eventually.
Pres ented here is a draft of the document as it will appear on m y website. If anybody has anything to add to this, or any c orrections, pleas e pos t a reply.
The Preparation of Ammonia
Amm onia is quite useful for a verity of c hemical applic ations, but alas it is not something you can get at the store. The only commercial source of ammonia is on the farm where it is sprayed into the ground as fertilizer.
Industrially ammonia is prepared by the direc t c ombination of hydrogen and nitrogen, thems elves obtained from water, air, and natural gas heated to high temperatures and c ompressed at enormously high pres sures . This proces s is not economical on the laboratory scale, although it
can be done at atmospheric pressure with cons iderable waste of reac tants.
It is more convenient to prepare ammonia in the laboratory starting with commercially available ammonium hydroxide, available in any supermarket. There are a few different methods, but they are quite similar. They involve decompos ing any ammonium salt with a strong bas e to liberate
a m m onia.
Amm onia can either be prepared as a gas, or as a solution of ammonia in water. Depending on your needs the proc edure c an be modified to fit the applic ation. It is not nec essary to use the reagents described here as the presented reac tions are quite versatile. Any am monium salt
such as the halide, s ulfate, s ulfide, nitrate, acetate, and phosphate will work about the sam e. Furthermore, any strong bas e suc h as the hydroxides of sodium , potass ium, lithium, or calcium, as well as calcium oxide or c arbonate will work.
For matters of economic convenienc e, using am monium chloride as the ammonia s ource, and either calcium oxide (lime), calcium hydroxide (slaked lime), or c alc ium c arbonate (lim estone) as the base is bes t. Am monium chloride is easily prepared from readily available materials, and
slaked lime is quite c ommon as a fertiliz er. Please refer to the appropriate precursor s ections for synthesis information on ammonium chloride and the calcium compounds.
Equipment Setup
It will be found nec essary to have a suitable apparatus s etup in place before comm encing with ammonia generation. This also applies to having the intended reac tion in place and underway, for gas eous ammonia, as it is not easily s tored for future us e. For preparing aqueous solutions all
that is required is a means of bubbling the gas into water. For in s itu generation of am monia the amm onia generator can be affixed to the desired apparatus by an appropriate means.
In either cas e it is advantageous to assem ble a flask to contain the reaction (500 mL should be fine for most applic ations), a one-hole s topper, a s hort length of glass tube, and a length of plastic or rubber tubing to convey the ammonia. Insert the s hort length of glass tubing into the
stopper such that the tube is flush with the bottom of the stopper. If you intend to us e the ammonia immediately, the tubing may be connected to your apparatus in the usual manner. For aqueous preparations the tubing m ay be immers ed into water. A bubbler or fis h aerator is
advantageous for this, but c ertainly not necessary. See the s ection on ammonium hydroxide s olutions below for more information.
For anhydrous ammonia it is necessary to affix a drying apparatus between the generator and the intended reac tion. One c an us e either a drying tube filled with c alc ium c hloride, hydroxide, or other s uitable inert drying medium, or one can use a bottle filled with the s ame that has a two-
hole stopper with a long length of glass tubing and a s hort length. In this m anner the ammonia is forced to diffus e through the drying medium whereupon any water present is taken up.
Solid Preparation
The preparation of gaseous ammonia from solid reactants is quite simple. Heating a thoroughly homogenized mixture of an am monium salt with a bas e is s ufficient to release ammonia. The resulting gas is slightly moist as water is made in the reaction. Pass ing the gas through a
suitable drying medium can easily dry it. Typically the base of c hoice is any of the calcium compounds with amm onium chloride.
Both the ammonium salt and the base are thoroughly powered s eparately and then well mixed to m ake a c ompletely hom ogeneous mixture. It is important that the two chemicals be finely powered and well m ixed because they mus t interac t as much as possible for the reaction to work.
U sing calcium oxide produces the least am ount of water, about 1 mol for each mol of amm onium chloride reacted. Calcium hydroxide produces 2 m oles of water in the s ame reaction. The us e of calcium carbonate poses s o m e s pec ial problems. U nfortunately c alc ium c arbonate is the
m o s t plentiful version of calcium com pounds that c an be obtained from retail sources and s o is the m ost logic al choic e for improvis ed us e. The reaction of calcium carbonate with ammonium chloride ac tually produces ammonium carbonate in the reac tion. As ammonium c arbonate is
quite unstable under the elevated temperatures of the reaction it dec omposes into am monia. Further information on using calcium carbonate is pres ented later on.
Example: Separately prepare dry and finely powdered am monium chloride and calcium hydroxide or calcium oxide. Weigh out a portion of ammonium c hloride (ex. 50 g) and an equal m a s s o f c alc ium oxide (50 g) or 1.5x of c alc ium hydroxide (75 g). The base exis ts in roughly twice the
molar amount needed to c omplete the reaction. Mix the two powders as thoroughly as poss ible and plac e them in a suitable container as described in equipment setup above. Apply moderate heat to the flask throughout the reaction. Ammonia gas will be released according to the
following equations:
2NH4Cl + CaO --& gt; 2NH3 + CaCl2 + H2O; 2NH4Cl + Ca(OH)2 --& gt; 2NH3 + CaCl2 + 2H2O
The exact same reaction setup as above c an also be done with calcium carbonate with a few es sential modifications. The major difference in us ing calcium carbonate as the bas e in the reaction is the production of significant quantities of ammonium carbonate. Ammonium c arbonate is
ac tually a mixture of amm onium bicarbonate, NH4HCO3, and amm onium carbamate, NH4NH2CO2, in roughly a 2:1 ratio. The presenc e of ammonium carbonate will clog an ordinary apparatus and will contaminate a reaction if the amm onia is used as is. A means of c ondensing the
carbonate during ammonia produc tion is es sential. The ammonium carbonate can also be c ompletely converted into amm onia with further effort.
The sim plest means of condens ing the carbonate is to affix a c ondenser or an empty container similar to the setup for a drying apparatus. An empty bottle immers ed in cold water will be sufficient to remove most of the carbonate. This bottle should be closed with a two-hole s topper
having a length of glass tubing in each hole. An improvis ed condenser would acc omplis h the same purpose a bit better. The wider openings of the c ondenser provide less chance of becoming clogged. The additional use of a drying tube should rem ove the last traces of errant carbonate.
U nfortunately the presence of c ondensed ammonium carbonate on any glass surface of the reaction vessel can lead to breakage. The difference between areas of expansion of coated and uncoated surfaces c an lead to great stress on the glass . Substituting a metal c ontainer in this
reac tion will avoid any breakage problem s, or dis posable glas s ves sels could be used. As im provised c ondensers are often made of metal, they are ideal.
Since ammonium c arbonate is also a useful source of ammonia it too can bec ome a valuable sourc e ins tead of a was te product. Adding the entire amount of ammonium carbonate to cold water will diss olve only the carbamate portion leaving ammonium bic arbonate crys tals. On
exposure to air the c arbamate will eventually become ammonium bicarbonate. Bubbling air, or better s till carbon dioxide, into this solution will acc elerate the process . After a s uitable amount of time the c rystals of ammonium bicarbonate can be placed into a s mall amount of water, which
is brought to a boil. The high temperatures will dec ompose the bicarbonate into ammonia, whic h will pass over along with water vapor. See the section on amm onium hydroxide solutions below for more information on preparing am monia this way.
Aqueous Preparation
A weak ammonia s olution, about double the concentration of that which can be purchased in the stores, can be made by conduc ting the reaction in the aqueous state. A saturated solution of am monium chloride at room tem perature holds about 0.5 moles per 100 mL. Adding this
solution to an equal molar mass of base will produc e an amm onia solution of about 8.5%. After allowing suffic ient time for the reaction to be com pleted the am monia solution can be boiled to expel the ammonia. This proc ess c an also be conducted with straight ammonium hydroxide
although increas ingly larger amounts of water vapor will be released at lower ammonia concentrations .
U sing soluble alkali bas es, such as s odium or potassium hydroxide, is best for this type of reaction. Calc ium hydroxide will take longer as it is not very soluble in water. However, the presence of ammonium c hloride will increas e its s olubility. Calcium oxide will react to form calcium
hydroxide when in solution, whic h works the s ame way. Calcium carbonate is insoluble in water, so it is unacc eptable for aqueous preparations.
Example: Dissolve 25 g of amm onium chloride into 100 mL of tepid water in a small flask or bottle. Add 35 g of c alc ium hydroxide or 19 g of sodium hydroxide to the solution. Cap the flask and s et it aside for a few hours to allow time for the reaction to go to completion. The rate of
reac tion of c alc ium hydroxide m ay take longer, but it can be as sumed to have gone to com pletion when most material has dissolved. This reaction will prepare amm onium hydroxide and either c alc ium c hloride or s odium chloride depending on whic h starting material is used.
Amm onium Hydroxide Solutions

Amm onium hydroxide is the old name for s olutions of ammonia dissolved in water. There is actually no suc h com pound as ammonium hydroxide, but by convention that is what it is c alled. The bes t m eans of storing ammonia in an improvised lab is by diss olving it into water. Water c an
hold a c onsiderable volume of ammonia at lower temperatures. At room temperature a 31% ammonia solution can be had, at 0 degrees C the conc entration can be up to 47%. Com mercially ammonia solutions are between 20-30%.
When heated thes e solutions readily give up ammonia gas. At higher concentrations m ore ammonia will be released with les s heat. This is important as the amount of water vapor also rises with more heat. By gently heating a highly conc entrated ammonium hydroxide s olution a steady
quantity of m ois t ammonia gas can be prepared. This gas can be dried quite eas ily by passing it through a drying agent. Lower c onc entrations of amm onium hydroxide are more diffic ult to dry because of the increased volume of water pres ent. By varying the heat and ammonium
hydroxide concentration a steady amount of ammonia gas can be generated as needed.
To prepare a highly c oncentrated ammonium hydroxide s olution set up a series of bottles filled with water. Place a long and short length of glass tube into a two-hole s topper affixed to the bottles. The long end can have a bubbler attached to it to improve the solubility of ammonia. The
short length of tube should not go under the surfac e of the water. The bottles s hould be connected with plastic or rubber tubing with the short tube of one bottle attac hed to the long tube of another. In this manner the amm onia gas will be bubbled into the first bottle, any exces s will
pass into the next bottle, and so on. This setup will help to m inimiz e any was te of ammonia. At the bare minimum one c an stick a length of tubing into a bucket of water.
The ammonia s ource c an be either the solid or aqueous preparations above, or from a weaker ammonium hydroxide solution. As previously mentioned it is more difficult to do this with weak solutions such as grocery s tore ammonium hydroxide. The ammonia generator is connected to
the firs t bottle in the series and the reaction is c ommenced.
The longer this reaction is conducted the more bottles that will be needed. Eventually the first bottle will bec ome completely saturated, while the sec ondary bottles will have decreasing concentrations. Cooling the water bottles, or more appropriately only the first bottle can inc rease the
maximum conc entration.
Drying Ammonia
The bes t drying agent for am monia gas containing traces of water vapor is calcium oxide. Calc ium oxide will remove c ons iderable amounts of water while remaining unaffected by ammonia. Other suitable drying agents include potass ium or s odium hydroxide, potas sium carbonate,
aluminum oxide, c alc ium s ulfate, magnesium perchlorate, and magnesium oxide. The us e of calcium chloride is not recomm ended as am monia can react with it.
rikkitikkitavi October 4th, 2002, 01:33 PM

Im a bit s urpris ed that it seems hard to find ammonia OTC in USA, since you s o readily can buy sulfuric acid as drain cleaner and many other chemicals rest ric ted in Sweden. (I c an get 5 liter 25 % NH3 for 10 in m ost pain shops)
Anyway I have a couple of propos als to make in the manufac turing of NH3 gas.
Amm onium sulfate dec ompose upon gently heating ac cording

(NH)4SO4 =& gt; NH4HSO4(l) + NH3(g) (@ 150 C)
NH4HSO4 in solution or molten is very c orrosive towards metals .

The NH4HSO4 c an be further reacted with Ca(NO3)2 to CaSO4,NH4NO3 and HNO3!
Both (NH4)2SO4 and Ca(NO3)2 are available as fertilizer, the former getting m ore and more rare. NH4Cl can also be available in som e shops selling fertiliz ers.
U rea decomposes into Isocyanuric acid and NH3 at roughly 200C. I have a excellent PDF desc ribing the mecanism which I will upload to the FTP. The name of the file is a9908sch.pdf , and can probably be found by Google (that is how I found it by searching for U rea + decompos ition)
Neither decompos ition releases water at the temperatures given.
/rickard
[ Oc tober 04, 2002, 12:36 PM: Message edited by: rikkitikkitavi ]</sm all>
meg aloman ia October 4th, 2002, 01:59 PM

Do you think you c ould calculate a yield based on the cost of urea in your area, rikkitikkitavi? The reason I as k is I am trying to find the cheapest source of amm onia pos sible for various areas. I don't have any pure urea in my area that I have pric ed, just mixtures. I just wonder if the
urea route can beat $0.99 a gallon for 4% am monia.

I was reading through the article again and found out that a numerous types of reactions take place.
I als o made a few errors reading and interpreting the article, a mistake I often do being one eager bastard....
NH2-CO-NH2 => NH3(g) + HNCO (g) (isoc yanic ac id) takes place at lower temp than stated. (150C)
The NH3 and HNCO reacts forming NH4NCO which decomposes at higher temperatures. This is probably going to cause a lot of los s e s o f N H 3 .
At higher tem peratures more complex pathways comes in place.

Some involve forming water so the previous s tatement that water wasnt form ed is not true. I recommend reading the artic le...
One major reaction is which is binding up HNCO.
H2N-CO-NH2 + HNCO <=& gt; H2N-CO-NH-CO-NH2 (biuret)
Biuret can decompos e in various ways but reaction rate is slow below
200 C.
I make the conclusion that producing NH3 from Urea maybe isnt as feasible as I thought first bec aus e of the reac tions.
But as for a comparision:

I dont have t he price for U rea, but I ass ume that it is nt more expensive than other N-fertiliz ers whic h costs about 25-30 for a 50 kg bag. Given this rough est im ate and the first reaction and 100 % yield .
50 kg = 50000/60 = 833 moles giving 833 moles NH3 or 14 kg or 14/0,04 = 365 kg 4 % solutio n (for 25 )
I hope this is of some help
/rickard
Boob Raider October 5th, 2002, 06:03 PM

Don't take me in the wrong way guys but if you have ever been to one of those public piss cans that are very rarely c leaned then you m ust have noticed a strong ammonical smell whos e sourc e is the urinal. Actually what it is , is when the urea from our piss conc entrates a kind of
bacteria grows on it which breaks urea down by ureas e into NH3 and CO2. That to me looks like the most economical way for producing NH3. Ferm enting Piss in a pot with a dash of urease produc ing bacteria :D . Also that would leave a lot of phosphates overtime for WP extraction in a
wood burning stove. I don't have a s ource of that bac teria but .... one was to ferm ent a strong solution of urea or piss with a teaspoon of garden s oil, a little bit of NH3 soln and nothing else, only urealytic bacteria s hould grow in it.

Ec onom ical, yes . Practical, no. Dis gusting, yes. Hygenic, no. That reminds me of a bit I read about the original alchemic al preperation of phosphorus using two hogs heads worth of anim al urine allowed to putrify for a few months, boiled down to a paste, and processed. Oh god I don't
feel well, imagining a big buc ket of skanky putrid anim al urine is n't doing it for me.
Boob Raider October 6th, 2002, 03:10 AM

Mega I didn't mean to really use piss unless one can't find Urea ..... otherwis e fertilizer grade urea would work very well. I am not too sure but if one was to heat protein in an alkali .... the amino group is liberated as NH3 (I am not suggesting this as an economic al s ource just one of
thos e extrem e sourc es). Other economical and a s elf-sustaining NH3 producing system would contain nitrogen fixation bacteria. I think peanut plants have nodules on their roots whic h are ric h in these bacterias. The s ystem whuld only need s ome es sential m icronutrients, H2O and N2
bubbling through it. But as far as the K.I.S.S thingy goes .... NH4+ s alts work well.
Oh BTW the most disgusting I heard off was the old methods of the extrac tion of tes tosterone. Some c hinees e clan/tribe whatever us ed testosterone as an aphrodasiac (sp? ). To obtain 100g of crude crys tals the had to concentrate 600L of piss by boiling and c onstant stiring <img
border="0" title="" alt="[Eek!]" src="eek.gif" /> . Eeeeewww !!!!
[ Oc tober 06, 2002, 02:15 AM: Message edited by: Boob Raider ]</sm all>
vir sap i t q u i p au ca loq uitu r October 6th, 2002, 12:55 PM

i thought that testosterone was too large to pass across the basement membrane within the nefron of the human kidney ? ? ?
The way in which the french concentrated ars enic:

poison a sow, pour ars enic powder onto body, collect putrid fluid and boil that down to have some "biologically conc entrated" form of ars enic
do you like the idea of collec ting rotting pig fluid :( makes me feel quite queasy !
[ Oc tober 06, 2002, 12:02 PM: Message edited by: vir sapit qui pauca loquitur ]
kin g sp az October 6th, 2002, 06:12 PM

the worst part is i ac tually have that sm ell in my head because i found a rotting seal on the beach once...fucking hell, nothing sm ells worse than rotting flesh <im g border="0" title="" alt="[Eek!]" s rc="eek.gif" />
Boob Raider October 7th, 2002, 10:26 AM

We piss out quite a bit of large molec ules. Little bit is normal but larger quantities is not so I guess thats why they need roughly 600kg of piss to get 0.1kg (0.017%)of the stuff that makes us horny. We piss uric acid and pherom ones too and they are big molec ules, much bigger than
sugars. Although pheromones attract the oppos ite sex, the use of pis s, however, is not rec omended. If you need pheromones use sweat for extraction .... way better than piss (don't ask me how this is done cause I am not quite getting laid 10 times in a day) :D .
Anyways back to NH3 sorry Mega for the smelly piss tangent :p .
Marvin October 9th, 2002, 01:37 AM

I have the greatest respect for what you have done here mega (forums, your s ite, the organising). But some of your sources stink wors e than kingspaz 's rotting seal. I'm a far from perfect chemist myself and on this forum I'm in the c ompany of a fair number of very competant
Log in
October 4th, 2002, 03:32 AM

therm ore, it appears that
wn home lab, and to put them
nia for now as I dont have
laboratory scale, although it
alt with a strong bas e to liberate
rsatile. Any am monium salt
adily available materials, and
preparing aqueous solutions all
ength of glass tubing into the

ubbler or fis h aerator is
d with the s ame that has a two-
ass ing the gas through a
ssible for the reaction to work.

tely c alc ium c arbonate is the
As ammonium c arbonate is
e exis ts in roughly twice the

eleased according to the
nate. Ammonium c arbonate is

means of c ondensing the
osed with a two-hole s topper

ast traces of errant carbonate.
ting a metal c ontainer in this
c arbonate crys tals. On

a s mall amount of water, which
per 100 mL. Adding this

aight ammonium hydroxide
will react to form calcium
o to completion. The rate of

material is used.
olving it into water. Water c an
m hydroxide s olution a steady

the heat and ammonium
he solubility of ammonia. The

e first bottle, any exces s will
nia generator is connected to
e first bottle can inc rease the
e, potas sium carbonate,
October 4th, 2002, 01:33 PM
ng for U rea + decompos ition)

mixtures. I just wonder if the

iss conc entrates a kind of
overtime for WP extraction in a

and processed. Oh god I don't

conomic al s ource just one of
l m icronutrients, H2O and N2
and c onstant stiring <img

molec ules, much bigger than
a day) :D .

umber of very competant
chemis ts inc luding yourself, which was why I joined. I am very well read on inorganic nitrogen chemistry, its s omething of a s pec iality of mine, so I think I can m ake s ome reliable suggestions, at least in terms of theory. In prac tice, its often different, and I'm les s well covered in that
respect.
At atmospheric pressure Id expec t the haber bosc he process to yeild nothing detec table. You never waste gas, as the was te gas is always in the right proportion for ammonia produc tion regardless of how much ammonia has been produced. The only tricky bit is pum ping in the right
amount of extra gas to maintain this from small im balences.
Quote "Any ammonium salt s uch as the halide, sulfate, sulfide, nitrate, acetate, and phosphate will work about the same"
There is a big differenc e between eas e of liberation of ammonia between them, and other problems . Sulphide is a very weak acid, and you would expect a lot of s ulphide impurity in the product, its also very voltile which m akes the problem much worse. Heating the dry salt with a half
decent base is likley to occur at quite a high temperature, ammonium c hloride is also quite voltaile.
Quote "Furthermore, any strong base s uch as the hydroxides of s odium, potassium, lithium , or calcium, as well as calcium oxide or carbonate will work."
Calcium hydroxide isnt a strong base, I suspect this would work in the pres ense of boiling water, but not very well under the c onditions des cribed. CaO should produce the leas t water this is true, but I would expec t this to be a very difficult reaction to get to work properly. I think much
easier reaction would be a caustic alkali with the salt and add water and heat. Amm onium nitrate s eems to be the best producer of the s alts Ive tried, better than the sulphate, but since I can get the s ulphate much easier, thats what Ive used in the past.
Calcium carbonate. I didnt think this would work at all,at leas t in the c ase of ammonium chloride, rather supris ingly, it does. I think what is going on, is when the salt sublimes it disoc iates in the vapour phase. The HCl generated attacks the carbonate, liberating carbon dioxide, and
water. This is the mixture that results from the salt. Id expect the product to be potentially contaminiated by unreacted NH4Cl.
Quote "After a s uitable am ount of tim e the crys tals of ammonium bicarbonate c an be placed into a small amount of water, which is brought to a boil. The high temperatures will dec ompose the bicarbonate into am monia, which will pass over along with water vapor"
It will decompos e into ammonia, water and 2 carbon dioxide, which will mess up whatever the ammonia is intended for.
Consequently this isnt a m ethod of s eperating the ammonia from the salt at all, since it is a s alt, you need a bas e, may I sugges t Ca(OH)2 and dec anting. :D
The ammonia generator, regardless of what method it uses needs a trap to protec t it from sucking up water. Ammonia is very s oluable, and this can force water very quickly into the reaction vessle. This is a c ommon problem when generating s oluable gas ses and with dry s alt methods
us ually res ults in the destruction of the hot glas s containor. An empty c ontainer 'backwards' to the normal way youd bubble a gas through a liquid works very well provided its at least the s ame volume as the liquid diss olving the gas .
Avoid using a pump, with the liquid method and a little heat it will generate a substantial pressure of ammonia. Pumps corrode, and its another thing to go wrong. Drying materials. CaCl2 forms adducts with water (which is why its useful) and also with alc ohols and ammonia. U sing this to
dry ammonia is a very common m istake on the internet. CaO s upposidly will do ok, Ive been told it also forms adducts with alcohols , but this seems to be ok for amm onia, it has a low ultimate partial pressure of water, but its suppos ed to be very slow acting. My personal favourate is
anhydrous MgSO4, cheep, easy to dry, lower H2O partial pressure than CaCl2 and as far as I can tell pretty inert. A better drying agent is previos ly fus ed KOH If you are after completely anhydrous ammonia I sus pect this will not be dry enough and I cant think of anything offhand that
will do a better job unless you c an get s odium metal or NaNH2.
Ive jus t looked up the partial pres sures and CaCl2 is a pretty crappy drying agent, its 3 orders of magnetude behind fused KOH. For mos t reactions fused KOH will provide eas ily adiquate drying, use a predrier of your choice to vastly reduce the work it has to do.
Quote "U nfortunately the presence of c ondensed ammonium carbonate on any glas s surfac e of the reac tion vessel can lead to breakage. The difference between areas of expansion of coated and uncoated s urfaces c an lead to great stress on the glass ."
I have no idea where you got this from, its not right. Glass will expand the same amount reglardles s of what its caoted with. Glass will generally only break due to ununiform heating. Pyrex has a very low thermal expansion and is virtually free from this. Heating thick soda glass is just
as king for trouble.
Quote "A s aturated s olution of ammonium chloride at room temperature holds about 0.5 moles per 100 mL. "
There is no reas on to be limited to the amount of ammonium salt you c an dissolve in water. Dissolve the strong base and add to the solid ammonium salt/more powdered strong base as required. The reac tion will proc eed very readily and ammonium chloride will dissolve and sodium
chloride will prec ipitate as am monia is evolved. Ammonia solutions can be made vastly s tronger this way than the ammonia will diss olve at room temperature.
Quote "Calcium hydroxide will take longer as it is not very soluble in water"
Thats definatly true, but it neglects a major reason. As its a pretty weak bas e its preferentially kic ked out from solution by the ammonia/amm onium hydroxide base, due to the equilibrium between calcium hydroxide, c alc ium ions and hydroxide ions . As a result a muc h lower
concentration of ammonia dorm s in s olution and mus t be expelled before more c an form. Capping the flask when c alc ium hydroxide is us ed will thus not go to completion.
Quote "Am monium hydroxide is the old name for s olutions of ammonia diss olved in water."
Ac tually spirit of hartshorn is the *old* name for amm onia in water, ammonium hydroxide is distinctly new in c omparason. Ok, I'm being unfair here, but this applies to what I have to say next.
Quote "There is actually no suc h com pound as ammonium hydroxide"

This is quote wrong, there is no *s olid* substance as ammonium hydroxide at room temp but it does exist in solution. I'll furthur admit that amm onia in water solution is by far mos tly on the left side of the following equilibrium,
NH3(aq) + H2O & lt;=& gt; NH4+ + OH-
But to s ay it doesnt exist isnt true.
Quote "Other suitable drying agents include potass ium or s odium hydroxide, potassium carbonate, aluminum oxide, calcium sulfate, magnesium perchlorate, and magnes ium oxide. The use of calcium chloride is not recom mended as ammonia can react with it."
Youve mentioned ammonia reac ts with it, but not c orrected its use furthur up in the text. This list contains a wide range of drying agents , with a lis t like this you should add how good they are. Aluminium oxide isnt a drying agent to all intents and purposes , its a glass y inert material
whic h several gemstones are m ade out of. The CRC rating is based on ads orbtion, same way activiated charc ol works . This should s hould be left out as its completely impractical.
Mass water in dried air.

Anhydrous magnes ium perchlorate, unweighable in 210 litres.
Fused KOH, 2mg/litre
Fused NaOH 14mg/litre
CaO 3m g/lite (but slow ac ting, my comment)
anhy CaSO4 5mg/litre
I hope these commends are cons tructive, and are recived in the spirit that was intended. I'm also very curios what you want anhydrous ammonia *for*, just oxidis ing it to nitric oxide to make nitric acid? or are you planning a reaction in liquid ammonia? or making az ides? Give us some
hints. This seems a bit extreme for jus t nitric acid.
Have you checked Mellor volume 8/2 about ammonia production? Its us ually quite exhaustive. If not I'm willing to OCR just that sec tion when my new sc anner is next setup. My old sc anner had an accident involving a s crewdriver and a c urios mind. I havnt read the sec tion recently, I will
and if it adds to or contradic ts anything Ive said I will amend or add to this post as apropriate.
Edited due to gaping great blunder.
[ Oc tober 09, 2002, 03:01 PM: Message edited by: Marvin ]

The means of producing ammonia via the Haber-Bosche proces s is not in reference to any indus trial method, but rather to an improvised proces s. The s imples t means of doing so is to run hydrogen and nitrogen gas into heated s teel wool. The yields are pitiful as the amount of
unreacted is vast, all of which is quite difficult to recover on a sim ple improvised s etup. This does work, I have setup a system myself, which is why I do not recommend it.
Of c ourse those other salts react different. About the same as in the same reac tion mechanis m and formula. That is exactly why I have not used those compounds in m y exam ples. The docum ent is not meant to be an exhaustive treatise, only an improvides means of produc ing
a m m onia in a down and dirty way.
I have direct references the us e calcium com pounds. I have the very s ame c ompounds in my lab and I will be adding to this docum ent considerably experimental results . I am not satis fied with the references myself, and I want to add s ome pictures as well to support my des criptions .
All of the ammonia does indeed form from thermal decompos ition, to mention so is unnecessary when the end product is ultim ately ammonia. I have a considerable amount of references (all quite old) that us e calcium carbonate.
The use of bicarbonate was never intended to be for the direct production of ammonia, but thaks for the reminder of the CO2. I shall clarify my document more in the next draft.
You are right about the trap. I have one in my own setup but did not mention it in my writeup. I shall add it in the next draft.
The presence of c ondensed carbonate was a rather vague warning that I did not iterate well enough in m y draft. It has to do with the poss ibility of the glass c ooling before the c arbonate does, or perhaps it was the other way around. Ever heat a beaker and accidentally set it down on
the c ounter? When it c ools suddenly it c an shatter. This is the s ame principal. I will have to find the reference again as I forget whic h cools faster. Perhaps the pres ence of water vapor can rapidly cool the carbonate leading to shattering. Either way I saw several references that
sugges ted us ing only m etal c ontainers, no glass. I am unwilling to experiment on this front, standard taper condens ers do not come c heap. I will save this for my pickle jar and beer bottle portion.
You are right about the ammonium s alts not needing to be dissolved before the reaction proceeds. This is in fact what I had in mind for the calcium hydroxide. The solid remains undissolved and the reac tion proceeds with it dissolving along the way. This may not fully reac t, but it will go
to completion in its own way. Indeed I will try this through experimentation. It is not a very useful reaction anyway, so I may replace it with s omething m ore suitable.
I am not s o sure. I remember a chemis try lecture some years ago that distinctly s aid no suc h thing as am monium hydroxide exists . I suppos e your one of thos e people who says glass is a liquid? :)
Spirits of hartshorn is getting a bit medieval I think. I dont consider any chem istry before the 18th century to be of muc h value personally. Not even tric kster marketers of today with their vague chemic al synonyms would label an ingredient that way.
The list of drying agents is provided for improvised use with the hope that at least one thing on the list will be available to people. You are right though, I should lis t their abs orptive properties s o they may be s tacked up against one another. I did remove the bit about calcium chloride
after I made the pos t, but on my document not in the pos t.
As to what I intend to use the ammonia for, the answer is yes . Yes to nitric ac id, yes to liquid ammonia, yes to azides . The document though is intended for broad applications. It is not written for me, but for anybody who would want ammonia for whatever purpos e they m ay intend.
My library does not have Mellors (A com prehensive treatise on inorganic and theoretic al c hemistry) but I can reques t it via interlibrary loan.
Thanks for the valuable feedbac k, it was just what I am looking for. I hope that my next draft will include experimental results to back up my information, as well as more us eful references and clairifications.
Marvin October 15th, 2002, 01:48 PM

Their are much rarer books you could get with interlibrary loan, Mellors is quite c ommon here, I will scan some of the sec tions as soon as my scanner is running. The Mellor s et and m yself have plans for extended 'quality time' anyway.
Water vapour from a flask c ondensing and running back has killed a lot of rhetorts, this sounds like the problem. For what its worth I consider glass a 'solid solution'. :D
g lip er October 27th, 2003, 11:06 PM

This gave me 2 ideas, 1 mabe Ca(NO3)2 or at least KNO3 + (AN4)2SO4 under s ome c ondition = CaSO4 and AN4NO3.
2nd (AN4)2SO4 and (AN4)OH or better uria are c omposted with OU T ashes, (AN4) go's to NO3 as always but the (X)SO4 combin with all of the m etalic ions NO3 normally combines with leving ether HNO3 or far more likely AN4NO3 or uria NO3.
g lip er November 1s t, 2003, 04:19 AM

Sorry, I was in a hurry when I wrote that post by (AN4) I ment NH4. To late to edit it.
b lin d reep er November 1s t, 2003, 04:46 AM

It was only 4 days ago and you had the last reply in the topic . If you would have edited no one would have know!
For all newbies!
http://img.villagephotos.com/p/2003-11/464886/whatyoudidwrong.JPG
Yay the big 200 posts!
Rhadon November 1s t, 2003, 06:12 AM

It really was too late to edit that pos t, normal users c an only edit them for a certain time.
b lin d reep er November 1s t, 2003, 07:04 AM

Oh sorry my bad :( All that work making and uploading that beautiful image for nothing.
meg aloman ia September 5th, 2004, 06:58 PM

Recently it has come to m y attention that a local agriculture company s ells urea in vast quantities. I was just reading up on amm onia preperation m ethods again and I came accros s several methods of urea hydrolysis methods. I now see this has already been mentioned here.
If the calculation by rikkitikkitavi relating the number of moles available from urea vs. 4% ammonium hydroxide is correc t than it would cos t about $90 to buy enough 1 gallon jugs of hydroxide to equal the same ammonia in 50 kg of urea for $40 (25 pounds s tirling thereabouts). W hile I
do not recall the price of the urea, I do not think it is nearly that expensive. $15 for a 50 lb (22.5 kg) sack sounds about right, making it around $33 for 50 Kg.
I am going to try and experiment with this partic ular method. Ac cording to my researc h a 50% wt/wt urea in water solution heated to 155 C should give maximum volume of ammonia at near 100% convers ion. At what pressure this will be I do not know, that's one of the things I need to
find out. Another problem I do not as of yet s ee a solution to is how to add m ore urea s olution into the pressurized reaction vessel. Getting optimal ammonia flow will require much experimentation because there are many c onditions that can be varied to produc e more or less ammonia.
(1)The higher the c oncentration of urea in solution the greater the mass of ammonia generated per unit time.
(2)The higher the temperature the greater the m ass of ammonia generated per unit time.
(3)The higher the temperature the higher the pressure, and the higher the press ure the fas ter the ammonia velocity.
A steady flow rate of fres h urea s olution into the boiler held at a steady temperature will produce a cons istent flow of ammonia. Then the pressure can be adjusted ac cordingly to speed up or slow down the ammonia s o it can achieve the optimal residence time over the platinum catalyst
when m aking amm onia.
Would anyone happen to know how to lower the press ure of suc h a sys tem to slow the gas down? Would a pipe of large volume be enough? I don't know enough about chemical engineering to know what exactly to do here. For example heating a boiling water s olution to 155 C may get
the pressure up to 10 atm or m ore, way to high I would think. If all I need is say 2 or 3 atm of pressure pass ing over the c atalyst how can I lower the pres sure? Or can I lower the pres sure of the boiler by using a smaller tank, like a pipe vs. a 15 gallon tank?
Dave An g el September 5th, 2004, 10:52 PM

mega: I wonder if you could include c oolant pipes in the boiler s omehow. By altering the rate of flow of coolant you could therefore c hange how muc h of the water is in vapor form and thus the pressure.
You would need many pipes of large surfac e area to effect a good, responsive control, and some s erious welding m ay be in order, the result being a 'grid' of pipes cros sing the top of the boiler chamber. I hope you c an see what I m ean from this des cription, I've drawn a very crude
picture to help c onvey my idea.
U K members should be able to find a readily available OTC sourc e of NH4Cl in the form of "Witch" powder (a chimney cleaner iirc) at Wilko's. I have some s omewhere, hopefully with the price label still on, s o when I find it I'll give more details about it (price and mass).
(edit) W itch is a "soot and smoke abater" and c omes in a green/white packet, with a black witches hat on the front. It c osts 89p for this 175g packet of ammonium c hloride - cheaper per kilo than even bulk bought lab supply I have ac c e s s to.
If anyone wanted to be daring and liquefy their ammonia then readily available dry ice has a low enough temperature to do it. I believe that LPG propane tanks (NOT butane however) should hold it as propane has the s ame vapor pressure as ammonia at a lower temperature, although
this is only theory so there are likely flaws in the idea.
Dry ammonia is unreactive towards metals (from the MSDS), although if there was mois ture in the system your container might be endangered s o you would really have to dry it well.
There is also the task of getting it into the container, and this where the whole idea might just be a dream. I know little about this, but I have a feeling that one would need a pressurised s ource of liquid ammonia in order to fill the tank, whic h is going to lead to a catc h 22 situation.
(edit) I've jus t looked at som e lab supply c atalogues and the more I think about it... it's probably a bad idea to attempt to refill c ontainers with liquid ammonia. Properly c onstruc ted stainless s teel c ontainers are required, and the regulators, valves and s uch s hould probably all have PTFE
components so that they don't get destroyed by NH3. But, then again, if you can afford the right gear then go for it!
d I'm les s well covered in that
y bit is pum ping in the right
ating the dry salt with a half
to work properly. I think much

.
ating carbon dioxide, and
er vapor"
s ses and with dry s alt methods
hols and ammonia. U sing this to

ting. My personal favourate is
think of anything offhand that
s to do.
eating thick soda glass is just
de will dissolve and sodium
esult a muc h lower
h it."
, its a glass y inert material
making az ides? Give us some
t read the sec tion recently, I will

itiful as the amount of
vides means of produc ing
well to support my des criptions .
d accidentally set it down on

several references that
ay not fully reac t, but it will go
e bit about calcium chloride
ver purpos e they m ay intend.
October 15th, 2002, 01:48 PM
October 27th, 2003, 11:06 PM
November 1s t, 2003, 04:19 AM
September 5th, 2004, 06:58 PM

been mentioned here.
ds s tirling thereabouts). W hile I
hat's one of the things I need to

roduc e more or less ammonia.
time over the platinum catalyst
ater s olution to 155 C may get

ank?
on, I've drawn a very crude
e and mass).
lower temperature, although
ad to a catc h 22 situation.
h s hould probably all have PTFE

Just some food for thought anyway. I hope at least the OTC source will be of use for some.
meg aloman ia September 7th, 2004, 06:30 AM

Clandestine drug m akers use propane c ylinders all the time to s tore ammonia. The valve screws off leaving a pretty decent opening that you c ould fill with liquid ammonia via a funnel. The downside to us ing these is many tend to us e bras s parts that will corrode over time. Fortunatly in
the U S you can exchange propane cylinders for new ones.
I am starting to think using urea as an ins tant ammonia generator may be a bit more diffic ult than I firs t expected. The list of equipment required to do this keeps going up and getting more expensive. While I am sure this c an be done I am not yet at the point where I need to spend
$1000 designing an ammonia delivery system when I have yet to determine if the c atalytic nitric proc ess even works. Adhering to the KISS moto will have to do. Us ing urea as an ammonia sourc e is s till a good idea I think. I will have to do s ome ec onom ic calculations once I get s ome
measurable yields.
As s uch there are already excellent instructions provided by the Hive for the liquifac tion of gaseous amm onia by dry ice. The ammonia is passed through a drying tower and liquified in a cold trap kept cool by dry ice and acetone. Simple and effective. One would then adjust the size of
their catalyst to be useful over the pressure range of liquified amm onia stored at room temp in a tank.
Dave An g el September 7th, 2004, 06:19 PM

The same applies here in the U K, cylinders can be exchanged. One will have to pay for the refill, (lest ques tions be as ked about why one wants an empty c ylinder), and then use up the propane, so pairing this with a propane burning furnace project m ay be a good idea. In fact, the cos t
of a propane refill is minim al so simply burning it off would be no great financial loss .
A couple of useful links for those going down this route...
A rhodium page on the liquefaction of amm onia:
http://www.rhodium.ws/chemis try/eleusis/ammonia.html
And a supplier's ammonia page, the data on the page being the us eful part:
http://www.airliquide.com/en/busines s/products/gases /gasdata/index.as p?Gas ID=2
I searc hed the Hive and there is a thread (https://www.the-hive.ws/forum/showflat.pl?

Cat=& Number=51521& Search=true& Cat=& Threads =& Search_s imple=& Name_s imple=& Text_simple=& N a m e = & Subject=&Body=& Text=am monia%20propane& U sertitle=&Signature=& RateRemark=& Pos tNo=& Limit=25& DateFrom=m enu& DateTo=menu& From=all&To=now& FromDate=12-
31-97& ToDate=09-07-04%2022%3A14& TypePos t=on& TypeDiges t=on&RateMinus=& RateNeutral=on& RatePlus=on& Order=date& Sort=DESC& Preview=on&PreviewChar=500&NoHelp=0& Searc hID=mQq6djxMqsbmeWww&U RLForums =All_Forums%3Don&Cache=1&Searchpage=2) in which a
poster details how to prepare a propane tank to hold ammonia, which may be of some use.
n bk20 0 0 September 9th, 2004, 09:04 PM

Is there any way of dry disassociating the urea into ammonia? As am monia-salts reac t with a base to liberate the gas, wouldn't the ammonia containing urea do the same?
meg aloman ia September 10th, 2004, 02:19 AM

U rea can be directly decompos ed, dry, by heating past the melting point, but the reac tion is far more effic ient in the presence of water. Urea technicially is not an ammonia salt, s o it will not react like the other usual sus pec ts will in producing am monia with a base. In fact the urea
decomposition works even better in acidic conditions, of course that is of no practical value in most instanc es since the acid will be neutralized by the am monia. Adding a strong base like s odium or potassium hydroxide will act as a catalyst in the reac tion c ausing more ammonia to form
at a lower temperature. The best catalyst, though, is vanadium pentoxide.
n bk20 0 0 September 10th, 2004, 03:20 PM

Isn't vanadium available at the ceram ics s uppliers as a glaze coloring or such? If s o, then jus t using a dry mix of urea and vanadium at atm. pressures would be far more preferable than needing high-pressure steam vessels.
meg aloman ia September 14th, 2004, 10:00 PM

Vanadium ac ts as a catalyst in the hydrolysis reac tion only. In a dry mix it is no longer a catalys t, but a reactant, and as a reactant it would noit be a strong base.
The problem with directly dec omposing urea is the yield is much less than the aqueous reac tion. To get the mos t for your money the pressure proces s is the winner. I am going to try to find my pressure cooker this weekend and s ee what temp I get.
Incidently I bought a 40 lb bag of urea for $9.50. I als o found this gem of government propaganda: http://www.tfi.org/TFImeth05.pdf Save the m oral fiber of the U S, just say no to amm onia!
vBulletin v3.7.2, Copyright 2000-2008, Jels oft Enterprises Ltd.

September 7th, 2004, 06:30 AM

orrode over time. Fortunatly in
point where I need to spend

calculations once I get s ome
would then adjust the size of

e a good idea. In fact, the cos t
om=all&To=now& FromDate=12-
=1&Searchpage=2) in which a
eptember 10th, 2004, 02:19 AM

th a base. In fact the urea
c ausing more ammonia to form
eptember 10th, 2004, 03:20 PM
eptember 14th, 2004, 10:00 PM

Improvised Manufacture of Nitric Acid > Nitric Acid Experiment Pictures
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megalomania June 10th, 2002, 05:35 AM

I have taken some pictures of my most recent experimental setup to prepare nitric acid. These pictures show the apparatus
that I set up including an ammonia generator, catalyst chamber, and a bubbler. Unfortunately the experiments were plagued
with difficulty exposing some weaknesses with my design. Ultimately I was unable to produce nitric acid, or not enough to
detect. No matter, I have redesigned the entire apparatus to correct for the problems. I will post the new plans some time
soon. I will build it soon after as I already have the parts I need.
This first picture shows the entire setup.

<img src="http://www.roguesci.org/megalomania/experiments/web1.jpg" alt="" />
This second image shows a close-up of the ammonia generator. Here I use a 500-mL round bottom flask with standard taper
connections to hold my ammonia. I use here ordinary ammonium hydroxide straight from the store. The flask is heated by a
Thermowell (hotplate). The sep funnel acts as an addition funnel. The condenser helps return some of the water vapor that
comes with the ammonia. The air compressor to the right supplies the air through the hose that goes straight down into the
flask. This supplies both an excess of air, and increases the velocity of the vapor flow. As it turns out the air compressor
produced way too much airflow, even at its lowest setting. The air kept frothing large amounts of water into the catalyst
chamber.
Here we see the catalyst chamber itself. I have employed 3 lengths of steel tubing connected together. The center tube
contains the catalyst, and is heated by the torch. The other 2 tubes are supposed to be heat sinks, but this did not work out
well. I wrapped them with cold towels as a temporary measure, but they still run hot. Most of the new design centers on
creating a better way to keep the inlet and outlet cool before it contacts the plastic tubing.
Here is a close-up of the bubbler. This particular setup has the outlet tubing connected to a glass tube that extends to the
bottom of a glass cylinder. This setup is unacceptable for actual nitric acid production as a third of the product would be lost.
As it is here, it is easy to see.
This picture uses coloring to demonstrate the intended reaction and makes the liquid portions easier to see. The blue liquid in
the flask and addition funnel is ammonia, stating from the generator. The red liquid in the cylinder is the nitric acid.

Here I am modeling the setup. These pictures are like the above. Check out those legs.
nbk2000 June 10th, 2002, 09:07 AM

Nice gams there, Mr. Wizard!
:p
But seriously, you need a couple of U bends on the ends of your reactor. These are immersed in water, with a constant flow of
cold water being supplied by a hose. The overflow goes to the drain. This way, your hoses will never get hot enough to melt.
Using a spiral coil, instead of a U, will greatly cool down the nitric acid vapor as well.
<img src="http://server3001.freeyellow.com/nbk2000/nitric.gif" alt="" />
And, if I'm not mistaken, isn't vanadium oxide also useful as a catalyst? If so, then you can get that by the pound at ceramic
suppliers.
[ June 10, 2002, 10:59 AM: Message edited by: nbk2000 ]
Alchemist June 10th, 2002, 10:59 AM

Hello Mega,
Very nice. What are you using for the catalyst?
P.S., I have sent you some e-mails, but they came back! Have you changed adddress? Email me when you have time.
mr.evil June 10th, 2002, 11:01 AM

Nice set up you got there mega! do you have more pictures of your lab?
stanfield June 10th, 2002, 01:45 PM

I don't understand something :
it's so easy to distill nitrate+sulfuric or low concentrated nitric acid... so, why do you bug yourself by setting up an "home-
industrial" plant ? I would like to know how much nitric acid do you get at the end of your apparatus, and, ofcourse, what's its
concentration ?
see ya !
mr.evil June 10th, 2002, 02:25 PM

You can see that the HNO3 is orange, so it must contain lots of NOX, is there any way to prevent this? like bubble it under
vacuum?
where do you get such nice glassware? There are many Glassware company's in my city, but none of them sells that tiny little
pieces of glassware and industrial stuff...
Anthony June 10th, 2002, 02:53 PM

The orange liquid is just coloured water to show what the setup would look like if it was working.
If the compressor is giving too much flow, a simple hose clamp around the about tube should enable you to regulate it a bit. A
valve would be better but a hose clip is a few second job and costs a few cents.

Here is a pair of pics of selected excerpts of my notes detailing my next design. I intend to user a copper preheating coil
wrapped around the catalyst chamber with both a pre- and post-cooling reservoir. The first picture shows an overview of this
design, and the second shows a more detailed close-up of the catalyst chamber.
<img src="http://www.roguesci.org/megalomania/experiments/design1.jpg" alt="" />
<img src="http://www.roguesci.org/megalomania/experiments/design2.jpg" alt="" />
Often my email box gets filled to the max. Because Hotmail has become a cheap bastard about this, they bounce all emails
back when it is full. Try sending it again, eventually I will clean the thing out. I am preparing to move to a new account for
private correspondence.
The reason behind using this method is one of economy. Not all people have access to nitrate fertilizer, but everyone has
access to ammonium hydroxide. The efficiency of this process makes it far cheaper as well. Furthurmore, this is the most
suitable method for making 120% fuming acid, or ever 100% acid. You can only do this from nitric oxide fumes, which
distillation does not give. Also, this setup does not require exotic glassware. I may be using exotic glassware here, but that's
just because I have it. My final design will be set up in such a way that all of the equipment, chemicals, and connectors will be
from everyday hardware stores and grocery stores.
[ June 11, 2002, 02:46 AM: Message edited by: megalomania ]
10fingers June 11th, 2002, 06:35 AM

*
[ June 12, 2002, 08:51 PM: Message edited by: 10fingers ]
DBSP June 11th, 2002, 07:17 AM

It looks very nice, only I don't excactly understand the process. If anyone has any texts or chematics on this I'd really like to
see them. I'm especially interested in seing some simplifyed drawing of the setup, like the one posted but with the
substances put out as well. And what yields can you expect from this method. To me this method is very interesting since I
only have limited acces to sulfuric acid.
Sorry if its a lot of questions at once.
[ June 11, 2002, 06:20 AM: Message edited by: DBSP ]

yeah i like to see some documents of the above method... :)
(i have lots of H2SO4, and i can get it very cheap but anyway)
Flake2m June 11th, 2002, 08:48 AM

Meglomania, could you please post a chemical equation on how nitric acid is produced from ammonia and air. I am a
chemistry student so this would help me to understand how this proccess works.
My other problem concerning this production is:

Most store bought ammonia products contain about 1 mol per litre, they also contain impurities in them (soap etc) that may
interfere with the production of ammonia.
Where would I be able to purchase a bottle of concentrated ammonia, something in region of over 5 moles per litre?
Microtek June 11th, 2002, 09:10 AM

The ammonia that is sold in the stores around here ( Denmark ) is at least 20% and more often 25% NH4OH which would
make it almost six and a bit more than seven mol per litre, respectively.

i can buy very easily 25l cans of 15% Ammonia, and in stores 5-10% Ammonia. I have also some 25% Technical
Ammonia(5L) For the europeans here, in Belgium you can buy lots(!) at the drug store, they even sell Hg Salts!! <img
border="0" title="" alt="[Eek!]" src="eek.gif" />
But anyway, if you have some common 5-10% Household ammonia, i suggest you destillate it...
(on the link below you can see a picture of the NH4OH purification...and some other pics) :)
<a href="http://www.geocities.com/tshadowpp/temporarypreviewfile.html?1023798912390" target="_blank">http://

www.geocities.com/tshadowpp/temporarypreviewfile.html?1023798912390</a>

*

I belive that you can buy conc ammonia in sweden too, about 25%.
What catalyst is best to use, both in the perspective of acuisition and performace?

Hello All,
The Formation Of Nitric Acid From Ammonia
Nitric acid (HNO3) is made from ammonia (NH3).
The reaction happens in three stages:
1. Ammonia and oxygen from the air are reacted together to make
nitrogen monoxide and water.
They are heated to 300 0C and passed over a catalyst of platinum (other catalyst's
have been used).
(A catalyst speeds up a chemical reaction without itself being
changed).
The reaction makes its own heat (exothermic) and is cooled down by
using more air than is needed to react with the ammonia.
4NH3 + 5O2 --------> 4 NO + 6 H2O
ammonia + oxygen -----------> nitrogen monoxide + water
2. The nitrogen monoxide is reacted with more oxygen from the air to
make nitrogen dioxide which is a brown poisonous gas.
2 NO + O2----------> 2NO2
nitrogen monoxide + oxygen ---------->nitrogen dioxide
3. The nitrogen dioxide is dissolved in water in the presence of air to

make nitric acid.
4NO2 + O2 + 2 H2O----------> 4HNO3
nitrogen dioxide + oxygen + water---------> nitric acid
[ June 11, 2002, 10:39 AM: Message edited by: Alchemist ]
rikkitikkitavi June 11th, 2002, 02:18 PM

I think the major obstacle is that the rxn
2NO + O2 is a very slow one at atmospheric pressures and low conc of
NO, < 10 %
Kinetics doesnt work in our favour :(
Found the following data in a text book.

Time of rxn for 50 % of original NO to react.
@ 60 C 760 mm Hg
Starting concentration (% volume)
O2 NO time (s)
6,5 5 25
6,5 3 40
6,5 2 57
6,5 1 112
6,5 0,5 225
6,5 0,1 1100
6,5 0,05 2200
10 2 37
6,5 2 57
4 2 98
(damn it , who do I get a nice table? Spaces just get squirked together)
reaction speed r ~ [O2] * [NO] ^2
(solving the differential equation
d[NO]/dt = - [O2] *[NO]^2 gives a expression of how NO varies with time
The reason why they build BIG houses covered with lead sheets in the lead chamber process was just for the reason of giving
the NO=> NO2 reaction enough time to take place.
So instead of leading the hot gases directly to a absorbtion vessel we have to give the NO time the reaction come through.
And chemical reaction kinetcis learns that letting the gases enter a large chamber
(where they would be dilutied, both through large volume and rxn) between the catalytic cumbuster(sorry couldnt help it:) and
the absorbtion vessel is less favourable than simply using a looong hose(or tubing ). In the latter case the rxn is the only
factor lowering NO-conc and thus reaction time.
How long? Experiments is probably best way to find out since there is many variables.
/rickard
[ June 11, 2002, 01:52 PM: Message edited by: rikkitikkitavi ]
vulture June 11th, 2002, 04:22 PM

10fingers, the catalyst from an automitive is designed to convert NOx into N2 and [O], if there was any NO produced in your
process, it would have immediatly been converted to N2 and [O].
PYRO500 June 11th, 2002, 05:03 PM

You know, that flask with the bright blue vapor/liquid, it looks alot like an XTC lab I have been to where the were producing
freebase :) .
Alchemist June 11th, 2002, 05:40 PM

Hello all,
This is a very small scale demenstration of the process only!
Also, oxides of iron with traces of oxides of other common elements have been used!
Catalytic Oxidation of Ammonia
Equipment
250-mL Erlenmyer flask, rubber stopper for flask, barbecue lighter, rod to support wire across the top of
the flask, coiled platinum wire. The coil should be approximately 7 mm in diameter and loose enough that
the adjacent coils so not touch.
Reagents
25-75 mL of concentrated aqueous ammonia solution.
Presentation
1.Pour the ammonia solution into the flask and stopper it.
2.Attach wire to its support.
3.Adjust the length so that the end of the platinum is 1-3 cm above the surface of the ammonia
solution.
4.Unstopper the flask.
5.Heat the end of the platinum wire until it begins to glow red.
6.Quickly, put the wire down into the flask.
7.The wire will glow brightly.
8.The wire may be removed from the flask and it will cease to glow.
9.If the wire is returned to the flask before it gets too cool, it will again glow brightly. This may be
repeated many times.
Hazards
Concentrated aqueous ammonia can cause burns and is irritating to the skin, eyes, and respiratory tract.
Nitrogen dioxide is an extremely toxic gas. It is irritating to the respiratory tract.
Discussion
Ammonia is catalytically oxidized at the platinum surface according to the following reaction.
5 NH3 (g) + 5 O 2 (g) 4 NO (g) + 6 H2O (g)
The reaction is exothermic and as written releases 920 kJ of energy. A second reaction proceeds
automatically from the first reaction.
2 NO (g) + O 2 (g) 2 NO2 (g)
The second reaction is also exothermic and as written releases 112 kJ of energy. These two reactions
taken together make up two thirds of the Ostwald process for the synthesis of nitric acid. If the NO2 (g)
were put into contact with liquid water, nitric acid and NO (g) would be produced. The initial heating of the
wire with the lighter provides the actvation energy for the reaction. Once the reaction begins, the released
energy will provide more than enough activation energy for subsequent reactions to occur. An interesting
variation of this demonstration is to substitute a thin copper wire, approximately 0.2 mm in diameter for the
platimun wire (2). The heat from the reaction is sufficient to melt the copper wire. The molten copper will
spatter and make a spectacular effect. Additionally, some of the copper will oxidize and turn the ammonia
solution blue by forming a complex ion between the Cu 2+ ion and the ammonia [Cu(NH 3) 4] 2+. This
variation does not work as consistently well as the platinum version does.

The technical details I am keeping to myself because there is a lot to write. I have also concluded that using the straight
ammonia is probably not good. The ammonia in the US is 2-3% on average, and if you are lucky you may find a 5%. I have
used the $0.99 a gallon 3% variety thus far. I have a few more experiments to try with this type of ammonia because
anything more concentrated requires more materials, and more expense.
The key to the reaction is the residence time of the NH3 on the catalyst. The ideal time is 0.04 s and the ideal amount of O2
is a sixfold excess. If the residence time is to long you will decompose the ammonia into nitrogen and water, if it is too short
you will get ammonia with your nitric acid and end up with ammonium nitrate in your product. The choice of catalyst will also
affect residence time. Copper, which is what I am starting with because it is the cheapest, is more likely to decompose
ammonia if the residence time is too long. Platinum, the catalyst in automotive catalytic converters, is the best, but it is also
very expensive and difficult for many people to obtain. Notice the catalytic converters are quite large (long). This forces a
lengthy residence time, resulting in mostly harmless products. I have a cross section of a cat converter that I have not
experimented on yet. When I use it, I will use a cm or less.
I will experiment with a variety of catalysts. The one good thing about all this, even with an expensive catalyst like platinum
you lose very little over long periods of time. In a low-pressure system like mine, you may not lose any at all. My copper
sponge is straight from the grocery store, dirt cheap, and allows airflow. Platinum from a cat converter is either small spheres
(older ones) or a honeycomb mesh, which also allows airflow. Using powder catalysts, and other metals, will require it be
attached to a suitable surface to allow a free flowing system. I have ways of doing that, but again, that adds extra expense
and materials most people may not have.
Alchemist, your forgot to mention in your equations that 3NO2 + H2O --> 2HNO3 + NO
You will lose 1/3 of all the NO2 produced this way. That is why I mentioned my bubbler is unsuitable. Of course I am not
concerned with peak efficiency as of yet, just getting the thing to work (one problem at a time please). I have not devised a
system, but my ideas range from the simple several bottles in series to a complex water mist tower.
The reaction is indeed very exothermic. Once it gets going you will be able to stop external heating, and regulate the temp by
controlling the flow of ammonia and air. I have net developed my experiments to the point that I need constant temperature
and pressure/gas flow measurements, but anticipate I will to get the best experimental results. I do not anticipate these
things will be needed in the final system; they are just to find optimal conditions. While I am on this topic, does anyone know
of any chemical engineering equations to determine the amount of a substance based on pressure, or air speed? Some links
to chemical engineering resources would help me. I havent found anything yet. I suppose that is because I dont know what
to look for.
The kinetics of the reaction are actually very, very fast. The reaction between NO and O2 is almost instantaneous at STP, or
near enough at small quantities as to look like it. In this reaction we are not at room temp, but up to 300-500 degrees, and
that will increase the rate considerably. Rikkitikkitavi, does that table take into account the diminishing volume of NO and the
increasing volume of NO2? If that is a closed system we would expect to see less and less NO2 being produced over longer
and longer periods of time. In my system we have a fairly constant ratio of NO and O2 at the site of the catalyst. The volume
of O2 tapers off as more NO2 is formed, and drops after being bubbled into water. When I develop a series of bubblers there
will need to be an additional source of air to react with the NO that forms. This new air source will be added after the first water
bottle. If you add too much air from the beginning you may push the ammonia through too fast.
I have seen the experiment done with both the platinum wire and copper wire. That is in fact what has inspired me to do my
current experiments. My designs are based on earlier experiments along those lines. I know this works; the theory is sound
and has been done for almost 90 years now. Knowing that a thing can be done is an important step to actually doing it.
nbk2000 June 12th, 2002, 08:49 AM

Just a note that the thorium coated gauzes used in gas mantle lamps are used as catalytic converters by clandestine drug
manufacturers to convert phenylacetic acid to P2P. Perhaps a thorium mantle would be a quick way to get started?
I've also got several yards of a screen material in storage in california that, even after exposure to intense flame and glowing
red-hot, remains intact and flexible. It's not metal, but some kind of synthetic fiber. I found it so I don't know what it is.
Brings to mind an idea of using a platinium salt to coat the screen and then exposing it to a reducing flame to convert it to an
activated form that adheres to the screening.
A process for making platinium black and sponge can be found in Dicks encyclopedia (might be in "Grandads wonderful book
of chemistry" by Kurt Saxon).
Also, I've read the a container filled with totally anhydrous Ammonium Nitrate prills will absorb a large amount of ammonia gas
and hold it like acetone does acetylene. In doing so, it reduces the pressure needed to contain it in liquified form to just a few
atmospheres, well within the range of a 2 liter soda bottle or fire extinquisher. :D
Pass the NH3 through two condensers, one with cold water, then drierite, then acetone/CO2 slush to liquify it. Then it'll be
purely anhydrous and ready for mixing with the AN for storage. Much easier to control a gas cylinder than a boiling flask. And
no dilution of the source material either with water vapor.

*
mega, first i like to say:
very impressive setup. A very thorough experiment.

now after cleaning my (brown ) nose to your question.
The table I took my data is to interpreted as the reaction time is the time for 50 % of the original NO-amount to react. No NO2
to start with.
Of course the NO and O2 conc decreases as the reaction progresses, and this is taken in account in the table.
Remember that at temperatures > 200 C the back reaction NO2 > NO + O2
also takes place, thus cooling the gases after the converter increases yield.
high pressures favours the production of NO2, but for us it is probably not an option.
mega, your question about equations? can you specify?

I can recommend some books on chemical engineering just goon look up the ISBN...dont have any online links though :(
/rickard
[ June 12, 2002, 04:42 PM: Message edited by: rikkitikkitavi ]
megalomania June 12th, 2002, 08:01 PM

My question relates to the calculation of the residence time of the ammonia on the catalyst. I want to know how to calculate it
with only simple measurements like a pressure gage, and by taking into account the surface area of the catalyst and the
length of the tube.
I have no hard data on the reaction of NO to NO2, but I have first hand observation which tells me the reaction is quite fast.
Perhaps on the industrial scale they consider it a problem. We have to deal with is the loss of 1/3 of all our produced oxide
anyway. By the sheer fact of having a series of bubbling containers, we extend the reaction time considerably. We will likely
have mixtures of oxygen and NO kept in solution or in the air above the water for several minutes. By using 4,5, or maybe
more depending on how industrious you want to be, water filled containers we can get almost all of the NO to react.
The temperature I quoted is only in the catalyst chamber. That is the site where NO is formed, and since the residence time at
that temperature is so short, the backwards reaction is unlikely to happen. That is what should happen anyway; this assumes
one can effectively control the residence time.
For furthur information, I suggest reading US patent 858,904 by Wilhelm Ostwald. He is the authority as he invented the
process. This patent is geared to the lab scale, and is perhaps the only available technical information not concerned with
industrial scale matters. Very few other resources give as many secrets and insights as that patent (not enough though).
Reviewing it now I see I misspoke earlier, you need a minimum of a sevenfold excess of oxygen. One may also note his
description on using different catalysts:
The speed will depend in every special case on the nature, the surface and the distribution of the contact bodies or catalytic
agents and must therefore be determined by experiment. The speed is increased until unoxidized ammonia can be tested in
the reaction products and the speed is then kept a little below this limit but as near to this limit as it may be practically
possible.
It is this that I am experimenting to find. Obviously right now my choice of a catalyst is less important than consistently
delivering proper ratios of ammonia and air, getting the temperature up, and sending it through fast enough to avoid
decomposition.
In reconsideration as I read the literature, I suppose it is not important for me to have chemical engineering equations. I
thought it may be helpful to calculate the right speed before experimenting, but I doubt I have the means to precisely
determine the equation anyway (short of experimentation which would defeat the purpose).
nbk2000, I am unfamiliar with a gas mantle lamp. What exactly is that, and where can I get one?
I have that info from Dicks and some related from Vogels and the Organic Synthesis series. It is not a problem to make
these kinds of things, and is in fact an issue in my notes, but not for my experiments as of now. The importance of making
your own metal gauze is if and when supplies of other ready made materials dry up. Copper sponge is the cheapest and most
readily available material for the vast majority of people. It is used in drug manufacture, so it will probably dry up in 10 years
(I am planning for the long haul). You cannot buy a used catalytic converter; it is illegal in the US to do so. Buying a new one
may be prohibitively expensive for some people. In my experience I had to pull some teeth to get the sample I have. One
can get platinum metal from jewelry or coins, as well as nickel, rhodium, ruthenium, osmium, and palladium to a lesser extent
from many sources. The amount of effort and chemicals needed to convert these things to a usable catalyst may be daunting
to some people. Not everyone will have this trouble, but many people will, and I want as many people as possible to be able
to enjoy the fruit of my labors. That means a lot of work that can side track me. I just want to know what is the easiest to get
and cheapest catalyst, for right now, in 2002.
I like that idea of mixing ammonia with ammonium nitrate, that could be very handy (to me). It is somewhat beyond the
scope of my experiments right now because CO2/acetone slurries are not for the common man. That is not so far fetched
though that many people could not do it. It gives me another option to try should straight ammonium hydroxide prove to be
unsuitable. I had a big problem with excess water vapors. I can exactly test for it, but I believe it drives the temperature way
down (at least with 3%). I plan to neutralize the ammonium hydroxide from the grocery store with hydrochloric acid from the
hardware store to form ammonium chloride, and then decompose that (after obtaining crystals) by adding sodium hydroxide
solution (made through electrolysis or bought as lye). I also intend to try using lime as an absorption medium after heating
the straight ammonium hydroxide (3%).
The more stuff you need, the more this whole things costs, the harder it is to get, and the more questions you have to
answer to the corrupt authorities. Still, there are many options and methods to use here, and so we are not limited by any
single one. That means if one does not work for you, you can try another way. I operate under the assumption that eventually
every chemical will be banned, or pulled from the shelves. That is why I focus on the easy innocent stuff, it will be the last to
go.
Edit: If anyone can get these to work, there is a website that supposidly has movies of many chemical reactions. Specificially,
<a href="http://chemmovies.unl.edu/chemistry/redoxlp/a28.html" target="_blank">Ammonia Oxidation Catalyzed by
Platinum</a> and <a href="http://chemmovies.unl.edu/Chemistry/RedoxLP/a20.html" target="_blank">Oxidation of Nitric
Oxide by Oxygen</a>
I think this may be a front page to get you to buy their video disk :( Or my media player isn't working. If somebody can view
these, tell me. Oh, the master index of many more interesting movies is at <a href="http://chemmovies.unl.edu/chemistry/
redoxlp/redox000.html" target="_blank">http://chemmovies.unl.edu/chemistry/redoxlp/redox000.html</a>

Mega, I saw the mov file in full and it is not very good! They turn the lights off after the flow is started and all ya see is the Pt
glowing.
Here is some info on another catalyst. Still expensive, but NOT as bad as Platinum.
COBALT OXIDE CATALYST
Cobalt Oxide Catalyst for Ammonia Oxidation reduces Catalyst cost

up to 75%
Nitric Acid or Nitrogen Oxide have been produced basically the same way since the
beginning using Platinum/Rhodium catalyst. Cobalt Oxide Catalyst is used as an
alternative to solve several problems such as the high cost of platinum; the short
operating cycles; and the by-product reaction producing NO. Cobalt oxide catalyst is
used in nitric acid plants as an alternative to the Platinum-based catalyst. By using
cobalt oxide catalyst, plants have shown increased production at significantly reduced
operating costs.
Cobalt oxide catalyst technology improves operating cycles and increase efficiency
over the platinum catalyst technology.
Benefits of Cobalt Oxide Catalyst in Ammonia Oxidation

The following are a few of the many benefits of using Cobalt Oxide Catalyst Systems:
Higher ammonia conversion efficiencies:

95% + for high pressure plants (90-120 psig)
98% + for low pressure plants (0-25 psig)
No plant shutdowns due to the catalyst

No need to change out the catalyst charges
No more catalyst inventory costs due to strength and longevity of the catalyst
Lower operating temperatures (about 1550 F) results in less heat exchanger failures
Reduced maintenance costs since there are no shutdowns to change out catalyst. Also, longer
runs and lower temperatures reduce equipment failures due to thermal cycling
Lower pressure drop in the system reduces steam consumption or increases the production
through the plant
Much less NO, which is an environmental pollutant
Economics of Plant Conversion using Cobalt Oxide Catalyst

Cobalt Oxide Catalyst Systems offer a simple short term payback of less than one
year on the initial investment and provides significant long term savings by reducing
catalyst operating costs; reducing maintenance cost; longer production runs; and
improved ammonia conversion. These outstanding savings are possible because
Cobalt Catalyst System reduces basic catalyst operating costs from $3-$4 per ton to
$0.50-$0.75 per short ton of nitric acid. Imagine a 350t/d plant saving more than
$400,000 per year in operating expenses alone. Add increased production from the
improved efficiency and reduced maintenance from longer run times and that plant
could see a yearly savings exceeding $500,000.
Some plant evaluations have even shown that they can recover 75% of the
capital conversion costs from the sale of the platinum/rhodium gauze in
inventory.
Mega, I know this is NOT a complete recipe for the catalyst, but it may give you some ideas.
*** SEE U.S. Pat. 3,931,391 ***
[ June 13, 2002, 05:44 PM: Message edited by: Alchemist ]
nbk2000 June 13th, 2002, 11:20 PM

Gas mantle lamps are available at most decent hardware or camping stores. The most frequent name is Coleman. It uses
propane as fuel (usually) and costs about $20. But you can buy replacement mantles for $1 for two mantle, so it's quite
cheap.
Obviously one wants to keep the process as simple as possible, but that's not always possible because of the need to make
ones own materials, adding steps. The drug chemists have the same problem, but are motivated by a huge profit margin that
us pyros don't have.
I've got a bunch of movies off that movie site from last year. Including one with the conversion of ammonia to nitric oxide via
copper. It's not all that informative though.

I did some reading on the ostwald proccess. I found that it generally uses a platinium/rhodium catalyst as you know these
catalysts are very expensive. However, I also found that a platinium/rhodium catalyst is used in car mufflers to turn unreacted
fuel, carbon monoxide and NOx into water, carbon dioxide and nitrogen.
This would give me an easy source of a decent catalyst - car mufflers. Since pretty much every car has a muffler you could
hypothetically steal the mufflers off a car for the catalytic converters they contain. You could also buy some old mufflers at a
junkyard for their catalytic converters (but i think they are removed when a car is salvaged).
Ammonia will disolve upto 400 times its own weight in water, or 1 part of water can hold 400 parts ammonia.
Meglomania - your "bubbler" system may be inefficent but it could be made more efficent by increasing the surface of the
outlet, that is instead of having one outlet to bubble out the NO2 use a hose (corrosion resistant) along the bottom of the
container with about 20 holes in it, this way the NO2 gas diffuses over a much larger area. You could also keep the water
moving, by stirring it while it is defusing, this moves the water/nitric acid mix around and helps it to diffuse faster
[ June 14, 2002, 08:48 AM: Message edited by: Flake2m ]
photonic June 14th, 2002, 03:09 PM

Ehh, the muffler doesn't contain the catalytic converter on a car. At least not as I understand it. They're two completeley
separate things.
Mick June 16th, 2002, 08:36 PM

yes, a car muffler does contain a catalytic convertor.
i don't know whats in them tho, as i have no use for them.
EventHorizon June 16th, 2002, 10:31 PM

You usually have a catalytic converter and a muffler both. Usually the catalytic converter is first in the exhaust flow, then the
mufflers further rearward.
Would be interesting if it would work. Most people get the converter hot, then dump water down it to break-up the honeycomb
in there. As far as I know, you should be able to get a "replacement" converter at a junk/salvage yard.
[ June 16, 2002, 09:34 PM: Message edited by: EventHorizon ]
10fingers June 16th, 2002, 11:57 PM

The catalytic convertor and the muffler are two separate things. The convertor will look somewhat like a muffler but usually
smaller. It will be between the muffler and the engine. Some convertors have two different catalysts inside, a platinum one for
oxidation of hydrocarbons and a platinum/rhodium for elimination of oxides of nitrogen.
If you have a grinder with an abrasive cut off disc you can easily cut through the housing of the convertor and pull out the
catalyst. The catalyst can be cut with a hacksaw into the desired shape.
I have heard there are state or federal laws prohibiting the sale of used catalysts. The probable reason for this is because
they don't want people using a possibly defective catalyst on their car. I've gotten a couple of them from the local junkyard
though without any questions asked.
Cobalt oxide can be purchased from ceramic suppliers. I have seen a patent for the farm manufacture of nitrogen fertilizer
which used a cobalt oxide catalyst for the oxidation of ammonia. Supposedly it worked better at low pressure than a platinum/
rhodium.
Ctrl_C June 20th, 2002, 05:56 PM

Just a question: why is it illegal to buy/sell used cats in the US?
SATANIC June 20th, 2002, 10:54 PM

i dunno about the US, but here in aus, you can get your car taken off the road / fines for not having one. it's all about
reducing greenhouse gasses etc, and the cat plays a vital part in that.
a friend took it out, (part of others mods to the car) and got fined, then had to have it replaced. it was under the engine, tho
in the exhaust line / system, not in the actual muffler.
megalomania June 22nd, 2002, 02:57 AM

Since they are quite expensive, some unscrupulous mechanic types try to pawn them off as new parts. You have to have one
there, but nobody really cares if it works (except the government). They are one of those things that if they dont work, who
would really know?
The catalytic converter has undergone some design changes in the past decade or so. Newer cars have it right after the
exhaust manifold, and some have another right before the muffler. Older cars have it before the muffler. Those are easier to
service because it just connects to the piping. Sounds like a mechanics con to me, but I guess the ones in the engine
compartment are more efficient, even if they do cost more and require more effort (aka $) to get at.
If I had my way I would remove mine completely. They sap some horsepower by restricting exhaust airflow. You can buy high
flow catalytic converters (cat backs) to give more horsepower, and when combined with high flow manifolds and exhaust pipe,
can really add some power. Of course if you want a non street legal car, you can use a manifold and no cat converter at all. If
I ever buy a high flow manifold, I may just do that because there are no exhaust testing requirements where I live. Of course
this is a post best kept on the Ford racing bulletin boards Yes, shopping for a new car has led me down gearhead alley, and
now I dream up ways to mod my car along with making chemicals.
PYRO500 June 22nd, 2002, 05:12 AM

Ah, the old remove the cat converter trick, most of the cars in our school parking lot have this done to them,(then again
there's only 40 something cars max) the students in the welding class make "Test pipes" (among other illegal things)
(straight open pipes that replace the cat converter) and they go race their cars on the dirt roads behind their trailers (fucking
rednecks) now I can understand why you would want this on either a newer car or a high performance car but all the cars
around here are stupid rusted out trucks. I believe there is a heavy fine for tampering with your emission control system. What
I have seen most often with people removing their converters is that they forget or ignore their oxygen sensors. in all fuel
injected cars the oxygen sensor plays a crutial part in maintaing a perfect air to fuel mix without it your car slowly adjusts till it
runs like shit or not at all then I think you have to manually reset the mix or install the sensor and wait for it to adjust.
NoltaiR June 22nd, 2002, 10:46 PM

A spiral tube would be most efficient (as NBK stated in a previous post) in working with the cooling process. However NBK
pictures that the U tube--as I call it--or the spiral tube as suggested would be sitting in a beaker of water I believe. I should
think that a way to have running water would be more favorable. Or if you were insistent on having standing water in a beaker
then possible an addition of NH4NO3 prills would easily keep the temperature down--such as used in instant cold packs.
P.S. In review of Mega's first post in this thread I would like to say the last pic draws the most attention.. and this may come
to my mind so quickly because I am a clothing salesman. Anyways I would like to say that you may be starting a new fasion
trend with the lab coat and shorts combo.. I'm diggin it! :D
nbk2000 June 23rd, 2002, 09:47 AM

"...a couple of U bends on the ends of your reactor. These are immersed in water, with a constant flow of cold water being
supplied by a hose. The overflow goes to the drain."
Read my posts more carefully in the future before commenting on them.
Thank you.
10fingers June 23rd, 2002, 11:41 AM

Another problem I ran into when trying to do this is that if theres any unreacted ammonia going into the water with the nitric
acid all you're going to be doing is making ammonium nitrate. Some way has to be devised to remove this unreacted
ammonia.
I think rikkitikkitavi mentioned this on a similar thread and it's the only simple way I can think of also. It would be to run your
NO into a container of water, before it has reacted with any more oxygen to become NO2. The water would absorb the
ammonia, I think the NO should pass through unchanged. This would also cool it down so that it can be led into a reaction
chamber with more oxygen to change into NO2. This reaction is slow and is better at around 20*C. Then lead the NO2 into
water again where it will combine with the water to become HNO3.
Does this sound workable?
megalomania June 23rd, 2002, 11:52 PM

If you do get unreacted ammonia, you would have to adjust the ammonia flow to decrease it a little until you don't get any.
One you have tinkered with the system enough that should no longer be a concern. If you let ammonia go through, you will
just be wasting it when it could be acid. It is better to eliminate this problem than to compensate for it.
I have a few ideas as to how to produce the nitric acid after NO2 formation. I will most likely set up a series of glass bottles
where the NO produced in the reaction can itself be reacted. The first water container would be the only one to absorb the
ammonia, if there is any. Only two thirds of all the NO2 gas actually becomes nitric acid, the other third becomes NO, which
passes over into the next bottle becoming NO2 along the way. Two thirds of that becomes acid, and so on and so on until you
have very little left. During the course of the reaction the first bottle will absorb less and less NO2 as it gets saturated. These
bottles will also get hot, leading to even less absorption. One would have to monitor these bottles to swap them out when they
hit maximum capacity. If you let the system run too long, you would end up having NO2 gas spew out.
Industrially they use a tall absorption tower. A continual stream of water if sprayed into the top while the gas is forced up from
the bottom. The NO rises and reacts along the way slowly diminishing to zero. The downside of this is they only get 60-70%
acid. I dont think such a system would be useful to me.
I have some trouble getting water where I need it without making a huge mess or redesigning my lab space. Anybody can
move a garden hose to cool the pipes, then what? I have no place to easily get rid of the water. Even so, it is the best way. I
have used water filled containers as coolers before, and in my experience they get real hot real quick. I cant make enough
ice, so cold water is far superior. Besides the static systems require lots of attention I dont want to give.
Again, I get ahead of myself. I am still concerned with optimizing NO production for now. I will tackle the other problems as I
come to them. In my next experiments I am going to try using pure ammonia.

It's fucking anoying, I had written a long good reply I hit the add reply button and then, :mad: , internet colapses.
Anyway, what I wrote was that if you have a grden hose that enters an eclosed container around the place that needs cooling
at the bottom and then exits at the top you get an effective cooling. The hos exiting could easily be lead into a sink or out the
garden. If you are ready to put some money on a pump you could just use a large drum or something to contain the water
and then since the cooling container is eclosed you can turn the pump on max and then get some very good cooling. This
setup could allso be set up in series. Look at the pic and you'll see what I mean.
<a href="http://w1.478.telia.com/~u47804009/E&W/pump.JPG" target="_blank">http://w1.478.telia.com/~u47804009/E&W/

pump.JPG</a>
I'm not shure this it what you ment though.

I think a sealed container might do the trick. I have large plastic jug for pure water. Even a plastic milk jug could do. Just seal
some nozzles on it and let the water flow.

This thread has rekindled my interest in working on my contraption again but I've been pretty busy lately. I will get to it again
eventually.
Agricultural suppliers sell bags of ammonium sulphate and calcium hydroxide for less than $10.00 per 50 lb. bag. This is what
I will probably use to make my ammonia.
As for the unreacted ammonia, I was under the impression that the catalyst was less than 100% efficient and that
consequently you would always have some ammonia exiting from the catalyst chamber. If it were possible to adjust the
mixture so that this did not occur, of course this would be the ideal.
I found a good way to monitor the temperature at the catalyst. I use a thermocouple from a gas appliance. You connect a
voltmeter to it and you have a crude pyrometer. Of course it needs to be calibrated to the desired temperature. Silver melts at
slightly over 900*C so you can place your thermocouple in some molten silver and note the voltage at which it solidifies.
cutefix June 25th, 2002, 03:47 AM

Qoute:
"Mega, I know this is NOT a complete recipe for the catalyst, but it may give you some ideas."
I have some patent refferences about this ammonia conversion to nitrogen oxides;and indeed there are other economically
practical about using cobalt type catalyst;
See this out also..for more details of making related catalysts.
Patent(US)# 3850851
#3767772
#3850851
#1918957
Mr Cool June 25th, 2002, 04:31 PM

10fingers: Al melts at 660*C, this could be another point to help with calibration. It'd be a lot easier than melting Ag, and not
everyone has easy access to Ag.
Personally I believe we will always have lots of nitrates, or if not then it'll be a long time before we lose access to them, so
HNO3 can be made from these, either with H2SO4 or by thermal decomposition:
e.g. Ca(NO3)2 --> CaO + 2 NO2 + 1/2 O2
then H2O + 2 NO2 + 1/2 O2 --> 2 HNO3
It'd certainly be a lot easier to use this method, though perhaps not quite as interesting!

ca(NO3)2 starts to decompose at 500 C, and at those temperatures NO2 immediately decomposes into NO+O2 , however they
recombine at lower temperatures of course.
But it has to be taken in account for if used in production of HNO3, fortunately the reaction time between NO and O2 is
probably very short in the comparativly high concentrations present after the decomposition chamber.
/rickard

I was not aware that calcium nitrate could be decomposed by heat to give off it's NO2. All you would have to do then is pump it
into some water and you would have your nitric acid. Has anyone here ever tried it?
I think part of the allure of the catalytic method is that you could make nitric from just ammonia, air and water. Plus it's an
interesting experiment and would be quite an accomplishment to achieve.
And then if you're really a glutton for punishment you could make your own ammonia via the Haber process with just nitrogen
and hydrogen. You could make all the nitric you could want from just air and water.
And then your could make your own methanol through the destructive distillation of wood.
And then the methanol could be catalytically oxidized to formaldehyde.
And then with formaldehyde and ammonia you could make hexamine.
And then.........
But by this time your backyard would look like an oil refinery.

Actually I have thought about other systems to get RDX starting from the saw dust --> methyl alcohol --> formaldehyde -
-> methanamine route. As it turns out, the same setup I have for making nitric acid can also be used to make
formaldehyde. By swapping out the catalyst pipe with some rusty steel wool I could also make sulfuric acid.
I recently read a proposal when researching microreactors about using the reactors as an onsite source of chemical for
farming. They calculated that 1000 of their reactors could make a few liters of nitric acid a day. Expanding on this, idea they
proposed a means of simulating the entire industrial route from the Haber process and the Ostwald process combined could
make ammonium nitrate for fertilizer in one package.
Natural gas is burned with steam to make CO and some H, air is added to complete the combustion giving only CO2 + H2 +
N2. The CO2 is removed by an amine scrubber (industrially), but they proposed some kind of membrane filter could do it on a
small scale. These gasses would be made into ammonia, the ammonia would be made into nitric acid, and the two would be
mixed to make ammonium nitrate.
This kind of thing gets me thinking. With a bit of money to invest this could be a workable setup. It would be marketable to
farmers just like they said. I am sure it would be a piece of regulated farm equipment to keep it out of the hands of all those
evil terrorists.

There are a lot of things you can do with a catalytic reactor once you get it working. I've also used mine for making
formaldehyde and acetaldehyde. I changed the catalyst to copper sponge. The formaldehyde I seemed to be getting quite a
bit but it used a lot of methanol and it was easier to just buy paraformaldehyde. I think the acetaldehyde was working a little
but it is so volatile and the temperature of the reactor so high that you really need a good cooling system to capture it.
frostfire June 27th, 2002, 06:13 PM

Mega, may I know an estimate cost of your distillation setup?, there's one in the dept lab and I'd like to compare the price
I get my equipment from so many different sources, and I rarely keep track of how much the stuff costs (impulse buys). In
short, I have no idea.
nbk2000 September 19th, 2002, 03:15 PM

I was at Wally-Mart yesterday buying a propane lantern because the power often goes out here for days because of the
weather.
Anyways, while looking through the Coleman shit, I saw a catalytic heater. After opening up the box and reading the papers
inside, I found out that it uses a platinum/pallidium catalyst in a ceramic matting to catalytically burn the propane into
harmless carbon dioxide, all while giving off tremendous amounts of heat.
So, what came to mind? Using the catalytic matting to "burn" ammonia and oxygen into nitric oxides.
Something to look into. The heaters are cheap too. Only about $20. :)
McGuyver September 19th, 2002, 09:58 PM

I've seen these replacement mantle things at wally world. They look like little nets shaped like a bag.
Pyro500, what are you talking about when you say that, when people mess with their converters they forget to adjust their
oxygen sensers? What does the c. converter have to do with the intake? I don't get it.
PYRO500 September 19th, 2002, 10:26 PM

Usually the catylitic converter has an oxygen sensor on the input side. Some people that put test pipes in tend to forget that
fuel injected cars need an oxygen refrence from a sensor and their test pipes don't have a sensor hole sometimes and they
forget to install the sensor in there.
Jhonbus September 19th, 2002, 10:44 PM

Gas-powered soldering irons like my cooly-named "Flame Master" also use a platinum catalyst in their tips. I don't know how
much catalyst you get compared to this lantern, and the tips probably cost somewhere around $5 each. But they are already
built into a stainless steel manifold which could be of use in this application.
vir sapit qui pauca loquitur September 20th, 2002, 11:39 AM

Now, please correct me if i'm sadly misguided, but if i were to set up a pair of chambers (one half the volume of the other)
and i was to pressurise the smaller chamber with nitrogen (at about 2000psi) and the larger with oxygen, (same pressure,
creating the 2:1 ratio of O2 to N2 ) and i was to open valves from both chambers in to ANOTHER chamber (there-by mixing the
gases). would it then be possible to pass a spark across the third chamber for a (long) while would i have NO2 ? (it would be at
about 1500/1000 psi range in this chamber while i let it cook,
my next idea woult be to have a pressure regulator allowing the chamber aptmosphere to leak out into a large volume of
distilled water, thereby creating nitric acid ???
please correct me if i need higher pressures or this is impossible

we were only taught the MOST basic ideas about the production of nitric acid (due to the liberal government restricting what can
be taught)
if this is possible (i need mega or nbk to say that it makes sense)

then i'll start the construction and post pics,
to my knowledge the factors favour it, the products have a lower volume (favoured by equalibrium reactions) and i can heat/
cool the reaction vessel by a considerable degree to increase the yield (by finding compromise temperature), and i can have
multiple spark units installed. i have read other posts on the subject of spark generation of NO2 but i wanted to know if there
was any particular tricks that i could do to increase the rate of reaction (aka kinetic collision formation versus thermal
decomposition of NO20
(p.s.) the max pressure that i can generate is about 2000 psi in the mixing chamber (but i prefer 1000 as it is easier to
obtain)
rikkitikkitavi September 20th, 2002, 02:00 PM

if I understand it correctly you want to prodcue NO2 by heating
N2+O2 under high pressure.
First reaction is
N2+ O2 => 2 NO (high temperature)
NO formed easily decomposes back into N2 and O2. All comercial systems using electrical arcs for heating makes sure that the
reaction very quicklu passes the heating zone to maximize yeild.
Second
2NO + O2 = 2NO2 is strongly shifted to NO and O2 at high temperatures.
And if you heat the gases in a pressure vessel , be adviced that a vessel withstanding this pressure loses much of its strength
at elevated temperatures, even as low as a few hundred C.
/rickard
vir sapit qui pauca loquitur September 20th, 2002, 02:34 PM

1. the number of moles of gasses is reduced (2NO + O2 = 2NO2 ) this goes from 3 moles (2 NO plus 1 O2) into 2 moles
(2NO2) this means that it is more likely (in an equalibrium reaction which i cant remember that if this is, i think so) and i said
that i CAN increase the temp, this would increase the forward reaction (formation of NO2) but also increase the back-reaction
(formation of NO) the ideal temperature takes these rates into account, as with a low temp, the formation of NO is low, but the
formation of NO2 is also low, due to chemical kinetics at that temperature (and the activation energy of the breaking of the
bonds being too high for much formation)
and i do know about charles's law (PV=NRT if i'm correct)

but you see i dont intend to heat up the reaction vessel much, i only intend to let it go on by its own accord and later on in the
day i release the gases into water and hey-presto i have a solution of HNO3
... IF this idea is valid (i do understand the limitations of it, as it is a process usually used on the INDUSTRIAL scale)
i have all the parts ready, so i'm just waiting for the A-OK from mr wizard or NBK as to the possibility of
1. explosion (low i believe but i'm not going to ignore advise from people such as the mods)
2. economy of production (if im going to get a tiny yeild unless i'm recycling the gases many times)
if both are to my liking then i'll proceed
p.s. is my sig too big :( [No, the limit is 3 lines]
EDIT [Moderator: Machiavelli ]
thanks Machiavelli, i was worried after seeing some sig's getting you mods a bit on the angry side, better safe then sorry :D
[ September 20, 2002, 06:04 PM: Message edited by: vir sapit qui pauca loquitur ]
megalomania September 21st, 2002, 03:18 AM

I am not so sure that the usual factors of chemical equilbrium affect the electrochemical reaction you have described. The
reaction is largely dependant on electricity, and if I recall correctly, does not favor the formation of NO. With that said I would
expect more NO to be formed by higher pressure since more molecules of N2 and O2 will be within the spark field. More
sparks will mean more products as well. The temperature should not be a factor. All necessary heat will be provided within the
spark only, external heat may only serve to break down your product.
What I see is a vast amount of oxygen being sparked. That sounds inheriently dangerous to me if there is anything besides
O2 around. I hope any such container is leak proof to avoid any accident. You will most likely get a large amount of ozone
from this reaction as well. Ultimately experimentation will be needed to calculate your yield based on low pressure vs. high
pressure, and the economics of electricity consumed. These methods were abandoned by the ancients about 100 years ago
because of the more economical Ostwald process, but that dosn't mean it won't work. As I must constantly remind myself,
industry is concerned with the bottom line, improvised is concerned with getting A product period.
I do believe there is already a thread that discusses a similar avenue of preperation.

How thick is the catalyst you are using?
Ostwald's platinum plug was only 2cm thick. You can calculate residence time if you know the surface area of the catalyst, you
assume all of the gas contacts it, which if you get neer complete oxidation to NO, it must be. You estimate the area required
for a single NH3 molecule, and the residence time falls out of the math. Estimating the surface area of the catalyst might be
fun. I cant think of a good way offhand.
Ostwald didnt invent the process btw, he was just the first to do a detailed study of the conditions needed to optimise it. Ferric
oxide is supposed to work as well as platinum with an 80-90% conversion to NO possible at about 700C.
I would suggest you get an ammonia cylinder, you need to test each part of this process seperately before stringing it
together. Accuratly, reliably and repeatably altering ammonia flow rate is essential for getting this to work, you cant do that
with an ammonia generator. If you can find optimal conditions for the catalyst, you can describe it exactly, and so people
copying your experiment wont have to test each part seperatly. Optimise in bits using the proper article, then reduce the
apparatus to easily available parts.
I would be surprised if there were places ammonia fertiliser was available but not nitrates. I wont be trying this, I value my
health too much.
simply RED October 18th, 2002, 03:54 AM

Very good!
but TOO complicated!!!,
Mega, you remeber the idoine sublimation and purification from the uni?
You remeber the aparatus with the cooling test tube in its center...
Got it?
:) :) :)
megalomania July 4th, 2003, 07:49 PM

I have completed another round of catalytic nitric acid experiments with rather disappointing results. In several attempts with
different setups I was unable to produce any nitric acid using a copper catalyst. There are any of a number of things that could
have gone wrong, but I ultimately feel that copper is a bad choice for this kind of work.
My experiments thus far are still relying on the ordinary household ammonia as purchased from the store. I feel this dilute
ammonia is more than sufficient to run the reaction even though it presents some moisture problems, as I will explain later.
I did some experiments to determine whether or not flame heat is sufficiently hot enough to sustain the reaction. The original
patent literature by Ostwald suggests a minimum temperature of 300 degrees C with a preferable temperature range of 400-
500 degrees C. My tests used a Tirill burner at a fairly modest heat could achieve temperatures ranging from 410-450 within
5-10 minutes inside the catalyst chamber as measured on a digital thermometer. I achieved a fluctuating temperature of 430-
450 that lowered to 410-430 when the air flow was applied as it would be in my later experiments. A minor increase of the
flame size resulted in a temperature increase of 10-15 degrees. I will have to conduct further tests at higher temperatures,
but I believe this range is quite adequate for the reaction. It is certainly hot enough to initiate the reaction.
My use of brass connecters and a copper cooling coil at the exit of the reaction tube proved to be a bad choice when using
moist ammonia vapors. Ammonia forms hexaaqua copper complexes with copper that also resulted in the formation of copper
hydroxide. At one point I obtained a considerable amount of a white precipitate that I hoped was ammonium nitrate. In
furnace tests this precipitate should have completely decomposed leaving no residue, whereas copper hydroxide would have
converted to copper oxide, a black precipitate. A black precipitate is what I obtained.
I added a lime filled drying flask in later tests that reduced the amount of moisture considerably. Earlier tests without the
drying flask left me with several mL of a dark blue copper compound dripping from my joints. Only a few drops of the copper
compound formed after nearly 1.5 hours using the drying flask.
In all tests unreacted ammonia was detected in the collection flask, but not enough to account for what was lost from the
original ammonia. Surmising that any nitric acid formed would have been converted to ammonium nitrate I boiled down the
water of the collection flask. I obtained no solid compound indicating the presence of ammonium nitrate.
Inspection of the copper catalyst after the reactions had subsided show extreme degradation of the material. The moist
ammonia as well as air oxidation really takes a toll on the metal. While the oxidized copper should still act catalytically, it is
even worse at it than copper itself. The reaction of copper with ammonia absolutely destroys the copper.
My conclusion is that copper is a less than effective catalyst under these conditions. This conclusion would seem supported by
the available literature. Copper is a poor catalyst to begin with, it is too reactive, and has a short life span during the reaction.
<a href="http://www.roguesci.org/images/NA-June-03_01.jpg">My experimental design</a>

<a href="http://www.roguesci.org/images/NA-June-03_02.jpg">A close-up of the ammonia boiler</a>
<a href="http://www.roguesci.org/images/NA-June-03_03.jpg">A close-up of the catalyst chamber</a>
<a href="http://www.roguesci.org/images/NA-June-03_04.jpg">A close up of the cooling coil</a>
<a href="http://www.roguesci.org/images/NA-June-03_05.jpg">A close up of the collecting flask</a>
<a href="http://www.roguesci.org/images/NA-June-03_06.jpg">The setup with the drying flask</a>
<a href="http://www.roguesci.org/images/NA-June-03_07.jpg">Copper hydroxide precipitate</a>
<a href="http://www.roguesci.org/images/NA-June-03_08.jpg">Before and after catalyst example</a>
blindreeper July 4th, 2003, 09:19 PM

Very nice pictures there mega. I think what your saying is that the copper doesn't work as a catalyst no? Well why not try
10fingers idea (sorry if it was some one else) well not really his idea but he did it and extract the pallium/platinum catalyst
with aqua reigia. Or maybe just using the cat converter straight. Then of course that isn't exactly OTC. Meh I'm tired
knowledgehungry July 5th, 2003, 12:28 PM

Maybe you should try a platinum catalyst, platinum is OTC just not cheaply(jewelry). If the platinum catalyst works than you
could look for a cheaper catalyst. but it would seem that you would want to make the setup works in the first place.
kingspaz July 7th, 2003, 01:08 PM

if you need platinum go to the scrap yard and rip a few catalytic converters from some old cars. they should already have a
decent surface area.
megalomania May 24th, 2004, 07:42 AM

Yesterday I tried the experiment again, but this time I used a platinum catalyst. I crushed up a portion of a used catalytic
converter and added it to my tube with copper sponge plugs at either end to hold it in.
I am happy to say I got absolutely n othing That is p rogres s, believe it or not, becau se the re was no trace o f ammonia
whatsoever in the collection flask this time. I at least know there is a reaction because all of my ammonia is decomposing. I
did add a rather large amount of catalyst, but I figured most of it is so choked with carbon that extra is needed.
I will be trying the experiment again today with a fresh batch of ammonia and fresh lime in my drying flask. I shall remove
half of the catalyst as well.
I have also prepared a catalyst tube of manganese dioxide. I dusted cotton balls with MnO2 and stuffed them in the tube. I
then heated the tube with an air flow to burn off the cotton. After 10 minutes or so no more smoke came out. The next day
when I examined it there was considerable ash falling out. I hope it does not settle and make a gap that the ammonia can
pass through unreacted. Perhaps dusting moist (so the MnO2 cakes) iron wool would have been a better choice.
10fingers August 30th, 2004, 10:36 PM

When I tried this experiment I learned one thing, it's not that easy. I also used household ammonia and heated it. With a
platinum catalyst I definitely did get some NO2, there was quite a bit of reddish brown fumes coming out of the reactor.
However it would come and go and was difficult to sustain. Also it seems to take a whole lot of NO2 to make any nitric acid.
After awhile it quit working and I was not able to get it going again. Perhaps the catalyst was contaminated with something.
I agree with Marvin, the amounts of air and ammonia need to be closely controlled, also the pressure and speed of the gases
through the reactor.
If I tried it again I would use a more concentrated source of ammonia and I would use adjustable pressure regulators for both
the air and ammonia. It's pretty easy to concentrate household ammonia, but it gets expensive. One could buy a tank of the
stuff but anhydrous ammonia is also used to make meth and I don't think I would want to have a bottle of it around. Another
way I might try is to mix ammonium nitrate and calcium hydroxide. I can get both of these from the agricultural supply for
around $6.00 per 50 lbs. You could put this in a pressure cooker with a regulator and pipe it into the reaction chamber.
I found a patent at the USPTO that explains in detail how to make nitric acid for agricultural uses. It's kind of a do it yourself
for farmers that want to make their own fertilizer. The process used a cobalt oxide catalyst. I have found cobalt oxide at a
ceramic supply co. It's used to color glazes. It's rather expensive though, $27.00 for 1/2 lb. but it's a lot cheaper than
platinum.
The other thing is that once the mixture is right all you need to get the reaction going is a spark plug. You just fire it and the
air/ammonia starts to burn and once the catalyst gets hot, you don't need to supply any more heat.
megalomania September 1st, 2004, 02:41 PM

Oh good, this thread is on top, s aved me from having to look for it
I will shortly be obtaining some additional equipment necessary to more thoroughly test this experiment. I will be getting a
cheap almost new catalytic converter to supply the necessary catalyst. I still think there is nothing better out there than this, it
has the best catalyst and is already shaped perfectly for a catalytic reaction. A single cat will probably last a lifetime.
I will also probably be getting a decent second hand mass flow meter. With these I am slightly out of my league because
these are professional instruments. Omega sells dozens of models of varying configurations, so I have no idea which one is
best suited to my nee ds. I don t even know if a mass flow meter is the right wa y to go, but it happens to b e all I ca n get
cheap. These things go for $500-$800 depending on the model when bought new.
From what I can gather a mass flow meter measures the quantity of a gas passing through it based on a calibrated standard
at STP and nitrogen gas. I will be using it to measure the flow of ammonia, but there are published conversion factors to get
an accura te result. I don t really ca re about the amount of g as, just the velocity o f gas over th e catalyst surface. All things
remaining equal an increase in the mass flow should equal an increase in gas velocity over the catalyst. Really a simple
rotometer gas flow measuring device might do the trick, but I can get the computer controlled digital meter for the same price.
The problem I have in picking a mass flow meter is knowing which maximum flow rate to get. These things are measured in
standard feet per minute, or standard liters per minute. They also come in standard cubic centimeters per minute, and in
inches. The one meter I saw has a max of 1 L per minute. That hardly seems sufficient to me. The one I am considering
now goes u p to 50 L per minute. That should be more than enough, but I don t kno w how th at is graduated. I guess I won t
know what I need until after I buy it, use it, and find out it is no good.
On the ammonia front I am going to try to use a real anhydrous ammonia tank if I can get one. This is another thing the
druggies screwed up for the rest of us. I am not sure ammonia is illegal per se, but sellers may be wary of anyone not a
licensed refrigeration expert. Failing this I will just make my own from fertilizer and store it in a pressure tank.
I still have to build my temperature controller and improvised electric furnace. I was also thinking about testing a small copper
wire system using an arc welder as a heating source. I would hook the wire up to the electrodes and just blast it with a high
current power source to see if the wire will heat up. Once the copper is at red heat the reaction should be self sustaining.
I found this company today while searching for ammonia suppliers: http://www.brainerdchemical.com/frameset_nitr.htm They
sell nitric acid. If you click the "view our nitric acid products link" you will see they are selling 55 gallons of technical grade nitric
for $131.32 + a $500 drum deposit. I think you get the deposit back. That is damn cheap, especially considering all their
other prices. I wonder if that is a typo, it is probably supposed to be $1310.20.
zerok September 2nd, 2004, 06:42 AM

Have you thoughed of using a pitot-static tube?
http://www.du.edu/~jcalvert/tech/fluids/fan.htm
What it basicly does is measure 2 different pressures. With those pressures you can calculate the speed of the airflow.
What you need is some sort of setup described on the webpage. A hole in the wall of the tube where you want to measure the
speed connected to a U tube field with a fluid. a small tube with an open end in the middle of the tube connected to the other
side of the U tube. The difference in fluid height in the U tube will be the pressure difference which can be calculated to speed.
I hope this is a usefull first post :)
10fingers September 2nd, 2004, 01:40 PM

That's a very low price for nitric acid! I have never found anything that low. I wonder if it's correct?
Using a new catalytic converter would probably help. The ones you get out of the junkyard may be contaminated or have all
the platinum burnt out of them.
The catalyst I used was was the ceramic honeycomb type. It's very easy to cut with a hacksaw. I just cut out a circular piece to
fit into the piece of stainless steel pipe I was using for the reactor.
I think buying anhydrous ammonia these days is definitely going to raise eyebrows with all the meth making going on.
Probably the main drawback I can see to the process is can you make or obtain ammonia at a cost that makes it worthwhile. It
may be more trouble to get the ammonia than it would be to make nitric with H2SO4 and a nitrate or buy it.
But I think it's an interesting project and I often go to great lengths and expense just to see if something can be done. It's
not a matter of it's practical or not. It's a challenge.
megalomania September 2nd, 2004, 09:58 PM

I would think compared with nitrate/sulfuric the cost of ammonia would be about the same, or less. It is more work getting the
ammonia of course.
kurtz July 25th, 2005, 03:18 PM

I was looking in Ind. Eng. Chem. at a picric acid article yesterday, and noticed that the next article (http://rapidshare.de/files/
3346985/iec_16_74_1924.pdf.html) was an interesting and detailed one, testing a variety of inexpensive, mostly Co3O4
catalysts on a small scale. In one example, 22 L/min air/NH3 and 14 g. 97% Co3O4/3% Bi2O3 catalyst @ 710-730C was
calculated to yield 8.36 g. HNO3/minute, with >94% conversion of the NH3. The author mentions a patent that he was granted
for one of the many catalysts that he tested and its use, US1399807 (http://v3.espacenet.com/origdoc?
DB=EPODOC&IDX=US1399807&F=0&QPN=US1399807).
kurtz July 25th, 2005, 03:18 PM

I was looking in Ind. Eng. Chem. at a picric acid article yesterday, and noticed that the next article (http://rapidshare.de/files/
3346985/iec_16_74_1924.pdf.html) was an interesting and detailed one, testing a variety of inexpensive, mostly Co3O4
catalysts on a small scale. In one example, 22 L/min air/NH3 and 14 g. 97% Co3O4/3% Bi2O3 catalyst @ 710-730C was
calculated to yield 8.36 g. HNO3/minute, with >94% conversion of the NH3. The author mentions a patent that he was granted
for one of the many catalysts that he tested and its use, US1399807 (http://v3.espacenet.com/origdoc?
DB=EPODOC&IDX=US1399807&F=0&QPN=US1399807).
meselfs July 26th, 2005, 12:26 AM
Whoa! But 700 C might be a bit too much for us. Can some sort of coil acheive and maintian that temperature without making
the outlets turn hot and smelly?
meselfs July 26th, 2005, 12:26 AM

Whoa! But 700 C might be a bit too much for us. Can some sort of coil acheive and maintian that temperature without making
the outlets turn hot and smelly?
megalomania July 26th, 2005, 11:41 AM

There are several very good articles in Ind. Eng. Chem. all of which I happen to have... History, I am afraid, has shown again
and again the platinum is by far the single best catalyst to use. Of course it is quite encouraging to know that there are many
different alternatives that rank "nearly as good" as platinum.
I have used manganese dioxide and copper sponge with little success. Now I have a platinum catalyst. Start with the best then
figure out the rest I say. It is the experimantal setup in this articles drawing that is most encouraging.

There are several very good articles in Ind. Eng. Chem. all of which I happen to have... History, I am afraid, has shown again
and again the platinum is by far the single best catalyst to use. Of course it is quite encouraging to know that there are many
different alternatives that rank "nearly as good" as platinum.
I have used manganese dioxide and copper sponge with little success. Now I have a platinum catalyst. Start with the best then
figure out the rest I say. It is the experimantal setup in this articles drawing that is most encouraging.
Alexires June 7th, 2006, 12:25 PM

Hey mega, what is the chances of getting the images put back into this thread? I'd like to see your set up.
Sorry to be a pain.
tmp June 9th, 2006, 08:58 PM

Mega, I wish you the best of luck in making nitric this way. It seems that
someday we'll all have to produce our own chemicals. I already produce my
own metal powders, chlorates, and perchlorates. It proves how fucking
useless the laws really are. I've made white fuming nitric via the vacuum
distillation of nitrate/sulphuric acid. Your method intrigues me. Any photos
of your setup would be greatly appreciated when you have time. Thanks in
advance !
inventorgp June 26th, 2006, 10:35 AM

Has anyone thought of using a high voltage transformer?
Get two electrodes encase them in a glass chamber, turn
the power on and let it arc.
Air -> NO2.

2N + 4O -plus HV-> 2NO2.
Please correct me if I am wrong,
although I think this is correct
Then bubble it in to water.
An easy to get transformer is a MOT -

Microwave Oven Transformer
I have about a million of these, space consuming and heavy:p
An apparatus could be set up; air compressor - arc chamber - water
c.Tech June 26th, 2006, 11:17 PM

Has anyone thought of using a high voltage transformer?
Get two electrodes encase them in a glass chamber, turn
the power on and let it arc.
I think youre in luck.
http://www.roguesci.org/theforum/special-project-1-nitric-acid/1919-hno3-air-using-electric-arc.html
http://www.roguesci.org/theforum/special-project-1-nitric-acid/4181-nitric-acid-air-water.html
The link "http://species8472.dyndns.org/no2/no2.html" contains detailed non-kewl information.
He also makes sulfuric acid using catalyst and does various other interesting experiments.
inventorgp June 27th, 2006, 09:49 AM

c.Tech kewls don't know how to do anything.
And are you suggesting I am one, I Think not
Yes It is a quick description.
If you are not implying this then I apologise:D
I don't have enough funds to do such experiments or

as much knowledge to produce a fully capable apparatus.:(
I consider the term "kewl" to be an insult, kewl as in lacking brains.
c.Tech July 1st, 2006, 01:34 PM

I was nt calling you a k ewl, sorry it was set o ut that way :o , I said "no n-kewl" be ca use th ere is a lot of shit floating a round on
the n et and I was trying to emphasiz e that it was good ex periment, which still doesn t make much sense of why I put it in,
even to me :confused:.
It was quite irrelevant, I didn t really think before I wrote it.
fractional distiller September 3rd, 2006, 12:17 AM

I am very new to synthesizing explosives and especially to synthesizing acids to be used in explosives. I have been
researching and saving money for some time now so I can buy myself a fractional distillation setup. My question to all of you
more experienced and knowledgeable individuals is if I buy my glassware set from
http://www.unitedglasstech.com/distillingKIT8.htm
along with this vacuum from united nuclear
http://www.unitednuclear.com/vacpump.htm
would it be the type of vacuum I need? I am also concerned that the fumes from the distillation of sulfuric acid will destroy the
vacuum and then the vacuum distillation of sulfuric acid and potassium nitrate to produce my fuming white nitric acid will
corrode the pump although it claims to have oil that is supposed trap these impurities and corrosive gasses. Do you think that
these two pieces will be the set up I will need?
Any and all help would be greatly appreciated.
megalomania September 8th, 2006, 09:21 PM

On first glance that is a decent kit. However, a few seconds later I realized this is not appropriate for you at all. First and
foremost the flasks are FLAT BOTTOMED. You do not want to use flat bottomed flasks in a vacuum operation because they are
not designed for low pressure work. Only ROUND BOTTOMED flasks are vacuum safe. Unless a flask is specially reinforced, like
a heavy walled Erlenmeyer, you need a round bottom for vacuum work.
Second, those two flasks are quite large at 1000 mL and 2000 mL. I am not saying it is bad to have a flask that large, but
you need to factor in what kinds of reactions you are doing. I have rarely needed to use anything beyond a 500 mL flask, and
I try to confine most of my experimentation to 25 mL and smaller. Microscale is the wave of the future. Of course, if you are
planning on manufacturing something in larger batches, like acid, large is good. I think the only manufacturing some of the
typical customers would have in mind is of the recreational pharmaceutical variety.
Also, keep in mind how you will heat such a large flask. Heating mantles abound for smaller sized flasks, but bigger sized
ones cost big bucks. You may have to use an oil bath, sand bath, or build you own steam jacket. If inorganics are your bag,
then there is nothing wrong with using the ol Bunsen burner.
A Vigreux column is nice, but personally I prefer a glass bead filled Liebig. I can swap out the glass for copper sponge,
ceramic, plastic, etc., depending on what I wish to distill. It lets me keep my options open. I think a glass bead filled column
offers more theoretical plates than a similar sized Vigreax, depending on the size of the beads. That Vigreax column should
be just fine for acids though.
Personally, I prefer to shop at a company called Chemglass Scientific Apparatus at chemglass.com. They have a large
selection of standard taper glassware. Get their free catalog. I find their prices to be very reasonable as far as standard taper
glassware goes.
The vacuum pump at UN is a very decent price, assuming the quality of the pump is up to par. A good pump can run you well
over $400, but there are cheap models. The manufacturer and model number of that pump is not specified, which I consider
to be a bad sign. As vacuum pumps are reckoned, some would not consider 40 microns to be high vacuum. Something
seems fishy to me. They do not specify the horsepower of the pump, nor do they mention the CFM pumping capacity. CFM is
cubic feet per minute, a rating of how fast the pump will remove a certain volume of gas.
To protect your pump from acid gasses I suggest you install a trap on the line capable of adsorbing acid fumes. I am not sure
of the exact setup, but google is your friend there.
wymanthescienceman November 8th, 2006, 11:15 PM

Hi all! I've been looking into distilling nitric and have a few questions and I couldn't find them by searching the forums, the
search engine sucks balls. But here they are:
When distilling HNO3 by mixing a nitrate with H2SO4, will the HNO3 be only as pure as the H2SO4 used? I was planning on
using a cheaper alternative to my 98% H2SO4 by using a drain opener which is roughly ~90% H2SO4, the rest being water and
some kind of inhibitor dyed brown. So being 90% will my HNO3 be AT BEST 90% pure? Also will the inhibitor have any effect on
the outcome of the HNO3? I can't distill under vacuum yet but I was thinking of doing it the way seen on the "Nitric Acid the
Easy Way" thread by using a vessel inside a vessel and catching the HNO3 by condensing it on a glass or saran cone in the
outer vessel, using a water bath at about 60-80C.
I think I'm going to try this and see what happens anyway and I'll post after I try, but what do you guys think about the final
water content of the distillate I will get, and if I do it under vacuum will it be better? I mostly will be using the HNO3 for
nitrating experiments but not RDX so it doesn't have to be 100% obviously.
nbk2000 November 9th, 2006, 05:09 AM

Oh boy...
Dude, this whole section is nothing BUT nitric acid and related questions. Read, read, and read some more.
Some words that might help with a search are 'mixed acids', 'nitrating', 'drain', 'anhydrous'.
c.Tech November 9th, 2006, 06:38 AM

Another handy search tip: If you can't find information on the forum or google but are sure it must be around the forums
somewhere you can search quotes.
Because Rouge Science is a public forum web spiders are free to browse as they wish so google is sure to have the forum
stored somewhere on their database.
Go to google, type in a quote eg. "mixed acids" then let google know the site it's to be searching by typing
'site:www.roguesci.org'
Now in total it should say...
"mixed acids" site:www.roguesci.org
Putting the words in quo tes on ly looks for those two words a side of each other, I ve found it very use ful s o far.
megalomania November 11th, 2006, 09:09 PM

The purity of your distilled nitric acid depends on what exactly the contaminants in your sulfuric acid are. Nitric acid is a
relatively volatile chemical, and as such it should be rather pure after distillation. I would suggest redistilling the pure nitric
acid after you make it if you are concerned.
You will absolutely get a purer and more concentrated nitric acid from using vacuum distillation. Distilling nitric acid under
atmospheric pressure leads to an increase in decomposition of the acid, and to much larger quantities of water distilling over.
tmp November 12th, 2006, 04:34 AM

I won't risk my mechanical(rotary vane) vacuum pump for making HNO3.
I use it for for air-conditioning work. It pulls 29" of Hg - more than
sufficient for A/C. My cheapass little glass aspirator(cost me $9) is the
best vacuum source I have for chemistry. Slower than the mechanical
pump but does a good job with nitric in the winter months when the water
is very cold. I keep the H2SO4/KNO3 mix below 60C to prevent the damn
decomposition. An added benefit - obnoxious fumes go down the drain.
This thing also works great with filtration flasks. The hand pump that came
with the flask wears out my hand.
megalomania November 13th, 2006, 11:04 AM

Use a trap between the nitric acid and the pump. A vacuum flask, or even a mason jar, with a little base (like NaOH preferably)
will neutralize any acid fumes that do not condense.
The acid fumes are bubbled into the base solution, and the vacuum source is above the liquid level in case anyone was
wondering how that works.
The sophisticated version: 'http://www.ars-fla.com/images/Accessories/ADS-Bubbler.jpg'

Improvised Manufacture of Nitric Acid > HNO3
Log in
View Full Version : HNO3

Hey I'm planing to build a distillation apparatus for nitric acid and I have a question: can I use Al tubing without problems ?
:confused:
If no, what can I use exept of glass ? thanks <img border="0" title="" alt="[Wink]" src="wink.gif" />
BrAiNFeVeR January 6th, 2003, 01:11 PM

You can only use Al tubing if it is very pure, any impurities will compromise your destillation setup and fill your lab with HNO3
fumes.
The other material choice would be PTFE ...
There is a very interesting topic on HNO3 destillation here:

<a href="http://www.roguesci.org/cgi-bin/ewforum/ultimatebb.cgi?ubb=get_topic;f=15;t=000023" target="_blank">http://
www.roguesci.org/cgi-bin/ewforum/ultimatebb.cgi?ubb=get_topic;f=15;t=000023</a>
And this is my page on this experiment:

<a href="http://www.geocities.com/brainfevert/hno3.html" target="_blank">http://www.geocities.com/brainfevert/hno3.html</
a>
[ January 06, 2003, 12:37 PM: Message edited by: BrAiNFeVeR ]
ShockWave January 6th, 2003, 02:15 PM

Hey brainfever, your way of getting the HNO3 is great, but are you using plastic from just a normal plastic or something?
doesn't it melt ?
zylion January 6th, 2003, 02:38 PM

Better use highgrade stainless steel, it cools better and does not get soft en bend. Turning a coil of it won't be such a problem
I think.
problems occuring with distilling at normal pressure (760 mbar??) is the forming of the red dreaded gas, that can be
minimized by vacuumdistillation(aspirator type) and collecting the nitric acid in a supercooled (> -28 centigrade formed by
dry ice and rubbing alcohol or aceton)flask. Placing the nitric acid in the freezer keeps it longlasting. The collected nitric acid
will be of +98% strenght as long as the xNO3 was dry and the sulphric acid was of >98%
[ January 06, 2003, 02:14 PM: Message edited by: zylion ]

Brainfever clear HNO3 is perhaps the most beautiful thing i have ever seen. That is a great method im gonna do it tonite in
my dreams most likely.
PyroTech January 6th, 2003, 07:09 PM

Brainfever I really like your methode but isn't it a waste of time?
You can buy HNO3 >98% I guess it's cheaper than spending/wasting all that H2SO4, but that's my opinion. I'm going too
try it though, just for fun, might give me some more experience with chemicals.

Where can you buy 98% HNO3????
I'm sure that it is not cheaper than using sulfuric, i can get my H2SO4 for 7 dollars for about 4 L, and a 50 lb bag of kno3 for
40 bucks s/h included.
ShockWave January 6th, 2003, 07:32 PM

Pyrotech, do you mean HNO3 from FLEX ?
Or are there more company's that sell 98%HNO3 ?
Sparky January 7th, 2003, 01:18 AM

Brainfever, that seems like a very good way to make nitric. Reminds me of a solar still to seperate salt from water and such.
Very scalable since you can pump hot water into a large tub and don't have to have a heat source underneath.
Aaron-V2.0 January 7th, 2003, 02:40 AM

That is a great way for distilling HNO3! Because 1) An average Joe will have all the parts for the setup (Aside from the chems.)
99.99% of the time. And 2) A stainless steel pot setup in a backyark doesnt look as suspicious as an all glass distillation
setup.
This is definately on my list of things to do now. :D

Though I'm still going to get a condensing tube from <a href="http://www.sciplus.com" target="_blank">www.sciplus.com</a>
along with more glassware. :)
Also, just a thank you to everyone who has synth's public that show the use of XNO3 in place of HNO3, it's a real wonderful
deal for those who cant obtain Nitric.
zylion January 7th, 2003, 05:54 AM

Try Firm Boom in Meppel, or J.T.Baker in Deventer you Dutchies among us. J.T. Baker doesn't sell it off the shelf, I think it
has to be ordered. I couldn't find it in their catalog.
The best way in my opinion is to distil it with the usual method.
Following the procedure in Uncle Fester's Homemade Workshop Explosives is top off the bill. It produces the fuming WHITE
nitric acid.

Yeah, nice, nice!
Brainfever did you try to make nitrocellulose with the acid.
The speed was so low because of the mixture that does not produce precipitate, the low "s"(don't know the word) (cm2) of the
collector(nylon) and the relatively low temperature.
megalomania January 13th, 2003, 08:31 PM

Out of all the posts from the other server while the board was closed, and only this one has any value... anyway I have
brought it over to continue the discussion.

I will be trying Al tubing, Stainless Steel Tubing, PTFE and I will be trying others. In other words, I will be testing which works
the best for me and I will tell you guys. :rolleyes:
Anyway I can't do it right now because I (well.. my parents :o ) don't want to do that inside my house and here it's very cold
and there is very much snow. So I have to wait to this summer to test it. <img border="0" title="" alt="[Frown]" src="frown.gif"
/>
Mendeleev November 27th, 2003, 12:56 AM

BrainFever, the procedure for distillation on your page is so simple and ingenious I am kicking myself in the ass for not
thinking of it myself ;)! I think this is definately the procedure I will use, considering it is a much cheaper alternative to buying
a 5L distillation apparatus for $350.00. Anyway, I saw you used a rather small beaker in a slightly larger beaker. I was going
to supersize this procedure and use a 5 gallon (18.9L) pot, with a 1000mL beaker inside. The pot is about 40 cm in diameter
and I doubt that saran plastic wrap will hold such a large amount of ice :mad:, so I was wondering I you know any other
materials onto which nitric acid will condense, but much stronger, like industrial grade. I was thinking of using a conical metal
pot top, but this wouldn't be good for two reasons, 1. it isn't clear, so I wouldn't be able to see inside and monitor the
experiment and 2. the nitric acid would corrode the metal. Also does anybody know which metals nitric acid does not corrode
:confused:? I think stainless steel was mentioned?
Thanks
blindreeper November 27th, 2003, 01:53 AM

While it is simple it is no where near as effective as a proper still. I think its jsut an experiment, probably best not use it if you
are really serious about nitric distillation.
photonic November 27th, 2003, 02:35 AM

I thought that Teflon was the only sort of plastic resistant to Nitric Acid? Why don't the fumes eat through the plastic(low
purity?)? Also, could you use a sheet of Aluminum foil in place of the plastic sheet?
Mendeleev November 27th, 2003, 01:19 PM

Yes, blindreeper you are correct it isn't nearly as effective, but right now I live under the oppressive household of two asshole
parents who are highly suspicious, and they are both scientists with Ph.D's so if I buy something like a distillation rig, they will
be really pissed. I was thinking of buying one anyway for $350.00 and having it delivered to my friend's house, so my parents
wouldn't know, but in the meantime, I am forced to stick with improvised methods that might unfortunately seem a bit kewl...
Sorry. Also when you said it was not as effective as a proper still did you mean in terms of concentration or yield?

I think yeilds and concentration.

Well for the time being I am forced to stick with the pot method :( untill I get order the rig to my friends house. So... in the
meantime I thought up a method to supersize this distillation. Use a large metal pot like the one I am, instead of saran wrap
use a clear plastic shower curtain, and attach it to the pot using zip-ties. On BrainFever's site, he got half a test tube of clear
HNO3 with density 1.5 g/cm3, from a pretty small beaker, so that means >90%, which is good enough for all my purposes I
think: NG, TNP, RDX, and guncotton. Furthermore if he got that from that tiny beaker I think my 5 gallon pot should fill up the
1000 mL beaker with > 90% HNO3. After I get my apparatus delivered offcourse I will move on to bigger things hopefully. I
was thinking some of those new superpowerful explosive like the ones mentioned in the medina post under the high
explosives section, hexanitrobenzene, would be really cool :D. It would also take a huge chunk out of my budget :mad:.
0EZ0 November 30th, 2003, 11:36 PM
Actually, yield and purity would not suffer as much as you think. The rate of distillation is very poor though. You can produce
small amounts of very high purity nitric acid if you are willing to heat the apparatus for a few days at low (50-60oC)
temperatures. You get minimal loss from decomposition due to the low temperatures. If you use high concentration (+98%)
sulfuric acid in the procedure, then the end product is highly likely to have a concentration of over 95%.
I thought the original idea was rather ingenious. It uses readily available materials for construction and gives quite good
results considering it's simplicity.
There is not really much point in investing in a large capacity laboratory still unless you intend to use it regularly and for other
applications as well. A small capacity (think 500ml distilling flask and 250ml recieving flask or smaller) will do you more than
fine for most needs if you do want one. You can't really store large amounts of high grade nitric for risk of contamination and
it's subsequent deterioration. Distill it as you need it.
wrench352 December 2nd, 2003, 07:03 PM

Ok,Im sure this has been done to death somewhere else,but I have waited forever to try this synthesis,and I would like to
post my findings.
Using Brainfever's method I first did a "dry run" in my kithen using a water bath,and for safety reasons,electric heat.However I
ran into several problems when I took the still outside.
First I thought the temp I was shooting for was 80 C When in fact the temp I needed was 65 C.Next problem I had was the
heat source,an electric hotplate,which when trying to get to a specific temp is tricky at best.However I found it easier actually to
get it to 65 C.(as it pertains to my first synthesis the temp unfortunately hovered around 85 C,although if it matters the out
side temp hung around 10-15 C).In addition I found oil heats up more rapidly than water and does not dissipate it easily.
Next I mixed 940 gms H2SO4 w/ 455 gms KNO3,although a large yellowish gas plume appeared,I was disappointed I did not
get the dark red plume Brainfever got,but I think its my vessel size which I figure to be + - 14.6 liters.The initial process was
rushed due to my inexperience with the process coupled with a healthy respect for NOx.Also the process was interuppted twice
causing a release of NOx which of course would lower yield.
The end product is about 100ml of crystal clear (I presume) crap.That I will try and reuse at a later date.How can I anylize the
end product for purity?
Incidentely the first go round I used ACS grade H2SO4,the next go round I will be using drain cleaner as it is much cheaper.
my next batch of synthesises will be KNO3+H2SO4 redux,NH4NO3+H2SO4,ACS H2SO4+ACS 70% HNO3,to determine best
yeild.I think the most interesting experiment will be the NH4NO3 as all equiptment and chemicals will be purchased at walmart.
Mendeleev December 2nd, 2003, 07:26 PM

Those aren't too bad results considering you had errors such as temperature control and interruption. Anyways I found out I
can use a stainless steel pot, heres a website which gives the corrosion resistance of some common metals, to just about all
chemicals: http://www.srcoils.com/corros.html
wrench352 December 4th, 2003, 08:36 PM

Hmmm,my first attempt with the NH4NO3 was a total failure unlike the KNO3 the yeild was terrible,yellow and the collection jar
contained a large amount of sediment.Also at the rate Im goin through H2SO4,I am going to forgo the ACS H2SO4/HNO3 for
now,and am goin to concentrate on the KNO3 and ramp up production.Question?In regards to my first go with KNO3,I forgot to
mention my HNO3 fumed.
Mendeleev December 4th, 2003, 09:21 PM

Your HNO3 should most definitely fume! Nitric acid has relatively weak intermolecular forces, and thus a higher vapor pressure,
hence the fuming. If it fumes it means that it is above 80% concentration. I don't know why you haven't heard of it mentioned
before, I always see references to "fuming nitric acid". Anyway that means you have good results :D. I had a question as to
what kind of hot plate you used, was it a laboratory hot plate or a regular kitchen plate like those sold at Wal-Mart? The
reason I ask is that I have a regular Wal-Mart plate, because it was cheap, about $8.00, and I have heard that such kitchen
sources let the heat fluctuate, so that it becomes very hot then stops, then hot, etc. Also did your distilling container touch the
bottom of the pot with the water bath, or was it suspended in the water? Thanks.
Edit: Oezo, would I really have to heat the apparatus for 2 days? I was hoping for 8 hours for 1L of hno3 :(. Could I do it in
shifts, like 8 hours one day, then 8 hours the next?
wrench352 December 4th, 2003, 10:50 PM

In regards to the fuming issue: Doh!I was mistaken and will edit that,Ive been very excited lately, as this is my first real
research,and it slipped my mind.Thank you Mendelev,for the reminder.I put the cart before the horse there.First go round
must have produced some good shit huh?
My hot plate for the time being IS a walmart special(should have a hotplate stirrer by May).Indeed they are hinky,
tempermental things,but although it seems settings vary from unit to unit I was able to keep the temp fairly stable(I
monitored constantly) and with both units(yep,Im gonna run two at once) Im using I can pin it to 65C fairly easily.The water
baths I originally wanted were out of season so I improvised and am supporting the vessel on a 6" deep stove chrome plate
reflector bowl.I know what your thinkin,convection but its immersed in an gallon of mineral oil.Also original temp testing in
water showed it wasnt an issue.Looks like rain and Ill double check.Next go round Im gonna keep the temp real low and really
let it go, 36 hrs.
You showed me I need to go through the research once more before I start again.(My old lady is gonna kill me,ha!).Thanks
again this is what peer reveiw is all about I reckon.
Centimeter October 5th, 2004, 08:19 PM

Although this doesn't precisely fit in this thread, the title is generic enough that it should work. I mixed 250ml H2SO4 and
365g KNO3 and distilled under a vacuum. As you can see, I added quite a large excess of sulfuric acid. Theoretical yield is
around 150ml fumming HNO3, however I was only able to get about 50ml of ~90% HNO3. I drove the reaction as hard as I
could but that was all I could possibly squeze out of the system. I raised the vacuum to about 100 torr but nothing. I raised
the temp to just under 80*C but nothing. The combination of a vacuum of 100 torr and 75*C should have been more than
enough to drive the reaction forward if it was at all possible. Further more, such a large excess of H2SO4 should have pushed
the equilibrium of the reaction in favor of HNO3 production. Is 30% theoreticle yield realy the best one can get out of HNO3
distillation? Perhaps I am doing something wrong?

Keep the vacuum as low as possible.
My gut reaction is that your end point is far too low, maybe by as much as 100 degrees. Sulphuric hangs onto nitric in a similar
way it hangs onto water, you have to drive it off and force the reaction forward. Excess sulphuric certainly helps reduce the
temperature, which is probably why you got any yeild at all at these low temperatures, as will use of vacuum. My own
experiments without vacuum left the sulphate/bisulphate salt molten at the end, not unlike the old industrial process, I was
using slight excess sulphuric as would be needed to form pure bisulphate.
nbk2000 October 8th, 2004, 01:09 PM

Vacuum is dangerous, though, unless you're equipment is in good shape, because if the reactor implodes, there's going to be
nitric acid sprayed everywhere.

If I rase the temp any more, the nitric will decompose and I will get red nitric acid. I thought that the entire idea of using a
vacuum was to lower the boiling point so that you don't decompose as much HNO3. If decomposition is not a problem, then
why use a vacuum at all? I was under the impression that red fumming nitric acid was no good for nitrations. Well, I guess all I
heard was that it's bad for RDX synthesis, and I assumed it was bad for other explosives too. Other than when nitrating
hexamine, why wouldn't the dissolved NO2 result in a better nitration, after all we use sulfuric acid to protonate the nitric
anyway?
tmp October 9th, 2004, 11:22 PM

Point well taken, NBK2000. This is why I stay away from any glassware
labeled "BOMEX". It doesn't take heating too well either. I was purifying
KClO4 in a beaker made of that shit-glass and it developed a hairline
crack while it cooled. BOMEX has its place for measuring and mixing but
don't use it for heat or vacuum applications. I use KIMAX filtration flasks
for vacuum applications - they're designed for that.
Centimeter, even 75 C seems too high for concentrated HNO3 vacuum

distillation. You need a lower vacuum, but as NBK2000 has already pointed
out - BE CAREFUL !
Mendeleev October 10th, 2004, 08:31 PM

I have never had heat trouble with bomex, like boiling sulfuric acid repeatedly in the same beaker. But it is pretty shitty
quality, with gas bubbles from the glassmaking. I have tested by bomex erlenmeyer flask in 720 mm vacuum and it was
suprisingly fine, but the only vacuum application for which I recommend consistent use is a bong. This job it performs quite
nicely. The problem with using a very strong vacuum when boiling a nitric/sulfuric mixture is if it is too strong you either won't
condense your nitric or everything in your receiver will boil away. To prevent this you could circulate -20 C IPA (-20 C is about
the limit of a typical freezre on max) using a device such as this:
http://www.rhodium.ws/chemistry/equipment/convective.circulator.html

For some reason my posts are taking a very long time to actualy show up. I think it us because I am a newbie. Anyway, in
case anybody missed my previous post, I was wondering why red nitric acid is a bad thing. Also tmp, I was wondering the same
thing; so what is Marvin talking about? I use second quality bomex myself and I haven't had any problems...yet. The guy that
sold it to me said it would be fine for use in a light vacuum. Perhaps a way to increase the integrity of a bomex distillation set
up would be to use smaller boiling and collecting flasks. I can not and will not use a vacuum greater than 100 torr to distill
nitric acid. I guess I will just distill at high temps and then redistill if neccesary. Although I have also been getting bad yields in
distilling slightly dillute nitric acid as well. I start out with 100ml 68% HNO3 and end with around 25ml 98% nitric acid after two
distillations. I just can't squeeze out anymore without decomposing the nitric acid. Perhaps I can take two fractions. One will be
what I can get while avoiding decomposition and then the other will be high temp distillation to recover as much of the nitric as
I can. What kind of yields do you guys get when distilling from xNO3/HNO3 plus H2SO4?
Isotoxin January 1st, 2005, 12:05 PM

I am getting ready to distill some nitric as soon as I get my vacume aspirator. I however have a few questions. With it I can
have a reduced pressure enviroment and with my 300mm liebig and ground glass setup I hope to distill ~500ml of white
fuming nitric acid from H2SO4 and KNO3. I have ~30L of 30% H2SO4 so I will concentrate it to ~94-98% and then add the
correct amount of KNO3.
Can someone show me the compleat equation of the reaction of H2SO4 and KNO3 so I can work the stoich?
I currently get my KNO3 in 100g jars for 2$USD at a local shop. I have heard you can get it in large bags for fertalizing but I
checked Home De' Pot and nothing. How can you convince the farmer warehouse type places to sell to you?
Marvin January 1st, 2005, 02:27 PM

If you can use the equation to work out the materials you need you should be able to balence the equation in the first place.
Either way its irrelavent. If you use theoretical amounts the temp at the end will be very high and a lot will decompose, or your
yeild will be tiny if you stop distilling at a low enough temperature to prevent this.
Use the suggested amounts, or a larger excess of sulphuric if the temp is still too high. You can always use the residue for
lower grades of nitric.
Pb1 January 1st, 2005, 04:35 PM

The equation is:
KNO3 + H2SO4 -> HNO3 + KHSO4
If you use equimolar amounts of each chemical, you will end up with a solid cake of potassium bisulfate before all your nitric
acid is out, so you have to add extra sulfuric acid.
knowledgehungry January 2nd, 2005, 10:26 AM

Red Nitric Acid just doesn't give as good yields for certain things, I am not sure why. Red Nitric Acid will work however for almost
all nitrations, just not as effeciently.
Centimeter January 4th, 2005, 09:20 PM

Red nitric acid can make a run-away nitration more likely...take for example RDX production. Based on my experimentle data,
it would seem that the H2SO4 is only donating one H+ ion. To test this, I ran a distillation using 1mol H2SO4 per 1mol
NH4NO3. I used 300ml H2SO4 and 400g NH4NO3. At first I tried without a vacuum, knowing that I could purify it with urea. For
some reason, I could not get the damn thing to distill over. Thus I put on an aspirator and began distilling at maybe 130*C.
The product was quite yellow, but it was easily purified with urea. From the reaction, I obtained ~100ml of 87% HNO3. At least
I think it's 87%. I assume that the addition of urea will change the density/concentration ratios, however considering it was
such a small amount of urea it should be negligable. I could titrate it...but I don't want to. If the H2SO4 did indeed only give
up one H+ ion, this would equate to aprx. a 50% yield. From what I observed in the boilng flask, I would have been hard
pressed to squeeze any more nitric out. Based on these results, it seems clear to me that the H2SO4 is not giving up both H+
ions. Is there some way to instigate the H2SO4 to give up that second H+ ion short of cooking the crap out of it?

No, equilibrium favors the HSO4- ion forming over SO4 -2. The only way I can think of changing the equilibrium would be to
cook the hell out of it, if that would even work.
Marvin January 5th, 2005, 01:21 AM

Red nitric acid contains NO2 and HNO2, these have a tendency to destructivly oxidise. Whats more when they oxidise, they
produce NO, which is regenerated by the nitric acid, the reaction ends up being autocatalytic.
It is possible to go all the way to neutral sulphate at high temps with an alkali nitrate but the temps are rather high and the
acid impure. Industrially it was continued to only slightly beyond the bisulphate stage so the molten mass could be poured
out.
Centimeter January 5th, 2005, 02:13 AM

How come everyone's posted procedures assume that the H2SO4 gives up both H+ ions?
I still have the left overs from the ammonium nitrate + H2SO4 distillation. Would it be such a bad idea to add 100ml 70%
HNO3 and use it to distill again? This would help to squeeze out even more HNO3 from the solution and it should result in a
more concentrated product. I guess I will try it and report back the results. This time I am going to just bubble dry air through
the acid. I don't like the idea of nitrourea being produced.
Edit- I got back 82ml of the exact same concentration of HNO3...which is some what surprising. I did however get a chance to
test the use of dry air w/o adding urea. The acid was quickly converted into a crystal clear liquid. From what I observed, it
worked just as well and rapidly as urea.
Gleng July 1st, 2006, 03:31 PM

I assume that nitric acid higher 70% will fume. It gives nitric acid at around this concetration and contains less NO2. Simple
distillation 120g NH4NO3 per 100 ml H2SO4 will work.
H2SO4 + NH4NO3 -> HNO3 + (NH4)2SO4 , distillation below 300 degrees

You will need a stirrer to distill again and maintain the temperature between 96 and 120 degrees . This gives a good result
slight red fuming nitric acid higher 95% and contains less NO2. 100 ml 70% HNO3 per 150 ml per 98% H2SO4 will work.
When giving measurements, you must always specify the unit of measure to be used.
'temperature between 96 and 120 degrees'...is this using °C or °F?
Gleng July 4th, 2006, 02:48 PM

This are the specific temperatures to the distillations.
HNO3 70%, 122 - 300 C
HNO3 80%, 95 - 120 C
HNO3 95%, 86 - 95 C
I`m planing to design a diagram which will give more information to the apparatus.
0010110 July 10th, 2006, 12:40 PM

When I distill nitric I use a homemade still that I made from 2 jars and a light bulb instead of the plastic as mentioned earlier
in this thread. I got the idea from a show about drug addicts smoking out of a light bulb! Any ways I usually distill around 180
deg F. The nitric that I got has a density of around 1.42 g/cm3. which I believe is around 70% concentration. I used KNO3 as
my nitrate salt. the heat source was a hot water bath. the still produced around 1-2ml/hr. i was pleased with the nitirc it
produced i have done this method many times.
The_Duke July 16th, 2006, 05:18 AM

Yeah, there is already a "diagram" in the first volume of Urbanski....
That and your figures are WRONG!:rolleyes:
Gothy February 25th, 2007, 04:53 PM

In general, I would say that it isn't necessarily 70%+ conc. if it fumes. I mean, I have some 62% which I usually buy at the
local beautyshop. And it fumes alright. It isn't much anyway, but white fumes slowly rise from the bottle.
And I also have a very basic question which I have thought about for a while. Please be patient with me if I come out as a
total retard:
The thing that puzzles me with distilling NA, from a low concentration NA and H2SO4, is the water in the solution. Why isn't it
evaporated along with the NA? I know that H2SO4 chemically bonds with water, but than what the heck is going on with the fact
that you can concentrate weak sulphuric acid by boiling off the water?
I don't understand why the water isn't evaporated in the NA distilling process, when it is in concentration of H2SO4.
I didn't want to start a new thread with this, since it might be seen as a n00b question.
And it really annoys me that this is my first question ever, since I don't see myself as a chemistry-dunce
megalomania February 25th, 2007, 09:42 PM

Any simple distillation (the separation of two or more liquids by boiling) will always produce vapors of all components. The
degree to which those components are vaporized is entirely dependent on their respective boiling points. The greater the gap
between boiling points, the less of the higher boiling liquid you get in the distillate.
For example, sulfuric acid boils at 290 C, whereas water boils at 100 C. Compare that to ethanol which boils at 78.5 C. Notice
the temperature gap between boiling water and boiling sulfuric acid is considerably greater than the temperature gap between
boiling water and boiling ethanol.
The closer in boiling points a mixture is, the harder it is to separate by simple distillation. Sulfuric boils at such a high
temperature that water can be substantially removed by boiling with very little sulfuric acid distilling over.
To answer your question more specifically, you do get a lot of water distilling over when you concentrate nitric acid. If I
remember correctly the maximum concentration of nitric acid you can get with simple distillation is 67-70%. Distilling under
reduced pressure not only helps prevent thermal decomposition of your distillate, but it can also widen the gap between boiling
temperatures with some substances.
Gothy February 26th, 2007, 05:33 AM

Sorry about that, I somehow got myself to believe that the boiling point of NA was 120 celsius... Doh. I can see now that is is
fairly close to ethanol i.e.
So anyways, if you were to distill NA by simple distillation, the only way to get it concentrated would be by the nitrate salt and
SA way yeah?
And on the sidenote: When lower conc. NA and conc. SA is mixed, the water will get an increase in boiling point because of the
SA right? Otherwise I can't see the point in that method

You can achieve anhydrous conditions, or near enough anhydrous, by distilling concentrated nitric acid with concentrated
sulfuric acid. I don't have any numbers handy, but there are many recent patents (last 20-30 years or so) about doing this.
The sulfuric acid acts as a dehydrating agent trapping the (small amounts of) water. The good thing is the sulfuric acid can be
reconcentrated and used again and again.
Enkidu February 26th, 2007, 10:42 PM

The reason you can't concentrate Nitric Acid to 100% using simple/fractional distillation in and of itself is that Nitric Acid forms
an azeotrope with water at ~68% by weight. According to answers.com, an azeotrope is a liquid mixture of two or more
substances that retains the same composition in the vapor state as in the liquid state when distilled or partially evaporated
under a certain pressure.
Mega is right, the closer the BPs of two liquids are, the harder they are to separate. That's where fractional distillation comes
in. However, azeotropes are impossible to separate by distillation alone. That is the theory of denatured alcohol (ethanol/
methanol azeotrope). Sulfuric acid also has an azeotrope with water. It's at 98%. That's why you can boil the water off car
battery acid (~35% conc. H2SO4) up until it hits 98% but no further.
The reason that you had 120°C stuck in your head, Gothy, was because that is the BP of ~68% conc. HNO3.
At least that's the way I understand it.
Khalnath April 22nd, 2007, 01:39 AM

No, equilibrium favors the HSO4- ion forming over SO4 -2. The only way I can think of changing the equilibrium would be to
cook the hell out of it, if that would even work.
Sulfuric acid gives up its first H+ ion much more readily than the second. In fact, due to the common ion effect, basically all of
the H2SO4 will convert to HSO4- before any of the HSO4- will give up the second H+ (technically it will happen an insignificant
amount, but not enough for even the pickiest chemist to care). If those H+ ions are being sucked out of solution somehow
(reacting with something, for example), both H+s will come off and react, but the second set will do so more slowly and this will
certainly affect your reaction rate, but probably not your actual products unless the sulfate ion is somehow undesireable.
H2SO4 is a strong acid that will fully dissociate into H+ and HSO4-.
HSO4- is a weak acid that dissociates in an equilibrium. The presence of H+ already in solution (from any source) greatly
inhibits its dissociation as a result.
Aristocles January 23rd, 2008, 03:22 AM

SHIT!
I have spent over eight fucking hours trying to distill HNO3. Without doubt it can be done sans vacuum, but I sure as hell did
not succeed. I painfully watched the temperature! But after five and one half hours I decided to up the temp a bit. I finally got
some distillate to come through but merely a few drops. After a little over eight hours I shut it down.
I spent all that damn time in a freezing fucking garage with the window and door open, as well as a fan going, and a small
ceramic heater. It was 13F when I finished rinsing off the glass (in cold ass water).
The real bitch was hoisting that siphon bucket over and over ad fucking nauseum...
Despite some really nice looking vapors, I ended up with drops...
Shit... I am TIRED
Charles Owlen Picket January 23rd, 2008, 10:05 AM

SHIT!
Let's take it from the top.....was your distillation rig TIGHT? The design is also meant to run downhill...your temp on the first
attempt should be fucking hot. Let it be a less efficient distillation at first but a workable one...you will find the best temp in
time. What was the heat source? Did it heat the whole of the flask? What was the ratio of solid nitrates or 70% HNO3 to H2SO4
?
The run for a 1/3 filled liter flask should take about an hour. Most of the time you can pull about 300ml of 1.52 for your
hassle.
Aristocles January 23rd, 2008, 01:56 PM

Let's take it from the top.....was your distillation rig TIGHT?
Charles, I think it was. Here is how it was set up: 1000 ml RBF with Ace 24/40 and 10/30 head, thermometer was inserted at
the 10/30 end via a teflon plug (just wrapped tape and then shoved until it seemed reasonably seated). Pyrex Liebig
condenser was joined to the head's 24/40 joint, then a curved adapter, and lastly a 500 ml receiving RBF. I teflon taped every
joint. After 5-6 hours I did notice some condensation leaking through a couple of he joints, I nigger rigged further taping. (I
even noticed some very small white NOx fumes escaping. Maybe not sealed well, but it's about as good as I can do, I think...
The design is also meant to run downhill...your temp on the first attempt should be fucking hot. Let it be a less efficient
distillation at first but a workable one...you will find the best temp in time. What was the heat source? Did it heat the whole of
the flask? What was the ratio of solid nitrates or 70% HNO3 to H2SO4 ?
It was downhill at an angle but I assume it could be sharper? Better quantify the minimum angle for me. :) That was a definite
fuck up. I got no results until I cranked up the heat. I mean zilch, nothing but a receiving flask with vapors. After I turned up
he heat I could clearly see vapor passing across the condenser but it was still pitiful, re: the product. The heat source was a
hotplate with pretty good heat adjustment. I heated a pen of vegetable oil and slightly suspended the RBF above it the
bottom of the pan. No, as to heating the whole, the 'liquid' was just under the oil. I believe this was another fuck up. I should
have wrapped it in glass wool? Explain, Charles. I used a 6/5 (ml to g) ratio of H2SO4 to KNO3, respectively.
The run for a 1/3 filled liter flask should take about an hour. Most of the time you can pull about 300ml of 1.52 for your
hassle.
Certainly screwed the pooch on this one... Damn, Charles these creaky bones feel that cold this morning. All those years of
lifting heavy weights combined with being off the juice for a year, have almost wrecked me. :D
Aristocles January 24th, 2008, 06:04 AM

Post whoring... mea culpa
Something else entered my mind: refluxing.
I noticed a significant amount of this... from prior threads it would seems indicative of not distilling rapidly enough. Advice? As
I stated earlier should I wrap the exposed part of distilling flask in glass wool?
Charles Owlen Picket January 24th, 2008, 10:57 AM

If you noticed ANYTHING leaking from the joints of the glass...that's most likely your issue. However, let's define some of the
parameters......"downhill" would be about at 10 degrees. The thing doesn't have to be extreme but must allow for gravity to
let fluid roll with ease.
What's taking place is the heat is producing gas...the gas condensing and forming fluid... that fluid rolling;condensing, into a
collection flask. Often the flask is maintained at a substantially lower temp (water bath or stronger). The distillation rig MUST
be air tight for these reasons.
The level of reactant must be such that it CAN boil - therefore that flask must be a least one third or more empty (half is
much better and 2/3's is great). Try water at first. Knock over plain water! If you succeed, your rig is set up fine. I still do this.
I use Vodka. I need ethanol so I use cheap Vodka to determine if I have everything set just fine - then I knock out about two
or more runs of HNO3 with solid nitrates. I am interested in efficiency and can sometimes get as much as 300ml anhydrous
nitric from 365 H2SO4 and my solids. But this is achieved through very careful temp control. Trial runs allow the user to test
temp with a thermometer and mark on the hot plate what is the settings needed. For nitric, I use a jump from 80-90C to 110
and back. But you CAN have a result from a simple boil.
I'm too old to lift heavy anymore. I also have bits of metal in me. I know about cold mornings and getting in gear (no pun
intended). Give it two years. The receptors will need that much to regenerate from any long term juice especially orals. Always
keep your sense of humor. The biggest joke is when we take ourselves seriously.
The Teflon taping was probably the culprit. When you (African-American)-rigged the thermometer. But ANY steam, smoke,
what-have you, must be eliminated. The portion for the connection of the vacuum tube is OK but before that...make it
snug......NOT too tight. That's why it's good to use a very light coating of chemistry glass joint compound. If you don't have it
try a tiny bit of vasoline. Any more than a tiny bit will yellow and contaminate. Don't snug dry joints with the force of the Gods.
totenkov January 24th, 2008, 10:58 AM

Maybe I didn't read correctly, but what amounts of reactants did you use? If you're using to little, its possible that there simply
isn't enough HNO3 fumes to condense, hence the yeild you got.
I would try using much large amounts of reactants and like Charles mentioned, cook the crap out of it at the beginning. Then
as the distillation continues, slowly start letting the temp fall (a few degrees every few hours).
Also, about reflux, its a good idea to wrap aluminum foil around the neck of your flask to avoid this, a couple turns is all you
will need to make sure the fumes actually get into the condenser.
Let us know how it turns out!
Aristocles January 26th, 2008, 09:16 PM

The forum has been down, thus I did not have the benefit of this wisdom.
BUT SHIIIIIIIIIIIIT
I cranked up the heat. And guess what? I am (thank God!!) standing sort of to the side and back a bit from my setup, when I
hear a loud noise... the thermometer blew off. I know it sounds comical but as that MASS of fumes came forth I saw my life
pass before my eyes. I bolted out the door, hell for leather.
I really ceased to process data at that point and had no real idea if my rig had fallen and been trashed... all I could do is
stand back and watch fumes pour out the window and door. Did I mention that I am completely paranoid about being exposed
to NOx fumes, in any fashion, let alone getting a lung full.
So after a couple of minutes, I decide that it's a must that I get the burner turned off. I take a deep breath, run in, turn it off,
and run back out. After a couple more minutes I do the same for the siphon hose.
After around 20 minutes I decide it has cleared out... surprisingly nothing is broken. I'm as nervous as a pregnant nun while
simultaneously being pissed that I have failed again. (Bordering on giving up the hobby, even if I survive this) So, I tear down
the rig and commence the cursory clean up. Lo and behold, I have a few cc's of nitric in my receiving flask!
So, I am thinking, if I live this might be a lesson learned... then, of course, as I am taking the hoses off my condenser, I
managed to take the condenser tip off with one of the hoses... damn...
I cleaned up and came home...
Totonkov: My reactant ratio is 6:5... thanks for the encouragement but I have, at least mostly, failed again.
Charles: I guess it would have helped if I had read the thermometer tip in your last post, before I started :D
Sheez... I almost started singing "Nearer my God to Thee" when I saw that thermometer blow out and all the fumes...
addenda: Should I make some sort of tiny stopper for thermometer to go through? I don't see how, it's an awfully small joint.
The still head is an 'Ace' 3-way distillation adapter, the top joint is 10/30 for a thermometer (other two are, of course 24/40).
megalomania January 27th, 2008, 10:04 AM

Reminds me of the time I had the same thing happen with a runaway nitration :) I held my breath, ran back into the rapidly
spewing cloud to grab my gas mask, then after donning the mask went in again to begin emergency ventilation and clean up.
It's funny now, not so funny then...

NOx is quite deadly but the human has to actually get a lungful first. The body recoils at the gas. it's actually very unnatural to
breath that shit unlike carbon monoxide; you KNOW when you're getting a whiff of NOx. Many a lad has gotten just a wee
taste of the gas and lived to speak of it's disgusting presence. It's good to recognize danger but in proportion to it's reality....
Aye, you're a better man for having seen the gas as she is. You can cope with a disaster of that nature.
Everyone has a story to tell of the 1st time they had to deal with NOx. I basically don't do most nitrations indoors for that
reason. Plus it's easier to use natural materials like snow if I'm outside. The only thing I have to cope with outdoors is UV and
that's not too difficult.
Emil January 27th, 2008, 05:44 PM

I'll be attempting my first HNO3 distillation in a few days which I am really looking forward to after all this time. After finally
collecting up a nice amount of labware and gear needed to try it, I have just a couple of small questions at this time.
Is it best to thoroughly mix the KNO3 into the HS2O4, just like you would with a normal salt acid mix?? I ask this as I didn't
want to waste any just from a small error like this. I was going to mix them in a normal beaker until the KNO3 had all
dissolved, and then pour it into the RBF.
Also Charles, I see you are doing your distillations at normal atmospheric pressure. What are your views on vacuum
distillation?? I have an awesome new vacuum pump (Teflon coated parts) which I got hold of. Do you do yours without a
vacuum because of the hassle of doing it with one, or because it is not really needed, possibly bubbling dry air through with
the addition of urea after obtaining your nitric to purify?
Tonight I am going to do a distillation like you mentioned with water, just to see if my rig is all ok. This will really help to show
me any little problems I might encounter before trying with HNO3. Any feedback would be great.
Please don't think I haven't read through plenty of the HNO3 threads, I have. It's just with so many different accounts from
people encountering problems and some having none, it's nice to get another persons point of view.

YES! Mix your materials first to a completed solution, then begin. IF you have a vacuum, you will have greater efficiency over
all. IF you can do so without damage to the pump, etc; by all means it's a much more efficient system. I use normal pressure
out of necessity and I have a great deal of materials and a damn fine condenser. Efficiency is improved with a vacuum.
I frequently will distill ethanol (via Vodka) with the distillation rig prior to anything else as it works the bugs out of the set-up
and let's me gage the hot plate temp. It has really paid off as it tells you a lot of things about the system. Every time you set
up a system of glass; there are variables, etc. It can be done indoors and is clean. It's a very fast method to determine if
everything is set to go. Making a mess with acids is a big chore. A watch your distillation; don't walk away from it for very long.
Issues may arise that you can clear up IF you see them coming.
I once used a aspirator that kicked back water (due to poor inconsistent water pressure) and it made a mess. I also had a
pump that I got as lab surplus and it died on me. If I had a good one; I'd use it.
My magic ratios are 690-700gr H2SO4 to 600gr KNO3 (or a little less if using Na or ammonium nitrate): from this expect
between 285-300ml anhydrous HNO3 before pulling the system down. Don't let it run till dry. Let your condensation continue
even after the "heavy" flow.
I have also experimented with cooking down surplus sulfuric (drain opener) & it wasn't worth the hassle. The only thing that is
worth the time is to really dissolve the solid nitrate in the sulfuric first. That, without question improves everything. I always
think about the process; I don't simply dump things into glassware and expect fine results.
As long as we are asking questions here - I have one. I have heard this question asked before and perhaps Mega could
answer it......if Urea contains more nitrogen than other solid nitrates why couldn't Urea be used in a solid nitration? What are
the foundational aspects of solid nitrate nitrations (as this seems to be the core issue)? Why do some aliki metal nitrates like
CaNO3 make for poor nitration while Na does so well?
Emil January 28th, 2008, 08:05 PM

Tonight I decided I would give my HNO3 distillation a go. Last night I did a test run with water and all was well. My Rig was
setup nicely, vacuum pump was working lovely, so I was quite optimistic about trying for some HNO3.
To start of with I cut the reaction down to 175gr Sulphuric to 150g KNO3.
It's late here so I got annoyed and gave up for tonight (work tommorow), but the problem was actually quite a basic one, not
even to do with the distillation.
There I was with my magnetic stirrer adding my KNO3 to my Sulphuric, happy as Larry, when all of a sudden my stir bar
stopped spinning. Confused, I fiddled with the stirrer and try to move the spin bar thinking it had just moved out of place or
got lodged, but I got nothing. I thought the Magnetic stirrer/Hotplate had given up on me. I decided to determine if it had so
I grabbed another beaker with water, placed in a spin bar and turned it on. It worked fine in the water.
My KNO3/HS2O4 mix was actually reasonably flowing, any ideas on why it would no longer spin in the mix? OK it's obviously
less flowable than water but it was not solid in any form which is why I was very confused when it just stopped. Could it be a
crappy stirrer/Signs of it being passed its best?
You may be looking at this post thinking, so whats the big deal?
Well the problem is without the magnetic stirrer, KNO3 is VERY hard to get to dissolve. Just using a glass rod stirrer was not
working well at all and would of taken me a long time.
I personally would prefer to use AN as the salt, but for me it is hard and expensive to get hold of. I don't want to be going
through kilos of AN for
HNO3 production, but KNO3 I'm not bothered about. This has annoyed me somewhat as It's not even an interesting problem
to discuss in the scope of chemistry. Any ideas Charles?? I know you've got a magnetic stirrer/hotplate.
Charles Owlen Picket January 28th, 2008, 09:31 PM

Yes indeed. It's the density of the solution and -- you're right; it's just too thick. Actually the stir-bars need to be big ones
(like the 600's or the ovals). Otherwise; I'd stir it by hand at room temp and -(neat trick)- make SURE your solid nitrate is
really fine. Use an old coffee bean chopper or an old blender. Blenders are actually very useful and can be used for all sorts of
things.
Many people find that Na nitrate is a better bet that potassium nitrate and they usually prefer ammonium nitrate the best (this
is a real opinion issue). Calcium nitrate is generally considered to be a poor choice (I'm not sure as to the chemistry in that
issue) however remember that the source can "coat" the prills with clay OR the actual salt may be so contaminated with crap
(seriously, there can be real contaminants in it).
Note that NaHO3 is very hygroscopic and that grinding it up in a coffee bean mill can show if there is a bit of moisture there.
Frankly, if I grind the nitrates prior to mixing, I can get it done by hand after about 3-5 minutes. I had two stirrers and one
had a hot-plate as part of it. The hot plate put more ROOM between the magnet and the stir-bar unit (!) and was always less
potent than the simple design (the old bastard burned out on me too). Stir it by hand at first. It will be OK. And attempt to
find one of the BIG stir-bars. They are expensive but there is an alternative. There is a large oval magnet used in veterinary
applications to keep a cow's stomach free from metal bits. You'll find them at the feed store and they can be coated with PTFE
or whatever.

Charles seems to be equipped with a helluva a lot of 'practical wisdom' (praxis). ;)
I stir mine by hand, takes me about 15-20 min. I use a bit more H2SO4 than you. My KNO3 is Spectracide Stump Remover.
Seems reasonably ground to me, but of course could be finer, it's something to consider. Maybe I'll put some in my handy
dandy rock tumbler...
I was going to post this last time, but didn't. 'Pour' is not a word I'd associate with getting that sludge into the RBF.
I wish you all the best and hope you succeed.
I may try again tomorrow, myself.
Hinckleyforpresident January 30th, 2008, 09:02 AM

A few days ago I vacuum distilled some white fuming nitric from anhydrous ammonium nitrate and 93% sulfuric acid (rooto). I
used 480g of ammonium nitrate and 420ml of 93% sulfuric acid.
I used a home made vacuum pump (a converted air compressor) to pull a 60 torr vacuum, distilling the nitric at 30oC. The
final yield was 200ml. I suspect I could have gotten more out of it, but I grew tired, and as soon as it cooled to room temp
(and without vacuum) the ammonium bisulfate immediately crystallized making further distillation difficult.
The distilled acid had a density of 1.49-1.51g/ml (98.6-100%). The yield was 80%.
By the way folks, I encountered no leaks while this doing this indoors. I simply ran the exhaust line from the vacuum out a
sealed window about 15 feet into a bucket of NaOH solution. No HNO3, no NOx, no nothin' inside :D!

A few days ago I vacuum distilled some white fuming nitric from anhydrous ammonium nitrate and 93% sulfuric acid (rooto). I
used 480g of ammonium nitrate and 420ml of 93% sulfuric acid.
I used a home made vacuum pump (a converted air compressor) to pull a 60 torr vacuum, distilling the nitric at 30oC. The
final yield was 200ml. I suspect I could have gotten more out of it, but I grew tired, and as soon as it cooled to room temp
(and without vacuum) the ammonium bisulfate immediately crystallized making further distillation difficult.
The distilled acid had a density of 1.49-1.51g/ml (98.6-100%). The yield was 80%.
By the way folks, I encountered no leaks while this doing this indoors. I simply ran the exhaust line from the vacuum out a
sealed window about 15 feet into a bucket of NaOH solution. No HNO3, no NOx, no nothin' inside :D!
My 'mityvac' arrived in the mail today. I think I'll give it a go. I need to figure out setting up a trap or two for it. It appears
that they fix it as a basic siphoning set up... this toy claims to be able to hold a decent vacuum, we'll see
I have read that 30-50 torr is sufficient for NA. Is this the correct formula for conversion: in. Hg x 25.4 = torr or mm Hg
Hinckleyforpresident January 30th, 2008, 02:03 PM

I have read that 30-50 torr is sufficient for NA. Is this the correct formula for conversion: in. Hg x 25.4 = torr or mm Hg
Yes. It's just a unit conversion.
Charles Owlen Picket January 30th, 2008, 08:40 PM

Aristocles: if it works well, give it a review! I for one am interested in getting something other than a aspirator. I've tried a few
little vacs and they didn't hold up past about 4-6 labs. At the half dozen mark they started getting some bad joo-joo due to
the acid. If the thing works well (especially after a FEW tries) write some feed back: product name, cost, performance levels
setup, components, design, etc.
Dr. M January 31st, 2008, 03:15 AM

Charles (and others using pumps for pulling high-vac) -
I'm sure it wouldn't be all too hard to rig up an acid trap in-line between the apparatus and the pump; all one needs is a
canister which will resist vacuum-implosion, two microporous plugs (e.g. cotton or glass wool, steel wool would work in a pinch;
hell, a coffee filter cut to size would probably be ideal) and a filling of prilled sodium hydroxide; calcium carbonate would
probably do in a pinch.
In a very rudimentary process flow diagram:
Distillation App. --> Hose --> Trap --> Hose --> Vac --> Exhaust
It's a lot cheaper to change out lye crystals and a short length of PVC than it is to repair a vacuum pump, agree? Furthermore,
if the trap is set up with sufficient absorptivity, the vacuum pump exhaust should be completely non-offensive.
Emil January 31st, 2008, 09:12 PM

Sucess! At last, tonight I had a sucessfull Nitric distillation.
24/29 Quickfit Rig:

2000ml Boiling Flask
500ml Receiving Flask
520ml Condenser
Anti Bump Bent adapter.
Bent adapter with Vacuum take off.
Cole-Palmer Vacuum Pump with Teflon tubing
After having some difficulties with my KNO3 (possibly due to an impure product) I decided to give some AN a try. The AN, like
my KNO3, was ground using a coffee grinder to a nice fluffy powder.
175g H2SO4 with 150g Ammonium Nitrate was used for this distillation and it was done with a vacuum pump. The exhaust was
run outside the door into a bucket of water, and heating via a portable gas stove. I do have an electric hotplate, however I
must admit I don't like using it. I find it takes a long time to heat up your materials.
At first I was actually slightly confused. I had left my mix of AN and Sulfuric overnight in the RBF due to having to cut my
experiment short the night before, and my initial thought was that the mix had taken in some water (both being greedy with
water). I applied the heat and it started boiling nicely. I don't have a measurement because I don't use a thermometer in my
rig. The nitric started coming over and it was so clear, I actually thought I was just distilling over water. How wrong was I! There
was no nox build up inside my rig and after checking the product in the receiving flask, I realised it was heavily fuming. I
turned it all back on and continued.
15 minutes later I had collected 70ml of white fuming nitric acid with a tiny yellow tint. It fumes alot! Tomorow I will measure
the density and post the results. It might be slighty lower concentration than what could be attained due to the fact there could
of been a slight bit of water introduced over night. However I am really happy with the yield!
The main thing is that everything works well, my rig is working beautifully, and now we just have to hope my vacuum pump will
live through the nitric acid fumes. It is meant to be a chemically resistant one with mostly teflon parts, so we'll have to see.
Charles Owlen Picket February 1st, 2008, 10:35 AM

Excellent job! Now if you experiment with ratios vs. temp ranges and time lines you will find optimum for specific materials. I
have always wondered at HNO3 productivity levels utilizing a variety of supplanted solids.
I used to keep my distilled HNO3 in a large heavy glass bottle with a glass stopper and refrigerate it. I would use .5 gram of
Urea to 100ml of acid and all trace of yellow would leave after a week. However, that is not a necessity. {I have used this to
maintaining acid density over the course of a year. If you put a lot of work into distilling acid, you may want to keep what
you've worked at.}
I still wonder if Urea could function as a solid nitrate... No one has ever written on that subject, that I could find.
I once lost some glass due to using too high a heat source. It focused heat in one area and not all around the container. I got
a crack and it spread. This occurs if the fluid is dense and cold (H2SO4) & sudden heat is not spread over the whole of the
container. I only use a hotplate that is a fairly decent quality now as I got so damn angry at my impatient attitude; I didn't
have to loose that tapered flask.
Emil February 2nd, 2008, 03:47 PM

Now that would be interesting if urea could be used as a solid nitrate. I have plenty of it that could be used for nitric
production, if it were possible. It's also dead cheap and easy even for me to get hold of.
Worth a try, maybe I shall give it a go when I get some spare time.
Yes, at the minute I have my distilled HNO3 in an Amber Pyrex bottle, chilling in the fridge, all covered up from any light.
Hopefully this will stop any significant breakdown.
Luckily the heat source I use doesn't just focus heat on one part. It is a portable stove which takes small gas bottles, and is
much like a ring on a cooker, which gives a reasonably wide flame. I would definitley hope not to crack any of my rig, as I
have already cracked a glass aspirator and that was bad enough. The only problem with glass aspirators is they have a weak
point, and that is the part where the stem thins down before expanding back out. The silicone hose was quite a tight fit and
when I pulled it off.. *Crack*
It doesn't help that I have a cluttered lab which needs sorting out.
Aristocles February 3rd, 2008, 02:49 AM

Well, Well
It worked out much better for me this time. Not too efficient but much better...
Rigged things up yesterday, but had a problem with my trap. Bad seal... kept losing pressure throwing water back into my
receptacle. So, I repeated this fuck up several times for sheer fun (masochistic that way, I guess). Actually, I got pissed and
abandoned it.
Went home got a 2-necked round bottom flask and a couple of rubber stoppers. Having no proper tools, I took my pocket
knife, sat there watching "House" and bored the holes.
Went in the next morning to my setup. Connected the 2-neck, pumped the mityvac up to around 24 in. HG, and turned on the
hotplate.. The vacuum pump held pretty well although I had to give it a pump now and then. Did my best to keep the heat
regulated, well considering my thermometer was in half from being hurled against the ceiling, in my last disaster. I had to
depend on keeping the temp of the oil within reason using a candy thermometer and understanding the transfer fairly well.
My setup was 24/40 throughout. I used 3.37 mol H2SO4 and 1.63 mol KNO3. I let it go for 1:55... yield was 50 ml.
So it was a learning exercise, but it worked. I put the nitric acid in a volumetric flask with a glass stopper and stuck it in the
fridge.
One thing that stuck me was the near implosion of the hose, from the vacuum adapter to the trap. It was almost "sucked"
together. I am assuming I need a stronger hose material....
Truthfully, I am quite pleased. If I had not been worn down from hoisting that five gallon bucket of water virtually over my
head and then leaning carefully over my rig to dump it into the supply bucket, I could have extracted significantly more, I
presume, based on the drips. (Had to do that every six minutes and thirty seconds) Lazy...
No dark fumes (NO3?), much easier to get it dripping nitric, and overall a success.
Emil February 4th, 2008, 02:31 PM

Well done, glad to hear of your sucess. It's extremely enjoyable when everything goes to plan. It's not failing that is the
frustrating part of chemistry. It's more the waste of valuable chems and the unecessary clean up that you create for yourself.
Thats interesting that you mention the "hose imploding". I have exactly the same thing occur when I have my vacuum turned
on. I'm not sure if this is meant to happen or not, but the hose I am using is proper 3/8 tygon tubing. However it is very soft
and collapses easily. If that's the case then I will have to get a suitable hose for the vacuum part. The main reason I chose
the tygon tubing is becuase I know alot of silicone and rubber based hoses will breakdown from the HNO3 fumes.
Like you Aristocles, I saw no NOx fumes what so ever during the whole distillation, which I was pleased about. Before
beginning the experiment I was a bit cautious and slightly worried about NOx escaping from my rig and me breathing some in.
I had the gask mask at hand, but luckily did not have to use it.
Next I plan to sort out my KNO3 troubles. It would be and ideal salt to use, because I can get so much of it for great prices. I
can personally get hold of 25kg's of KNO3 for the same price I could attain 3kg's or AN or Na.
When I distilled I didn't find it necessary to cool the recieving flask, or insulate any of the distilling flask. Just the cooling of
the condenser was enough for the entire procedure to run smooth. I was distilling at roughly 2drops a second.
Charles Owlen Picket February 5th, 2008, 09:20 AM

Charles (and others using pumps for pulling high-vac) -
I'm sure it wouldn't be all too hard to rig up an acid trap in-line between the apparatus and the pump; all one needs is a
canister which will resist vacuum-implosion
This is a very logical concept. I like it! It makes sense and is not expensive. :)
Emil February 5th, 2008, 02:09 PM

Good thinking, an acid trap may save alot of problems occuring. However "canister" sounds a rather brief description.
I'm not to sure what you mean by this....
Wouldn't the trap have to have some type of filter to prevent any of the harmful fumes travelling through the pump?
It also couldn't obstruct the vacuum flow too much, otherwise this would lower the performance.
Aristocles February 8th, 2008, 10:22 PM

Well I tried Sodium Nitrate tonight, not bad coulda used some habanero sauce... ;)
Anyway, I tried 2 mol H2SO4 (assuming it's > 99%, it's not) and 2 mol NaNO3 (assuming it's > 99%, might be), rather poor
choice considering things. To wit, the fact that I poorly crushed the prills. (I ended up with a bunch of locked NaNO3 in my
boiling flask.)
I was amazed at the clean nitration as well as the 'clean' distillation. Sodium Nitrate seems to work GREAT! Set it up... of
course I broke a 500 ml two-neck I was using as a trap. So I quickly grabbed a three-neck and an extra stopper, filled the
superfluous stopper hole with silicone rubber, jammed it in, and let it set up a moment.
I cranked up some heat and walked over to pump up the mityvac. I pumped it up to a bit over 25 in. Hg. I learned something
at this point. The mityvac will hold a vacuum and it is a fine little tool but at 25 in. Hg and above, it deposits some fluid into
the receiving flask. :( But being hard headed, I let it ride with a smidge of water. In less than an hour, I had roughly no fluid
left in the boiling flask, and a nice, albeit small, amount of nitric acid in the receiving flask.
The temperature stayed very low- the temp of the oil stayed around 75-80C- and I could have gotten significantly more had I
done a better job on the ratio of H2SO4 and NaNO3 and crushed the prills better. That SN was nice to behold boiling away at
such a low temp, virtually no visible fumes, very clean. My reward was a bit over 100 ml. of nitric acid.
So, I now know:
1)SN (I cannot 'say' enough good about it) is the go for me.
2) Keep the mityvac just below 25 in. Hg.
Getting that clump of shit out of bottom of the RBF took SEVERAL washes and time!
Nothing new for many but quite new for moi...

80 C is generally what I use. I also am a fan of boiling stones as I jumped to a 2 liter and with each of my runs - I try to
better 350ml acid distilled. At one time I actually filled a dark amber gallon acid jug with my efforts and refrigerated it for
about 6 months. Upon opening; it was fresh and delicious as the day it was distilled...... ~-= Ahhhhh=-~
ETCS (Ret) February 10th, 2008, 12:13 AM

My experience with Calcium Nitrate (solution grade prills) and commercial 93% Sulfuric Acid has been without disappointment.
I use a bottle (glass or teflon) with a screw cap and fill the bottle to near capacity with the Calcium Nitrate prills and shake
them down to get good settling. Then I pour into the bottle the Sulfuric Acid to just cover the prills and screw on the cap to
keep air/moisture out. The reaction begins immediately but as it takes quite a long time for the prills to convert to Calcium
Sulfate and release the Nitric Acid I set it aside in a dark cabinet for a week or two.
When all is finished the Calcium Sulfate will have settled to the bottom and the bottle will contain a clear liquid above. When
the cap is removed you will see instantly that you have fuming Nitric Acid (with perhaps a bit of Calcium Nitrate in solution)
which works very well in all of the nitrations I've attempted (nitrosugars, nitrostarch, nitric esters) without any additional
processing or distillation.
For those who require the purest product simply pour the liquid into your glassware, decanting to leave the calcium sulfate
precipitate in the bottle, and distill away. You'll find that there is very little residue left behind.

For those who live within the USA this is quite important. The availability of calcium nitrate will continue (TTBoMK) as the
Fertilizer Institute has begun a co-ordinated effort to minimize the packaged bag availability of ammonium nitrate and shift to
bulk vehicle delivery in accordance with the Be Aware America campaign.
The Fertilizer Institute as many know is the corporate entity of the mfg associations as an umbrella organization of firms that
manufacture chemicals, etc and have been working with the fedgov to minimize impact to agri-business from various political
agenda. Chuck Shumer (D-NY) attempted to actually BAN ammonium nitrate when he was told that such a move would destroy
American farm production (and it's impact on our economy would be devastating).
However such things would come frequently from the likes of urban dwellers who "know not what they do". Calcium nitrate is a
common fertilizer available as 40-50lb bags at about $14 per unit. However various patents illustrated it's use in explosive
materials so it's really "six of one, half dozen of the other" for the likes of Mr. Shumer.
Dr. M February 17th, 2008, 12:19 AM

Good thinking, an acid trap may save alot of problems occurring. However "canister" sounds a rather brief description.
I'm not to sure what you mean by this....
Wouldn't the trap have to have some type of filter to prevent any of the harmful fumes traveling through the pump?
It also couldn't obstruct the vacuum flow too much, otherwise this would lower the performance.
I say "canister" because it leaves a lot of room for creativity regarding the vessel one might use to contain the prilled base.
The absolute requirements would be:

1 - Gas-tight seal on all fittings/joints used to construct the canister;
2 - Chemically inert with regards to the filler material (i.e. doesn't dissolve in contact with NaOH);
3 - Resistant to reasonable vacuum pressure;
4 - Sufficient volume to contain enough filler material to be effective.
I would envision that schedule 40 or 80 PVC or ABS pipe with appropriate fittings would fit the bill quite nicely. All one would
need is an end fitting suitable for attachment to the vacuum take-off from the distillation apparatus (i.e. a stepwise series of
reducers taking 2" PVC pipe down to 3/8" I.D. vacuum line), an appropriate length of vacuum-resistant tubing with I.D. to
match your reducer fitting, a length of PVC pipe (say, 2" O.D.) which will hold a good handful of NaOH - 6" should do more
than nicely, and another reducer fitting which will run from the PVC acid trap to the vacuum pump. It would, of course, be
prudent to plug both adapter ends properly with glass wool or similar inert packing to keep particles of NaOH from entering
your pump or flowing back into your distillate. Cotton could be used in a pinch, but may deteriorate on the acid-input side over
time whereas glass wool would more than likely outlast the chemical trap's absorbent capacity.
Acid vapor is so well absorbed by loosely-packed NaOH that, provided one packs the setup well enough that there aren't any
large direct paths through the absorbent, not a single wisp of acid vapor will survive to the vacuum-demand side of the trap;
your pump will thank you. The restriction to vacuum flow is negligible - manually packed prilled NaOH will provide more than
enough slowly meandering passages to allow a full-rated vacuum to be quite efficiently established.
And as one final bonus, after sufficient usage (quite some time, I'd imagine), the NaOH should be converted largely to
NaNO3; in essence, recycling your acid trap after numerous distillations should give you a distillation all its own. After each
usage, one could simply detach the trap and dry it in a suitably warm place to eliminate any bulk water resulting from the
NaOH + HNO3 ---> NaNO3 + HOH double-displacement, in order to avoid an eventual NaNO3 slurry.
Emil March 5th, 2008, 07:55 PM

Well, I had an interesting experience tonight. Having tried both Potassium and Ammonium nitrate for Nitric acid distillation, I
thought it was time to try some Sodium nitrate.
Being fed up of paying high prices to suppliers, I dug around for a source of a cheap nitrate and have recently had a good find
(or so at least I thought). 3per kilo, labelled in the garden shop as "Nitrate of Soda", I looked up the MSDS to find it contains
97% Sodium nitrate. It however doesn't list the other 3%. Now me, not thinking the 3% could be of any interferance what so
ever, was suprised to find that actually it was a big problem.
As always with nitrates, it was finely ground using my trusty coffee grinder.. no probs. I measured out my Sulfuric acid and
began addition of the nitrate like usual. Straight away I noticed that my NaNO3 was not dissolving how I visioned it to. I
expected it to be like my AN. Thinking possibly it may just take slighty longer than AN I continued to add.
After 5 mins I started to notice something was not quite right. The mix was hardly fuming like it would with the AN or PN. It
also had a slighty different smell (not that I was purposley sniffing the vapours given off, but we all get a whiff). I stopped my
magnetic stirrer and thought it was time to grab my glass rod. However I noticed the Nitrate had clung together in about 20
seperate lumps and formed hard clumps of nitrate. They were also quite big.
It just was not dissolving, and after this discovery I dumped the reaction.
What I would like some advice on is my nitrate. Could that 3% really be that much of a substantial problem?? If so what do
you recommend, that I purify my nitrate via the hot water and filter route?? Any of you guys had this problem before with a
nitrate which wasn't "Pure"???
Any comments would be most helpful, as I am still a little puzzled.
Darkover March 9th, 2008, 09:37 AM

I've been testing extractions using calcium nitrate, as ammonium nitrate is no longer available here. Other than you need to
use an excess of drain cleaner ( I use an extra mol as a general rule) as calcium nitrate is double by weight per mol. It
extracts very nicely, at 27 inches of vacuum it boils at 30-33C.
I get my "double salt" fertilizer in prills that I cook at 250C (at 45C the prills melt and form a liquid) till all the water is gone
and its a solid again. Once cool it goes into a food processor and ground to fine powder that sieves through a screen to make
sure its all very uniform.
This was 164g of calcium nitrate with 100ml drain cleaner and produced 36ml of clear colorless nitric acid. This is less than a
mol, previous extracts have made 54ml per mol of nitrate. Normally I heat my acid to 280C to dry it, this was a test with my
new vacuum acid bottle with gauge. This gave me some insight on the strength of the raw drain cleaner I use and let me test
to see if the vacuum bottle removed the acid from the air stream going to the vacuum pump. Clearly I need to use more acid,
however the final product is beautiful even if there is waste in the extraction.
My extractions are done in a water bath, as only 33C is needed to bring the nitric to a rolling boil in this setup water boils at
approx 50C so the water bath is held digitally at 42C to keep water from distilling over.
The pictures show the slurry before extraction, I mix this in the 1L flask nitrate first then acid. As I was pouring the slurry into
a funnel and into the glassware long ago. I had 2 tiny drops of mixed acid too small to see hit my arm above my gloves, I
couldn't even see the drops on my arm looking down, but it felt like red hot needles being driven into my arm, and holding a
funnel of mixed acid I had to sit there and grit my teeth while I finished pouring... Mixing happens IN the bottle now. I've read
on these boards about people asking how they get the yellow off there whole hand or some such, after nitric. My first question
would be more like where's the painkillers.
The vacuum bottle during operation, this was filled with water with a large excess of sodium bicarb, the brass fitting going into
the bottle was green from corrosion and the bicarb-water was colored the same. The brass fitting leaving was only a bit dark
colored, this is exactly what I was hoping for. Very little acid vapor is reaching the pump.
The picture with the dangerous looking orange gas is after the pump and is at standard atm, this serves as a trap for
compressor oil that is aspirated out. As the gas passes through the pump its heated beyond 100C decomposing the nitric gas
that wasn't condensed or neutralized in the vacuum bottle. The end of this tube leads waaay outside.
Next is the leftover scum picture, this is the junk your gonna be scrubbing outta your glassware when your done, a dozen
rinses and good shaking with a gloved finger plugging it and it comes clean.
Finally the completed acid, at less than a mol (36ml) but perfectly clear and colorless it sits beside the freezer nitric, with the
slightest tint of yellow (was working out the bugs on the homemade digital hotplate from wallmart parts) from a previous
extraction and not used up.. yet.
1079
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Improvised Manufacture of Nitric Acid > Distilling HNO3 and fire hazards
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Trinitrotoluene January 28th , 2003, 01:26 AM

I can recall the first tim e I trie d to distill HO N 3 I l a c k p r o p e r e q u i p m e n t . B u t I d e c i d e d t o m a d e s o m e a n y w a y s . W e l l m y nitric
acid still I bu ilt was, 2 flask one 250m l a n d t h e o t h e r 1 2 5 m l a n d I placed 92m l of concentrated H2SO 4 in the 250m l o n e a n d
a d d e d 1 5 0 g r a m s of NaNO3.After that I m a d e m y own stoppers out of Alu minium foil and used m a s k i n g t a p e a s a s e a l . T h e n
a s m o s t p e o p l e s t a t e d t h e y u s e g l a s s t u b i n g b u t i n s t e a d I d o n ' t h a v e i t s o I u s e d s o m e clear PVC tubing that I stole from the
local hospital,connected the 125m l flask with the Al foil stoppers, seal with m asking tape,and started distilling. I'm not sure
about the tim e but I can see that my tubing was under attack by the acid but I continued on distilling. After I made 10ml the
poin t where the tubing connects the 250ml flask along with the Al foil stoppers started to m elt, then bubble , as theres it
started leaking HNO3 and NO2 gas I realized I was in trouble I turned off the hotplate and disconnected the tube le ading to
m y 125m l flask,backed away,but right when backed away the tower of HNO3 and NO 2 fumes ignited into a tower of intense
flam es. The fire was quite intense because HNO3 is a powerful o xidizer.As the fire burned I sent up a pretty good cloud of
black smoke that smell corrosive. After I think 10 m ore seconds the fire died down but was still burning I poured som e water
on it to put it out. I had some clean up to do. But I got off pretty lucky because had I was distilling HNO3 indoors, it would had
b e e n a d i f f e r n t p r o b l e m a s m y house would had burned down. I was thinkng about doing indoors but decided outside so lucky.
But after that I chang ed tubing as now m y tubing is pure alum inium.Then I distilled the rest of my stff and got 30m l of red
HON3.But I had learned from m y m a s t a k e s .
Zach January 28th , 2 0 0 3 , 0 6 : 0 6 P M

I stand corrected on the aluminum rea ction.
<sm all>[ January 28, 2003, 08:42 PM: Messag e edited by: Zach ]</sma ll>
knowledgehungry January 28th , 2 0 0 3 , 0 7 : 3 2 P M

It m ight not have been the HNO3 that rea cted with the Al foil but rather the products of the HNO 3 a n d P V C
reaction. HNO3 will not usually react too badly with HNO3 howeve r HCl and Al react pretty strongly a nd i believe that HCl is
form ed from the reaction of HNO 3 a n d P V C .
<sm all>[ January 28, 2003, 06:33 PM: Messag e edited by: knowledgehungry ]</sm all>
blindreeper May 15th, 2003, 08:21 AM

I know this is old, but doesn't HNO3 re act with Al?
I m ade a solar still type thing for nitric acid and after half an our the Al was eaten away, m aybe cause Al foil is not pure?
Arthis May 15th, 2003, 05:20 PM

Normally, pure Al wou ld be oxydised by HNO3 and form a s m all layer that stop corrosion (passivation). But any im purity is
goin g to allow the oxydation to dig further inside the m etal.
And norm ally passivation only happens with concentrate d acid (I think). Maybe the layer is taken away because of the water ?
Desmikes May 15th, 2003, 09:55 PM

I ve n ever trie d to distill any nitric acid b/c from what I ve read it is k i n d a t r o u b l e s o m e and t h e yield is not all t h a t g r e a t . S o I
d o n t know m uch a b o u t p roperties of that particula r acid, b u t a s f a r a s I know every single acid will react with m e t a l . I would
think that alum inum tubing is not the best choice b/c your conc. acid will break down to H2 and oth er things. Probab ly what
happened in your case was that nitric acid reacted with Al foil causing enough heat to melt the tubing, so if you use som e
o t h e r m aterial for your s t o p p e r s y o u s h o u l d b e f i n e , b u t t h e n a gain I a m not s p eaking o ut of e x p e r i e n c e , t h a t s s im ply m y
theory.
Arthis May 16th, 2003, 03:38 AM

Hue, he, ho ! If you had read my previous post, if you had search a bit before presenting us your "theory", then you would
h a v e b e e n a w a r e o f t h e p a s s i v a t i o n p h e n o m e n o m . Your theory is wrong.
And do you really think it could have m a d e t h e A l m e l t ?
Maybe you should get inform ed before sending posts.

Improvised Manufacture of Nitric Acid > Expedient Nitric Distillation
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john_smith October 21st, 2002, 05:26 AM

I h a v e t h e m isfortune to live in a dorm right now. The toilet facilities (and a sm all kitchen) are sha red by two room s/four
p e o p l e . M y r o o m m a t e i s g e n e rally so-so, but the guys from the neighboring room are real assholes with a record of voluntary
snitching. So basically I have neither running water nor a fum e h o o d .
So far, I've been thinking abo ut two ways of setting up the still:
1) taking to the wood s. At least no frid g e i s n e e d e d h e r e , b e c a u s e s n o w a n d i c e a r e a b u n d a n t .
2) setting it up right there on the window sill with the vent tube reaching outside. Com e to think ab out it, m a y b e e v e n p l a c i n g
the condenser outside and filling the o uter tube with antifreeze (the window is in two vertically opening parts and it's -4C
outside at the m o m e n t ) .
The questions:
1) How critical is the proper cooling in NA manufacture?

2) How noxious is the NO 2?
3) How bad does it stain? I live on the top floor and think about using a piece of PVC pipe as a stovepipe preferably reaching
over the roof level. Is it necessary - or, is it enough?
4 ) D o e s s o m e b o d y h e r e h a v e a n y e x p e r i e n c e w i t h e x p e dient nitric production in general, and does the setup described above
m ake any sense at all?
Thanks.
Edit: deleted m y ASCII artwork because it seem s that extra spaces get d eleted...so you've just got to guess...
<sm all>[ October 21, 2002, 04:40 AM: Messag e edited by: john _sm ith ]</sm all>
Marvin October 23rd , 2 0 0 2 , 0 7 : 3 9 P M

Dont m ake nitric acid in the sam e place you live/sleep/work. Wh ereever you do m ake it needs good ventillation, even if it
m a k e s t h e r o o m freezing in the process, if the room rem inds yo u of reporters on the outskirts of a hurricane, the room is well
ventilated, better yet is to do it outside. The woods are ideal, and snow/ice make excellent coolers for the distillate bottle. NO 2
is exceedingly toxic, fortunatly distillation only m a k e s s m all am ounts of it, done right that is. Nitric acid vapour is just nasty, as
youd expect a volatile corrosive to be. Temperture is less important than quantity of heat rem oved, an air condensor, even if
the outside air is at -4, simply will not do. A bucket of cold water with the condensing container, eg a whiskey bottle, is fine.
The containe r you m ust distill from needs to be one that wont shatter fro m t e m perature differences, this is usually the hardest
part when just beginn ing. I used chemistry set test tubes, quite large ones, and the am ount I got each batch was tiny, like
1 0 m l. I used a wax impregnated cork with a 90 d e g r e e b e n d g l a ss tube from it. This worked ok, m ost plastics get a ttacked.
Its very tem pting to want to scale up b efore you understand the nature of the chemicals. This is a very big mistake.
Nowerdays, Id use a quickfit setup, which isnt cheep, bu t its very reliable. As for speed, time vanishes in large am ounts for all
the chem istry I do, this means if your m aking nitric acid in a poorly ventalated room , t h e n y o u a r e e x p o s e d t o t h e v a p o u r s f o r
a long time (many hours). Just some suggestions from my very early days, if Id known what I kno w now, Id have m a d e m yself
wait until I could do it properly, and safely. I know you wont, because I know what I was like then.
Lastly, how b adly doe s it stain ? It eats through all natural fibres surprisin gly quickly. Its not a mop up job if it spills, its mop up
(eg sodium bicarb) and buy new carpet.
PYRO500 October 23rd , 2 0 0 2 , 0 8 : 2 8 P M

Another thing I'll add is that P VC is unsutable for HNO3 production, as with viynl tubing. th e only tubing I'd recomen d for
venting gas is Teflon (pfte) or Poly Eth ylene (PE) I currently use the latte r in my setup as som ething to con nect a vacuum
source to m y still. I would not recom end distilling HNO3 inside at all. anything plastic etc that the NO2 gasses touch are going
t o b e o x i d i z e d a n d t u rned to goo. Also the gasses will k ill you as there very deadly.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid >
Microreactor production of NO
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I have found some information about using microreactors to simulate the conditions of the Ostwald process for the production of nitric acid. Microreactors are small microchip
sized chemical reactors that have conditions similar to their industrial counterparts. I find this data relevant because it I am also trying to build a microreactor, although bigger.
First we consider the reactions we are going to encounter:
4NH3 (ammonia) + 5O2 (oxygen) --> 4NO (nitric oxide) + 6H2O (water) - 904 KJ
4NH3 (ammonia) + 6NO (nitric oxide) --> 5N2 (nitrogen) + 6H2O (water) - 1816 KJ
2NH3 (ammonia) --> N2 (nitrogen) + 3H2 (hydrogen) + 93 KJ
Experimental tests varying only the initial reaction temperature (pressure, 1 atm held constant) show that equations 1 and 2 are very competitive with each other at 400 C,
whereas equation 3 can largely be neglected. For equations 1 and 2 only, the amount of ammonia consumed is 70%, and the conversion into NO is 1.9%. Factoring in equation
3, the amount of ammonia consumed is 72% and the yield is 1.9%.
Increasing the initial temperature up to 1400 C shows that equation 2 becomes negligible, and equation 3 competes with equation 1. At this temperature we see 84% of the
ammonia being consumed and 46% being converted into NO.
Varying the temperature over a wider scale, a clearer picture of optimal temperature conditions can be seen. Keep in mind that at low temps, equation 2 dominates, and at
extreme temps, equation 3 dominates. We wish to find the best temperature range where equation 1 dominates, and the yield of NO is highest:
Temp: 200 C - 400 C 600 C - 800 C 1000 C 1200 C 1400 C 1600 C

Yield: 0.5% -- 2% ----- 26% --- 63% --- 74% ----- 63% ----- 46% ----- 31%
Notice that at 1000 C we get the highest yield of NO. It is the range, between 800 C to 1200 C, that we want to shoot for. Of course the reaction itself will generate heat, and
that heat will affect the equilibrium of the reaction. Furthermore, the catalyst chamber will be at different temperatures through its length. The temperature of the reaction will
increase until equilibrium is reached, and there will be different reactions temperatures from start to finish. The real world data on this are as follows:
Init temp:- 200 C -- 400 C --- 600 C --- 800 C -- 1000 C - 1200 C - 1400 C - 1600 C
Exit temp: 1406 C - 1566 C - 1637 C - 1695 C - 1744 C - 1790 C - 1838 C - 1894 C
Real Yield: 37% --- 39% ----- 37% ---- 36% ---- 33% ----- 39% ----- 25% ----- 21%
Now this shows us there is little real difference between any reaction temperatures, except at higher levels. Factoring in pressure drop as the reaction proceeds through the
catalyst chamber, we get a slightly different picture on our yield. The pressure drop is the result of reactants being consumed thus decreasing the interaction between ammonia
and oxygen. This does not mean the real pressure changes. Dont tell me in a whiny voice that the number of moles of substance could increased thus increasing the volume of
gas causing a net increase in pressure, because I can see that. This pressure drop is using a chemical engineers definition.
Init temp:- 200 C -- 400 C --- 600 C --- 800 C -- 1000 C - 1200 C - 1400 C - 1600 C
Exit temp: 1288 C - 1484 C - 1564 C - 1628 C - 1682 C - 1732 C - 1785 C - 1848 C
Real Yield: 26% --- 34% ----- 35% ---- 33% ---- 30% ----- 26% ----- 22% ----- 18%
Now we can see that a rise in temperature is actually bad for NO production. How does all this relate to a means of actually producing nitric acid on a scale that is useful? These
results show that the temperature of the system is the most important factor. The remaining data from these experiments shows that the actual pressure drop is about 50% to
0.5 atm, changing the length of time that the ammonia is in contact with the ammonia is best at 0.0003 s, and that the minimum ratio of oxygen to ammonia is 2:1, but these
factors change the actual yield very little.
As you can see, there is a big difference between starting this at 200 C versus 600 C. It would seem to me that once this reaction gets going, any external heat should be
removed, or reduced, so the reaction can commence. It also occurs to me that some means of measuring the temperature of the system might be beneficial. The final
recommendation of these experiments is to maintain a temperature at 1000 C.
There are a few insightful guidelines that can be gleaned from this data. First we will start with the ratio of air to ammonia. You may tell from equation 2 that the presence of
too much ammonia may contribute to that reaction. These experiments have demonstrated this is the case. It seems to me that you cant really go wrong with increasing the
flow of oxygen. There is only a slight change in the % yield by changing these ratios. All of the data I have indicates that an optimal ratio of oxygen to ammonia is around 7:1.
While this will vary from system to system, it is not really an important factor, at least at this time. Ramping up the ratio of oxygen would be the best way to start if you have
no flow control, such as my system. I may include some pressure valves in my future designs to assist in the more precise control of both the volumes and the pressure of the
gas.
That leads me into the second factor, the pressure of the system. Again, there is little change in the yields based on the pressure, but if you can increase the pressure by all
means do so. I have data that says a range from 1 to 100 atm is equally acceptable. Industrially they have both low and high pressure systems. Following their example and
applying it to our needs, we need not concern ourselves with pressure. We could get by with an open system at atmospheric pressure just as well as sealing it up to increase
the pressure a few atms.
Third is our residence time. This is tricky to calculate, but easy to determine experimentally. Every system will have different conditions depending on the catalyst, the length of
the catalyst chamber, the fluid flow around the catalyst bed, and the speed of the fluid going through it. One could regulate the speed of the gasses going in by pressurizing the
system or increasing the gas flow. As the gas speeds up, the residence time decreases, and the amount of nitric acid changes. Experimentally you can speed up the gas until
you start to get unreacted ammonia detected as ammonium nitrate. Slow it down too much and you get no acid at all. Somewhere in the middle it will be optimal for you.
Again, every catalyst is different, as is every system when you stuff the catalyst in your reaction chamber.
I have just begun to think about how to detect the presence of unreacted ammonia. The original patent literature assumes you smell it, but that seems rather dangerous to
me. I hate the smell of ammonia, and I dislike breathing nitrogen dioxide gas. The NO2 gas may be heavy enough to sink, while the ammonia is detectable, but this seems so
unscientific. One could titrate the nitric acid and weigh it on an analytical balance to see how much extra ammonium nitrate there is, but for how many people would this be
practical? Maybe just boiling off all the liquid would work. Anybody have any good ideas?
Our last, and most important, factor is temperature. I see now that the presence of so much water vapor in my earlier experiments was very bad indeed. Unless you can heat
this puppy up to 600 C to start with, you will be wasting ammonia and time. The good news is that as the reaction proceeds it heats itself, and so you should be able to reach
temperatures of 1000 C even if you start at a low 200-300 C. In fact, since the lower temperatures favor the second equation, and since that equation produces twice as much
heat energy, the amount of wasted ammonia may be minimized. The one set of data I do not have is how long it takes the system to reach its equilibrium temperature.
I have a pyrometer laying around somewhere; I hope it still works. I actually had some data that showed the equilibrium temperature of this system, but I lost it. I think it is
600-800 C, which is pretty good. Experimentation with temperature monitoring would seem in order here.
rikkitikkitavi June 20th, 2002, 08:00 AM

One idea about detecting NH3:
Any NO2 formed decomposes into O2 and NO above 300 C.
This means that the hot gases after the catalysts contain little NO2.
NO has very low solublity in water.
NH3 is very soluble in water. The dissolving process of NH3 is faster than NO + O2 = > NO2 and the NO2-dissolving process.
My idea:
letting the hot reaction gases after the catalyst enter a scrubber (washing column) any NH3 resident is dissolved , and the short resident time means that little NOx is lost this
way, and the sideeffect is that the gases leaving the scrubber are cooled, which is good for our synthesis of NO2.
Most of the heat generated in the catalyst is cooled away in the scrubber. But water has very high heat capacity, which is important since NH3 solubilty goes down when
temperature goes up.
Measuring the pH(f e x with a pH-meter) at the output could give a indication of how much free NH3 is present.
/rickard
vulture July 8th, 2002, 05:45 AM
The thing I'm worried about is reaction 3 competing with reaction 1, hot NOx, O2 and H2 in a reactor would very likely cause an explosion.
[ July 08, 2002, 04:45 AM: Message edited by: vulture ]

I did have some data on that, and there is that possibility. However, it cam be minimized because the temperatures required to do this are much higher than the system is run
at, and there is a rather narrow % gas mix to get explosion levels. By diluting the gas with enough air, you can bring down the risk. Proper temperature control will also
e,iminate the risk. If allowed to proceed with enough insulation, a system can just about double its heat to temps able to detonate the gas mix. This problem is only a problem
on a very large scale where thermal dissipation is more difficult. On the bench scale (and in microreactors) you can get it that hot because you could not pour enough reactants
into the system of this size.
If you allow the gasses to accumulate in a confined space for a long enough time, sure you can get an explosion, but this is very unlikely. In order for this to happen you would
need to just let it vent into the open in a tiny room. Why you would want this much heat in a tiny room with it just spewing nitrogen dioxide gas all over is beyond me. If this
is the case you are obviously not watching your experiment and you have other problems like nitrogen dioxide spewing all over.
THe_rEaL_dEaL February 19th, 2003, 10:53 AM

A question for the multiple flask process to ensure maximum NO2/NO conversion to Nitric.
Is pollyproplyene plastic resistant to concentrated nitric acid?

If so I have heard that the flexible, black reticulation piping sold in hardware and retic stores is polly pro. Also soft drink bottle plastic used in the 600ml variety is supposedly
polly pro.
This could be very useful plastic. :)
[ February 19, 2003, 09:58 AM: Message edited by: THe_rEaL_dEaL ]
Anthony February 19th, 2003, 02:37 PM

Plastic labware is made of polypropylene, and IME is HNO3 resistant.

Improvised Manufacture of Nitric Acid > Distilling Nitric Acid
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jarrod February 15th, 2003, 05:32 AM

I am in the motion of putting together a .pdf and maybe later on a homepage. Anyways I put this together and was hoping for
input, anything I left out or if you know a way of increasing yeld/efficiency, I dont have much experience in publishing so any
criticism is welcome. :p
If any see their work in here and dont want it to be a part of a .pdf just say and it shall be removed.
Distilling Nitric Acid
DISCLAIMER
This is NOT my work, but the work of others pieced together, not even the quotes are mine. I am mealy an editor aiming for a
complete simple guide for distilling nitric acid.
PREPARATION
Potassium Nitrate (KNO3)
Most agricultural grade nitrates come in the form of "prills". These are little BB sized pellets that need to be treated before
they can be used.
You'll first dissolve the prills in the minimum amount of boiling water possible. This will remove the coating that some
fertilizers have, and save you the hassle of grinding them to powder.
Once the prills are dissolved, filter while hot, and allow to cool while covered. The solution will precipitate out crystals of pure
nitrate. The longer it takes to cool down, the larger and purer the crystals.
Filter the crystals and wash with a small amount of cold acetone or 99% isopropyl alcohol to remove the last traces of
contaminants.
After letting the crystals dry out, you now put them in an oven to remove the water of crystallization. This is the water that is
molecular bound to the nitrate.
To remove it, you place the nitrate is glass or ceramic casserole dish so that it's spread out in a thin layer.
Turn the oven on to 250F (120C) and occasionally stir it till it no longer steams and falls apart into a fine powder.
Remove from the heat and immediately place it in pre-heated jar or can to keep it dry.
Sulphuric acid (H2SO4)
Chill the sulphuric acid in the fridge prior to distillation, a low initial temperature will help dissipate the heat during addition,
minimizing the amount of HNO3 disintegration to NOx that occurs.
DISTILLATION
Notes:
I would recommend only doing small batches, especially at first.
To determine the proper amount of nitrate to use with any given amount of acid, you divide the weight of the acid by 98.
Multiply the results by the molecular weight of the nitrate that you are using.
For instance, you have 196 grams of sulphuric acid. You also have potassium nitrate. Potassium nitrate has a molecular weight
of 101. So, 196 / 98 = 2, 2 multiplied by 101 = 202. Thus, you'd use 202 grams of potassium nitrate with the 196 grams of
sulphuric acid.
Though, in actual practice, you'd want to use a slight excess of acid to ensure a complete reaction
You MUST use an oil bath for this. The oil bath eliminates hot spots, and reduces the tendency to "bump". Vegetable oil is
ok, and it's cheap. Mineral oil is better. Don't try motor oil, it stinks like hell when you heat it.
Its a good idea not to fill the distilling flask more than one third full as the goo tends to foam up a lot.
RIG PREPARATION
Set up your distillation rig
Dont let the round bottom flask touch the bottom of the oil bath
DO NOT use a gas burner for this. This procedure requires the temperature to rise very slowly.
You need to fully submerse the flask (to neck base) to minimise refluxing.
If you don't have access to a fume hood, you can do this in front of a window with a fan. The vapours are intensely
poisonous, and the condenser will not stop some of the oxides of nitrogen, which are formed.
PROCEDURE
To start, place the concentrated sulphuric acid in the container that's going to be heated. Next, cautiously and in small
portions add with swirling or stirring with a glass rod, the dry powdered nitrate by means of a funnel. If there's any visible
fuming, STOP! Get upwind and wait a few minutes for it to stop. Then continue until the entire nitrate is added and well wetted
by the acid. There should be no clumps.
No matter how slowly you add the nitrate you will always get white HNO3 (nitric acid) vapour being emitted, although it's not
pleasant to breathe it's the red/brown N2O that theyre warning against.
After standing for about an hour in the closed flask, the mixture is heated cautiously.
The temperature needs to be brought up slowly to 83C (not over 86C), over the period of an hour (1.4C A min), because
there is a substantial lag between the temperature that the oil reaches and the temperature in the flask. You don't want to
overheat it
It took a fair amount of time after the boiling started for the acid to start coming
over, which tells me that you have to drive the reaction pretty hard in order to get the nitric acid form in the first place.
The first thing you get is a bunch of dark brown vapour, but it turns clear once the acid starts distilling over.
The round bottom flask, which is used for collecting the distillate, has to be cooled well, e.g. by placing it in a beaker that is
filled with ice water.
In the experiment the nitric acid that distils is almost pure (@83 - 85 C).
As soon as larger amounts of brown NO2 are formed and the distillate has a brownish colour, the reaction is stopped.
Are larger amounts of HNO3 to be prepared, one should use a ground distillation apparatus and distil multiple times under
vacuum in any case. The boiling point of the acid is about 36 - 38 C @26 mbar, so a water bath is sufficient for heating.
I am grateful for any input
thanx :)
xyz February 15th, 2003, 09:00 AM

Maybe some info about H2SO4 sources? Like bought H2SO4, boiled battery acid, drain opener, etc. Maybe also say that it can
be concentrated simply by boiling in a pyrex container.
jarrod February 15th, 2003, 09:18 PM

A Pyrex container???
How does that work, Ive heard of some pretty weird ways of obtaining H2SO4 but Pyrex containers. Wouldnt there be a large
amount of contaminants, such as ink, dyes in bottle, traces of contents from what was in the bottle, How pure would the
H2SO4 be?
xyz February 15th, 2003, 10:00 PM

Pyrex glass, the stuff that lab beakers are made of. It is glass that will not crack or shatter when heated. You can't use a
metal container as it would be attacked by the acid and normal glass tends to crack when heated.
All you would do is take your low conc. H2SO4 and boil it in a pyrex container until all the water was removed.
Edit: I am not saying that the H2SO4 is made from pyrex containers, I am saying that it can be concentrated by boiling it in
one.

Yeah sorry
I misinterpreted what you said
Marvin February 17th, 2003, 03:25 AM

Its mostly good advice, but writing a text on something you havnt tried at least several times yourself isnt a smart move.
I have to take issue with the oil bath though. In terms of decomposition, the oil bath is pointless, heating the flask above the
level of the contents is a bad idea, if your getting much refluxing you probably arnt distilling rapidly enough, and you should
speed up and/or lag the exposed glassware with glass wool.
If you have a pyrex distilling flask, then direct heating with an electric mantle, or carefully with a non luminous (only blue
should be visible) gas flame always below the level of the contents is fine.
If the glass distilling flask is in any way suspect (apart from having cracks in it, which is not acceptable), then very slow, very
even heating with a sand bath or low power electric mantle will be the method most likey to leave it intact at the end of the
distillation.
Glass bottles, containers etc not designed for heating break very easily, but for those people desperate enough to try it, a
sand bath is the way to go.
The temp at which the nitric distills varies a lot with the salt, the amount of water in the sulphuric, and the acid ratios, but
expect it to be a lot higher than the boiling point of nitric acid alone, particulaly neer the end of the reaction. Your driving it out
of the mixture, as one of the quotes says.
An oil bath containing a flammable unsaturated oil (If its liquid at RTP, then its doubtless unsaturated) at well in excess of
100C outside a flask containing nitric acid, oxidising salts and sulphuric acid at the same temperature is potentially the last
experiment someone ever does.
In my experience oil baths are never worth the trouble, even when they arnt dangerous. Buy a heating mantle, they are worth
the money is my advice, as is pyrex lab glassware for distillation.
You need some specific health information for both nitric acid, and NOx gasses, as well as what they do to you and why.
Search the web, read the MSDS, make sure it is accurate, under and over caution are often equally unsafe in a how-to text.

Thanx for the tips but a couple of questions
Im writing this for my own synthesis because I dont trust any I just read on the internet ( I had a bad experience with LEs
:mad: ), and after several successful distillations it shall be published.
Could any type of insolation (using common sense) work for the prevention of refluxing.
Money is the problem :( so a heating mantel is out of the question, for now anyway. I assume the sand for the sand bath
should be dry and as fine as possible.
THE MOST IMPORTANT question I ask is there a table with the salts/acid ratio. the main one I am after is KNO3/100%H2SO4.
Anthony February 17th, 2003, 11:05 AM

As Marvin said, glass wool is a good choice of insulation. It's cheap, easy to find, a good insulator and I doubt it would react
adversely if you were to get HNO3 on it.
If you're really broke, just go up to the loft of your house and grab a handful (wear gloves...).
For the KNO3/H2SO4 you can work out the stoichiometric ratio using a periodic table. Although it may be better to have an
excess of one reactant, I'm sure other members will advise.
Al Koholic February 17th, 2003, 05:12 PM

Even using a sand bath with glass that is not made for heating will not prevent the cracking of the vessle. The glass simply
cannot handle the temperature gradient you will require for this operation. I have tried mulitple times to heat standard glass
with a fine sand bath very very slowly and steadily and each time, hairline fractures form which only increase in size as you
continue heating. This was only to boil water mind you in experiments to see if it could be done.
Its really interesting actually. You'll be sitting there and all of a sudden, you'll hear a somewhat loud *snap*. Nothing will
happen and you'll think...oh, must have been some water vapor in the sand escaping, or the metal on the hotplate is flexing
or something. Then you'll hear another snap or two and get curious..."what could that be?!" You'll go to the jar which you have
been heating soooo ultimately carefully and the water in it is still there, its not boiling just steaming. You pick up the jar/bottle
with potholders and all of a sudden you have a steam plume coming at your face and sand/water splattering around because
the bottom of the jar just cracked to the point of separation from the body of the jar but nothing happened till you picked it
up. Ive never been able to avoid this with a sand bath and regular glass jars/bottles. Just my 2 cents so if I were you, just use
laboratory glassware made for heating. Especially with something like distilling HNO3....
ALENGOSVIG1 February 17th, 2003, 05:21 PM

For cheap insulation wrap fleece around the flask. If your really desperate, wrap some alumininum foil around the flask but
make sure its not tightly wraped. It should be like a dome around your flask with airspace in between the flask and foil. The
foil doesnt work nearly as well as glass wool or fleece but it works in a pinch.
And i dont think its necessary to remove the coating off the prill unless theres lots of it. Ive never removed the coating off my
fertilizers and ive never had a problem. My ferts contain very little coating though.
[ February 17, 2003, 04:27 PM: Message edited by: ALENGOSVIG1 ]

I tried a heating test of just normal glass containers about an hour ago and found beer bottles to be the best :D , but I only
tested 5 different kinds of glass containers. From these tests I have to agree that normal glass will not do and a distillation rig
is next on the list of things to buy.
I just found a supplier of H2SO4 who wants $24AUD for 5letres at 90%
Im a bit suspicious because the average price is normally $40 (if you shop around here) but is around 98%. Is there anything
to look out for when purchasing. I really dont want to kill myself :p . And also can store brought HS2O4 (floor cleaner) just be
boiled for concentration like in a battery
thanx

Where do you live? I can get 98% H2SO4 for $40AUD for 15L from the hydroponics shop near me, and I also know a chem
supplier 2 hours from where I live that sells it for $17.50 for 15L.
jarrod February 22nd, 2003, 08:34 AM

I live I northern Queensland (Townsville) and only 2 shops in my town stock it, out of about 8 industrial chemical suppliers.
The two hydroponic stores said they dont sell it or order it. One of the stores gave me lip, quote when I answered the phone
I said NQ hydroponic supplies not NQ chemical supplies. The lab supplies store wants $55 for 2.5l
If I used Teflon tubing with a bore of 20mm and a couple of ice packs for a condenser would this do. I ask because a
condenser is $352.25 from my supplier, does that sound right?
i think im getting screwed :mad:
thanx
xyz February 22nd, 2003, 11:04 PM
The H2SO4 from the lab supplier is probably so expensive because it is an ultra pure lab grade, you need to find a source that
dells the 99% pure industrial grade, not the 99.99% lab grade.
Condensers are so expensive because the Aus government thinks people will use them in alcohol/drug manufacture. If you
buy one, the lab supplies people have to clear it with the drug squad first.
I would simply have the teflon tube going into the top of a bucket of ice water and then coming out of a hole in the bottom.
Where did you get your teflon tube? I have looked for some before but then decided that my nitric acid still would have to be
glass.
knowledgehungry February 23rd, 2003, 07:16 PM

If they charged 352.75 in the US you would definitely be getting screwed... You can get them for around 40$ here. But i am
not sure about the exchange rate between US and AUS.

1$AUD is about half the value of 1$USD, so in Australia you SHOULD pay about $80AUD. Like I mentioned before, "they" think
that the stills you use the condensers in will be for alcohol/drug manufacture.
[ February 24, 2003, 03:43 AM: Message edited by: xyz ]

I found a cheap supplier. :D They want $14- 1000ml RB flask, $8 -500ml RB flask, $40- for quick fit glass joints (both) and
$85 for a condenser. They also had a 125ml retort for $4.50. Thats my rig set up for almost $150 AUD the only problem is
the glass is borosilicate BOMEX brand. I dont know much about this type of glass so does anyone know if it will do with the
strong acid fumes and heating. :confused:
Also would a longer condenser (700mm) be better for this purpose than (300 or 400mm) to allow for a longer cooling period,
or have I overlooked something.
Thanx
[ February 26, 2003, 04:02 AM: Message edited by: jarrod ]

All glass will withstand HNO3, and as it is lab glass it should take the heat, I am not 100% sure though.
NERV February 26th, 2003, 04:33 PM

I have several beakers, and flasks made out of BOMEX. They can esaly take heating, and are as chemical resistant as any
other type of glassware.
Mr Cool March 4th, 2003, 05:37 PM

I was wondering what people thought of using NH4NO3 and NaHSO4 to make nitric
acid by distillation? I wouldn't want to melt it dry in case the NH4NO3 decomposed, but what about
adding around 50mL of water per 80g of NH4NO3 / 120g of NaHSO4 and distilling off
fairly strong HNO3, for further concentration from H2SO4?
pKa's of HNO3 and HSO4- are -1.3 and 1.9, respectively. So although HNO3 is the stronger acid, might the fact that it can escape help drive the equilibrium towards HNO3? Would it
escape at an adequate rate for condensation?
I'd like to try it but I have no NaHSO4, maybe I will pick some up soon unless anyone thinks this is just a stupid
idea.
Then, the NH4NaSO4 will, I think, decompose on heating to give off NH3 and re-form
NaHSO4, which can be re-used.
If it works this method would have several benefits:
No H2SO4 is consumed, so it can be saved for other reactions;
NH4NO3 is very cheap, so HNO3 of around 60% concentration could be made for less
than 1/L;
NaHSO4 is re-formed so you don't have to spend money on large amounts of it, only NH4NO3 is consumed;
Only readily available, cheap chemicals are required.
What do you think? I know that NaHSO4 can be used at higher temperatures with k/NaNO3, but in
this case the NaHSO4 is consumed, leading to further cost. So basically, I need to know if this reaction will occur
at lower temperatures - are higher temperatures just used to melt the dry reactants and allow the reaction to proceed, or are
they necessary due to the kinetics of the reaction?
xyz March 7th, 2003, 07:42 PM

I am also interested in this method of HNO3 production. I have about 25-30Kg of NaHSO4 so I am not all that bothered about
using it up in the process (if I use KNO3). What sort of concentration could be reached using NH4NO3 and would the
concentration be any higher if you used KNO3?
knowledgehungry March 8th, 2003, 10:19 PM

Does silicone react with Nitric? I ask because i need something to seal my distillation apparatus.
I think it would. Use some teflon plumbers tape to seal it.
jarrod March 15th, 2003, 10:36 PM

Maybe just cotton bandages from a first aid kit, local chemist wherever dampened with distilled water wrapped tightly around
each joint. This way you can easily remove the seal whenever you needed to take it apart.
im not sure if there would be enough fumes to form a low conc. acid on the bandages. Anyway watch the fingers <img
border="0" title="" alt="[Wink]" src="wink.gif" />
[ March 15, 2003, 09:41 PM: Message edited by: jarrod ]
VX March 15th, 2003, 10:48 PM

You could use a thin layer of Vaseline, or silicone grease without problems, you could also use PTFE tape.
Do not however use wet cotton! This will not form an airtight seal, and the fumes will be strong enough to acidify the water,
and then react with the cotton, at the same time as the heat is causing the water to evaporate (making the seal even less
airtight) and the cotton to burn.
ALENGOSVIG1 March 16th, 2003, 03:44 AM

You really shouldnt use anyhting but glass or teflon throughout your entire setup. Anything else is liable to dissolve and make
a big sticky mess, or worse, catch on fire.
I once tried to use a plastic threaded thermometer adapter for distliing HNO3. Big mistake! I left it for an hour to go shopping
and when i came back theres was no adapter, just long black smear down the 3-Way Adapter. :o
Thought it would up for awhile longer than that!
jarrod March 17th, 2003, 08:30 AM

A bit off topic but would any one be interested in a full step-by-step document for purifying nitric acid using urea and
bubbling air through the acid.
I have almost finished composing this document and thinking about posting, if there is interest.

Please, post away! We're collecting all information on getting, making and/or purifying nitric acid, so that bit of information will
fit in nicely. It might be a good idea for you to start a new topic on NOx elimination if there isn't one already.

Well the silicone appeared to have melted and not only that as i was checking the seals during distillation my still kinda blew
up <img border="0" title="" alt="[Eek!]" src="eek.gif" /> . I got sprayed in the arms with some hot nitric... not plesant.
Fortunately i was wearing lab goggles. The glass didnt shatter... just the joints were blown apart. I think im gonna give in and
buy some DCM off Ebay instead of attempting any more distillation.
ALENGOSVIG1 March 17th, 2003, 10:54 PM

What kind of a still do you have? Ive never really had an incident when distilling nitric, and ive distilled gallons of the stuff.
Are you using proper glassware or is it ghetto rigged? Is it jointed glassware? Like 24/40, 45/50, etc.
[ March 17, 2003, 09:55 PM: Message edited by: ALENGOSVIG1 ]

Mr Cool or others , do you know any patient numbers or web sites/documents that relate to the topic of purifying the acid. I
cant finish my document until I obtain a little more information, and I have searched over four hours a day for many days.
Google, patient databases and science search engines as well. It is REALLY FRUSTRATING not being able to find anything
besides the limited info I already have.
Maybe a book that has been scanned or anything you can think of.
ALENGOSVIG1 - I have finished the final copy of the distilling procedure, and thought that uploading it to the forum FTP was a
good idea, but I do not have FTP access :( so I ask if you could do this on my behalf, if you are not to busy. (it is a M/S word
doc, size 633kb)
thanx
[ March 18, 2003, 06:48 AM: Message edited by: jarrod ]
ALENGOSVIG1 March 18th, 2003, 01:06 PM

Email it to alengosvig@yahoo.com and i'll be happy to upload it for you.

Here is the final copy. :)
Distilling Nitric Acid
DISCLAIMER
This is NOT my work, but the work of others pieced together, not even the quotes are mine. I am mealy an editor aiming for a
complete simple guide for distilling nitric acid.
Reference: <a href="http://216.239.39.120/translate_c?hl=en&ie=ASCII&oe=ASCII&langpair=de%7Cen&u=http://

www.chemikalienlexikon.de/cheminfo/betran/si_daten/0501-sic.htm" target="_blank">Safety references nitric acid </a>
ITINERARY
this got screwed up with the UBB coad
PREPARATION
Potassium Nitrate (KNO3)
Most agricultural grade nitrates come in the form of "prills". These are little BB sized pellets that need to be treated before
they can be used.
You'll first dissolve the prills in the minimum amount of boiling water possible. This will remove the coating that some
fertilizers have, and save you the hassle of grinding them to powder.
Once the prills are dissolved, filter while hot, and allow cooling while covered. The solution will precipitate out crystals of pure
nitrate. The longer it takes to cool down, the larger and purer the crystals.
Filter the crystals and wash with a small amount of cold acetone or 99% isopropyl alcohol to remove the last traces of
contaminants.
After letting the crystals dry out, you now put them in an oven to remove the water of crystallization. This is the water that is
molecular bound to the nitrate.
To remove it, you place the nitrate is glass or ceramic casserole dish so that it's spread out in a thin layer.
Turn the oven on to 250F (120C) and occasionally stir it till it no longer steams and falls apart into a fine powder.
Remove from the heat and immediately place it in pre-heated jar or can to keep it dry.
Sulphuric acid (H2SO4)
Chill the sulphuric acid in the fridge prior to distillation, a low initial temperature will help dissipate the heat during addition,
minimizing the amount of HNO3 disintegration to NOx that occurs.
DISTILLATION
Notes:
I would recommend only doing small batches, especially at first.
To determine the proper amount of nitrate to use with any given amount of acid, you divide the weight of the acid by 98.
Multiply the results by the molecular weight of the nitrate that you are using.
For instance, you have 196 grams of sulphuric acid. You also have potassium nitrate. Potassium nitrate has a molecular weight
of 101. So, 196 / 98 = 2, 2 multiplied by 101 = 202. Thus, you'd use 202 grams of potassium nitrate with the 196 grams of
sulphuric acid.
Though, in actual practice, you'd want to use a slight excess of acid to ensure a complete reaction.
You MUST use a sand bath for this. The sand bath eliminates hot spots, and reduces the tendency to "bump". The finest
sand possible (smallest grain) and it should be dry.
Its a good idea not to fill the distilling flask more than one third full as the goo tends to foam up a lot.
RIG PREPARATION
Set up your distillation rig
Use a thin layer of Vaseline to make an air tight seal around the joints.
Dont let the round bottom flask touch the bottom of the sand bath as a hot spot may occur.
DO NOT use a gas burner for this. This procedure requires the temperature to rise very slowly.
You need to insulate the neck and non-heated areas of the flask with glass wool to minimise refluxing.
If you don't have access to a fume hood, you can do this in front of a window with a fan. The vapours are intensely
poisonous, and the condenser will not stop some of the oxides of nitrogen, which are formed.
PROCEDURE
To start, place the concentrated sulphuric acid in the container that's going to be heated. Next, cautiously and in small
portions add with swirling or stirring with a glass rod, the dry powdered nitrate by means of a funnel. If there's any visible
fuming, STOP! Get upwind and wait a few minutes for it to stop. Then continue until the entire nitrate is added and well wetted
by the acid. There should be no clumps.
No matter how slowly you add the nitrate you will always get white HNO3 (nitric acid) vapour being emitted, although it's not
pleasant to breathe it's the red/brown N2O that theyre warning against.
After standing for about an hour in the closed flask with occasional swirling or stirring with a glass rod, the mixture is heated
cautiously.
The temperature needs to be brought up slowly to 83C (not over 86C), over the period of an hour (1.4C A min), because
there is a substantial lag between the temperature that the sand reaches and the temperature in the flask. You don't want to
overheat it
It took a fair amount of time after the boiling started for the acid to start coming
over, which tells me that you have to drive the reaction pretty hard in order to get the nitric acid form in the first place.
The first thing you get is a bunch of dark brown vapour, but it turns clear once the acid starts distilling over.
The round bottom flask, which is used for collecting the distillate, has to be cooled well, e.g. by placing it in a beaker that is
filled with ice water.
In the experiment the nitric acid that distils is almost pure (@83 - 85 C).
As soon as larger amounts of brown NO2 are formed and the distillate has a brownish colour, the reaction is stopped.
Are larger amounts of HNO3 to be prepared, one should use a ground distillation apparatus and distil multiple times under
vacuum in any case. The boiling point of the acid is about 36 - 38 C @26 mbar, so a water bath is sufficient for heating.
<a href="http://216.239.39.120/translate_c?hl=en&ie=ASCII&oe=ASCII&langpair=de%7Cen&u=http://
www.chemikalienlexikon.de/sichhinw/entsorg/entsorg.htm" target="_blank">References to the disposal</a>

It is standard lab glass however it is not a vacuum distillation. It is a flask an adapter then another flask.<blockquote>code:<hr /><pre style="font-size:x-small; font-
family: monospace;">
//============\
II \\
Il Il
/ \ / \
\__/ \__/
^^flame </pre><hr /></blockquote>Thanks Anthony.
[ March 19, 2003, 09:52 PM: Message edited by: knowledgehungry ]
Anthony March 19th, 2003, 09:04 PM

A few spelling/grammar errors.
"The finest sand possible (smallest grain)"
Is that really important? I'd have thought as long as it wasn't gravel, it wouldn't have made much difference.
"the goo tends to foam up a lot"
Nice tech term <img border="0" title="" alt="[Wink]" src="wink.gif" />
"Use a thin layer of Vaseline to make an air tight seal around the joints"
I'm not sure on this one, but it doesn't sound right - HNO3 vapour in contact with flammable hydrocarbons. IMO I'd use teflon
(PTFE) plumbing tape if leak sealing is required.
"If there's any visible fuming, STOP! Get upwind and wait a few minutes for it to stop"
I think you need to stipulate red/brown gas, rather than just "fuming", to avoid confusion. The appendum concerning NOx
added on the end seems disjointed, and why write something and then correct it, just say it right first time :)
"After standing for about an hour in the closed flask with occasional swirling or stirring with a glass rod, the mixture is heated
cautiously"
It would be useful to state *why* the mixture needs to stand for an hour. To cool down? Worth saying as it will be variable. To
allow it to react? Does it really take that long? I've never waited that long when doing nitrations with xNO3/H2SO4.
BTW knowledgehungry, use the CODE tags to stop UBB screwing with your ASCii art.
Mr Cool March 20th, 2003, 11:40 AM

Knowledgehungry, where's the port to allow the expanding gases to escape? Once the mixture and everything else is up to the
right temperature and you're distilling you shouldn't have a problem, but while you're heating it up the air will expand and pop
your joints out.
Anthony, I use vaseline to lube the joints. You don't need it to get a seal, but it stops the joints from jamming together. I've
never had a problem, and I doubt that I ever will. You only need a tiny amount, even if it did burn not much would happen.
And consider that it never gets above 90*C ish.

K, just wanted to be sure :)
knowledgehungry March 21st, 2003, 10:04 AM

Well that is kind of the problem. I didnt use an outlet for the gas to escape. I knew i should have but i thought that i would
have to keep the hole open the whole time, but now that i have been informed that there needs to ba a vent only while the
temparature is still climbing i think i might try it again with a vent of some sort. 90*C? Do you use a vac distillation?
Mr Cool March 21st, 2003, 03:42 PM

No, I don't use a vaccuum, but I do use 70% HNO3 + 98% H2SO4, instead of a
metal nitrate and 98% H2SO4. I haven't ever measured the temperature that it distils at, since the
thermometer that I have that can be attached to quickfit is not HNO3 compatible. But I would guess it to be no
more than 90*C, considering HNO3's boiling point.
Celtick March 23rd, 2003, 01:22 PM

How many ml of 98%H2SO4 do you use with an ?ml 70%HNO3?
Mr Cool March 23rd, 2003, 02:10 PM

I use a 1:1 ratio by volume of 70% HNO3 to 98% H2SO4.
To give you an indication of the usefulness (or otherwise) of the acid produced, 2mL of acid with 1g of HDN will give ~0.6g of
RDX using the common method (add HDN to acid at 20-30*C, raise temperature to 50-55*C once it has all dissolved, hold for
5 minutes, cool to 20*C, hold for 5-10 minutes (I chose to use 7 minutes, for no particular reason), dump into water, wash,
recrystalise from acetone, dry). That is with a single distillation at atmospheric pressure, with no attempt made to remove
NOx, based on a batch using 15g of HDN and 30mL of HNO3, yielding 9g of purified RDX.
The acid will also give yields of purified PETN of between 85% and 90%, based on batches using 10g of PE and around 35mL
of acid (therefore >19g of PETN).
simply RED March 26th, 2003, 03:00 PM

Mr Cool, what equipment do you use for this distilation?

Quickfit, a 1L rb flask to heat the mixture in and a liebig condenser about 10" long roughly, cooled by syphoning water from
one big bottle on my bench to another that is below. Then I have a delivery tube to drip the HNO3 into a
collecting flask. I normally distil at a rate of about two drops a second, ie, heating strongly but not really blasting it.
xyz March 27th, 2003, 04:04 AM

Mr. Cool, What did you use for heating, distributing the heat, and stirring?
[ March 27, 2003, 03:05 AM: Message edited by: xyz ]
bubbling_beaker March 27th, 2003, 04:05 AM

hi,
Mr Cool; Is your entire distilation setup sealed, or does the HNO3 just drop from the condenser into your collection vessle?

Heated with a bunsen flame from below, no extra effort is used to distribute the heat, no thermal insulation is used on the
flask containing the mixture, and the only stirring is that provided by the bubbles in the boiling liquid. I use a few pieces of
silica grit as anti-bumping granules.
So, just normal heating really :) .
My entire setup is not sealed; the end of the delivery tube that is attached to the condenser is open, allowing the acid to drip
into an open beaker (which, btw, I never bother to cool down).
To clarify, <a href="http://www.boomspeed.com/mrcool/DistillationSetup.jpg" target="_blank">here</a> is a picture of the

glasswear that I use for simple distillation. Also shown, on the left, is a simple fractionating column.
[ April 03, 2003, 01:20 PM: Message edited by: Mr Cool ]
jarrod April 5th, 2003, 06:47 AM

I have recently completed my purification method, sadly though there is very little information on this topic. :( If there is info
out there then I sure as hell cant find it. :mad: The information I have found left the reader open to interpretation, there for I
am positive the synthesis I have composed is going to have errors all through it.(this is why it is not a new poast) This is
where I ask that you let me know where I can fix it up, since multiple opinions is always the best method of obtaining the
correct information. (or close enough to)
Nitric acid purification
PURIFICATION
The nitric acid obtained at the end of my distillation is red to yellow-red. What this means is there is NOx present in our acid.
NOx is not wanted so we need to extract it using an air pump, Teflon tubing and urea. The air used for bubbling needs to be
dry, the air around us has too much moisture in it. To dry air is to desiccant air, for those that didnt know that <img
border="0" title="" alt="[Wink]" src="wink.gif" /> .
PREPARATION
Obtain a tube that can be used for drying gases eg, U-tube (an improvised tube will do) and fill tube with the drying media.
(Silica gel, Activated Clay (Montmorillonite) or others.)
Get your pump and find the inlet hole/valve, (this is where it sucks the air in) put your thumb over the hole to completely cut
off intake. Turn the pump on and see if air is still being pumped through. If so then take you pump apart and find where the
air is being sucked in,(some pumps have more than one inlet.) To detect the air intake if it is not easily seen, blow smoke on
the pump area and you should be able to see where the smoke is being sucked in. After these holes are found, block them,
leaving one inlet open (use glue, silicon or whatever it calls for.)
Attach the drying tube to this hole/valve. Do not attach the glass directly! Use tubing, because this is how you will brake your
glassware. (But we all knew that already didnt we.) Make sure there is NO leaks, reinforce your joints with plumbers tape,
this is the white tape that is often around plumbing joints.
Hook the Teflon tubing up to the tubing from the pump (using an improvised joiner eg: duck tape.) Again make sure there
is NO leaks.
PRODUCER
First fill a round bottom flask with your impure nitric acid (not to full to allow for error, 1/2 is sufficient) we do this because
this because we dont want any acid to spill on our skin or cloths, OUCH!
After inserting the Teflon tube into the acid start bubbling dry air through it, (A constant stream of dry air, not so much as to
cause the acid to foam up but enough to have lots of nice little streams of bubbles, youse your judgment.) You can slow the
flow of air by slightly clamping the tube using a peg or something else.
Ratio for urea addition is 1g urea to 100g acid
For 100g acid add the urea over a time of 1 hour (0.1g every 10min) and continue bubbling for another 2 hours. (If you have
twice the amount of acid double the urea and the bubbling time, if three times then triple it, ect.)
(this was an educated guess)
Swirl the flask (for a good minute) every time you add urea and then every now and again for the remainder of the bubbling.
When bubbling is finished remove the tubing from the acid and while still inside the flask let any acid drip off.
Our acid is now ready for use in other synthesises.
BUBBLER
There are many ways to make a bubbler this is just one idea, just remember it all needs to be Teflon or resistant to the acid.
Make a bubbler by blocking the end of the Teflon tubing and poking holes in it. Start by cutting two 10mm lengths of tube off
the end.
Cut down one side so it folds out and you have a rectangle of Teflon. Flatten this piece. (In a clamp, under some books
ect) after it is flat and will not curl, cut a circle out that has a diameter the same as the bore of your tube. (keep the scraps)
DO THIS TWICE
<a href="http://www.angelfire.com/pro/jarrod/images.html" target="_blank">pic #1</a>
Carefully insert the circles as to perfectly fit and block the tube (DO NOT glue, place it and leave it there)
<a href="http://www.angelfire.com/pro/jarrod/images.html" target="_blank">pic# 2</a>
Cut strip of Teflon from the scraps you saved. Poke a hole through the very end of the tube, now thread the strip through
the holes. Thus blocking the most of the airflow, there will be air still coming out. (it should not be to much)
<a href="http://www.angelfire.com/pro/jarrod/images.html" target="_blank">pic #3</a>
Now poke holes up the tube for the next 40mm (after the circles finish) and there is your bubbler.
Test your bubbler in water and tinker until you have lots of nice little streams of bubbles coming from each of the holes you
poked.
Hook it all up so youre ready to pump Dry Air.
So what do you guys/gals think?
stanfield April 5th, 2003, 04:47 PM

interresting...
why the addition of urea must be so long ?
Today, I've tested this method :

H2SO4 + Ca(NO3)2*4H2O = 2HNO3 + CaSO4
my sulfuric acid : 96%
so, thoritically, 10ml of acid with 44g of nitrate...
I poured 10ml of acid in a small beaker then added, about 20g of nitrate an the stuff became like a paste ! impossible to stir
!
How the hell could I add 44g of nitrate in so few acid ? is the equation right ? are my ratio right ? (I did these calculation
quickly, so, there may be an error...
bye.
Marvin April 5th, 2003, 08:32 PM

When you ppt CaSO4 from conc solutions thats what always happens. Even from dilute solutions you get something that is god
awful to filter. Letting it settle, decanting and writing off the loss of product is normally easier. but its useless in this case. You
may find an excess of sulphuric acid helps prior to distilling, but so long as the nitrate is anhydrous, it should distill ok to good
nitric.
Thanx for the answer...
I wanted to try this method because many people say this is the best. (?)
ok, so if I well understood, by distilling (and so, heating) the mixture, it should be ok, that's right ?
I prefer asking before doing because I don't want to waste my sulfuric acid.
By the way :
One day I mixed 1:2 low nitric acid/sulfuric acid, and distilled this. At the end of the reaction I obtained a very good yield of
concentrated nitric acid and the distillation time was fine too.
So, I get back diluted sulfuric acid that I boiled down today.
At the begining of the heating, (when the acid is always cool...), the color of the acid was transparent. Next, it became red/
yellow because nitric acid remained. Next the mixture boiled and red fumes were released. At the end of the heating, the
sulfuric acid stopped boiling, blank fumes were releasing but yellow color remained, why ?? I think I get back near 100%
sulfuric acid but what is this yellow color ?
thanx !
[ April 06, 2003, 12:58 PM: Message edited by: stanfield ]
IPN April 6th, 2003, 02:47 PM

Sulphuric acid is colorless when it is very pure, but usually it is yellow (this happens when the concentration is very high).
Mine is always colorless after concentrating (from battery acid) but after a while it turns yellow :confused: .
So you don't have to be worried about the color.
From ChemFinder:
<blockquote>quote:<hr /> Colorless (pure) to dark brown, oily, dense liquid with sharp, acrid odor. HYGROSCOPIC. <hr /></
blockquote>

cool, I get back very high concentrated sulfuric acid ! fine.
What are the white fumes released ? sulfuric acid only boils at very high temperature, so these vapours aren't sulfuric acid...?
[ April 06, 2003, 05:19 PM: Message edited by: stanfield ]
IPN April 7th, 2003, 01:35 AM

The fumes are prob ably a mix of SO2/SO3 (I m no t sure though.)
Nothing really concerning unless you are working inside the house..

I made the addition of urea so long because I did not find any information at all with time frames, :( and after a bit of
thought I decided that bubbling should go for three hours and urea addition for one hour to ensure elimination of NOx. Also it
can always be corrected if new information comes to my attention.
Just to clarify what I said in my previous post. (this is why it is not a new post)
I intend to post this as a new topic so anyone searching can find it rather faster than having to read through many posts, just
to make things simpler. :) Also I would prefer to have a relatively correct procedure as to save confusion due to jumping
around a lot with ideas.
So any comments before I make the switch.
thanx
Mr Cool April 7th, 2003, 11:40 AM

White fumes from hot sulphuric acid are probably just sulphuric acid droplets. Vapour will come off even when it is not boiling,
as the vapour/air mixture cools the air can hold less, so the vapour forms droplets of acid which appear as a fine mist.
I normally don't bother to add urea to my nitric acid, after distilation it is only very slightly yellow and clears up after a small
amount of hexamine is added. It seems to do the job of urea. Once, though, I had a batch of quite dark yellow nitric due to
careless distilation, and I added around 1.5% of urea to it. I can't remember exactly, but it was a small amount of acid, 50mL
maybe. I added the urea all at once, very foolishly, and got a vigorous reaction which made the acid much darker (the urea
reacted with the acid, forming urea nitrate and nitrourea, releasing heat, which decomposed the acid). So add it slowly, with
stirring.
Anthony April 8th, 2003, 03:04 PM

I don't think it is a good idea to specify a specific time for the additions, unless who have a good reference for it, or have
determined it yourself emperically.
An specific instruction that is found to be inaccurate could bring the entire process(es) into disrepute/distrust.

I always added my urea in one time... never got a problem when making PETN...
HypersonicGamer April 14th, 2003, 07:45 PM

So if someone originally had a somewhat lower concentration of HNO3 (70%) and mixed it in a 1:2 ratio with H2S04 (98%) -
and distill, the yield would be a high concentration of Nitric Acid?
mongo blongo April 14th, 2003, 08:38 PM

Yes. The H2SO4 will absorb water and hold it back during the distillation.

Anthony - I also tho ught along tho se lines, but wha t guideline s do you give this procedure that don t have a qu antitative
ring, and that is still able to make sense for those just beginning. :confused:

Try it and see?
Some other members have also given brief accounts of their experiences.
jfk April 24th, 2003, 07:44 AM

Just a few things which might be of use/interest.
100% sulphuric acid isn't an acid, for it to be acidic there must be some water molecules for it to dis-associate into H[+] and
SO4[2-] in.
And Borosillicate glass is the stronger grade of glass that lab ware is made out of. According to my supplier you can heat
borosillicate glassware quite a bit higher than the other grade, which i hazard to say is just tempered glass.
knowledgehungry April 24th, 2003, 08:22 AM

I f you want to get technical JFK(i thought you were dead) 100% H2SO4(unless in a perfect vacuum) will have at least 1 H2O
molecule as H2SO4 is hygroscopic, there is no such thing as 100% pure anything.
Einsteinium April 24th, 2003, 04:31 PM

100% sulphuric acid isn't an acid Yeah, that's probably why they called it ACID :rolleyes:... Anhydrous (or theoretical 100%
pure) sulfuric acid is an acid, it have no pH since it's not in aqueous solution but it still can give it's acidic protons to say,
NaHCO3 or NH3 in anhydrous conditions (very high-vacuum or under inert atmosphere)... It may also reacts, as an acid, with
water (a base) to generate a less acidic hydronium cation and a bisulfate anion... acid/base theory 'me boy!
jfk April 25th, 2003, 05:27 AM

ok, woah didn't want to get that technical, but one guy above did ask about using 100% sulphuric acid, since it is hungry for
those water molecules it will have at least one from the atmosphere unless its in a vaccum. so if its not in a vaccum, chances
are its absorbed at elast one H2O from the armosphere making it, what 99.9999999999999999999998 % pure or something,
right?
yeah jfk is dead, but my full alias, i thought Americans to be sensitive of, so i have recently changed it to just jfk.

For all practical purposes there will be water in the acid, but keep in mind there are ways to remove mostly all water from the
acid withouth the need for an extremly pure acid. You just have to add something that reacts with water to the acid (there are
thousands; lithium, acetic anhydride, LiAlH4 etc...) while performing this step under an inert atmosphere. Distillation, under
inert atmosphere, will give the anhydrous acid if everything else was anhydrous. It takes skills to achieve this properly and this
is quite useless since the 98% solution contains 98% pure acid and 2% impurities + hydroniums (water), bisulfates. Water
decreases the acid's power, it dosen't activates it's acidity. BTW, theoretical pure sulfuric acid is roughly 10^12 times more
acidic than a 1M aqueous solution of the same acid, respect the stuff :D
Marvin April 26th, 2003, 08:32 AM

Id expect both lithium and lithium aluminium hydride to react with sulphuric acid itself rather than just with the water, the
former liberating hydrogen to form a salt, and the latter reducing it to sulphur, amongst other things. I assume you meant to
concentrate sulphuric, since these options only get worse for the direct production of conc nitric. If acetic anhydride was used,
this would contaminate the sulphuric with destruction products.
I doubt more concentrated acid is needed than can be made just by driving off the water by heating, but for anyone that wants
less water, the method suggested to me to dehydrate sulphurc acid, was to heat sodium hydrogen sulphate to form the
pyrosulphate, and add to the warm acid, cooling deposits insoluable sodium sulphate (or possibly hydrogen sulphate). Some
sodium ions doubless remain in solution, but could be removed by distillation if absolutly required. The temp required to distill
conc sulphuric acid is a little high for most glassware, my books recommend quartz.
What jfk meant, I think, was that pure sulphuric acid is a bad conductor of electricity becuase its sparsely dissociated. Adding
some water to it sharply increases dissociation, and its conductivity.
10fingers April 27th, 2003, 10:02 PM

In regards to concentrating sulfuric acid I have always boiled down battery acid. I have found though that you need to continue
heating for about 20 minutes after white fumes start coming off to get a high concentration acid. I have gotten it to a density
of 1.83 doing this which is adequate for most purposes. I always use a coffee pot. If you do it on an electric hot plate though,
don't set the pot directly on the heating element, use some type of spacer to give it about 1/2 in. clearance. Putting the pot
on the heating element will cause it to crack.
For distilling nitric, don't mess around with bottles and shit like that, it's a wast of time. You can buy a complete ground glass
joint distillation setup from www.unitedglasstech.com for around $135.00. It is one of the best investments I have ever made.

If you want to quibble about the concentration of sulfuric acid, I've heard that an excess of up to 30% of SO3
(the gas) can be dissolved in sulfuric acid, thus giving a yellowish substance that is known as "oleum" if I remember well.
So you can get more than 100% sulfuric acid. :)

This morning i tried to distill some nitric acid but I fucked with my sand bath, as I don't have any power regulator (if anyone
has some plans to make one cheap), and I got lots of red fumes, and quasi no acid (very orange of course).
The problem is that I turned off the heater, to allow the temp to rise down, then when I started it again, nothing happened: it
seems that there was no more nitric acid to be distilled.
The fact is I used about 50g AN, with 100mL 92% sulfuric acid.
Do you think AN is good to be used, or would you advise KNO3/NaNO3 ?

My AN is fertilizer, it's written on the bag N from nitrates: 16%, from ammonium: 16%. I think it's normal pure AN but do you
confirm that ?
Thanks, I'm gonna try again and see what happens.
Note: after having stopped the system, as it wasn't distilling anything more, I put a thermomether in the flask, and it instantly
went up to 110C, its maximum. Why would the temperature have so rised while no fumes, nothing was being distilled ?
Marvin May 12th, 2003, 11:45 PM

I dont like the idea of using AN for producing nitric acid, mainly becuase of side reactions like dehydration that cant happen
with alkali nitrates,. Though some people here do it.
If you are measuring the temperature of the solution, expect it to go a lot higher than 110C. End point in a neutral alkalie
sulphate product reaction is something like 260C, youd never go that high with AN though, aim for mostly bisulphate if you
redo the math, or use existing figures.
The reason hot sulphuric acid 'fumes' is probably more to do with the reason conc HCl fumes than strictly condensing acid. The
conc acid vapour is very hygroscopic, so it absorbs water vapour from the air, the dilute acid has a lower vapour pressure than
the water did, so you get the fine mist. Just the ramblings of a bored mind.
Tuatara May 13th, 2003, 01:35 AM

Arthis, if you want a really easy power regulator for your hotplate/sandbath go to your nearest electrical wholesaler (the sort
electricians get supplies from) and buy either an oven thermostat, or an 'energy regulator' of the type used for controlling the
hob elements. I bought a thermostat (50C - 300C) for NZ$60 last week (about US$30), an 'energy regulator' would be the
same or less. The difference between the two is that the thermostat regulates temperature , the energy regulator controls the
average power . The latter would likely be of more use for distillation. Both should handle at least 2kW easily.
Vigo March 14th, 2007, 05:46 PM

Hello, this is my first reply and I hope I am contributing to the forum and the beast does not catch up on me!
To complete the guide on distillation:

Despite it being flammable liquid, paraffin can be used to create a heat bath because it has such a high boiling point, ussually
over 400C. It has a heat capacity of 2.13 kJ/kg.K which is about half that of water. Therefore it will heat the distillant evenly.
Paraffin is a mixture of hydrocarbons, hence its boil and flash point are determined by its composition (the larger the
percentage of large molecules the higher the boiling point). I know for a fact that it is used in determining the melting point of
aspirin (138C) in school labs in presence of an open flame (the paraffin is in a heat diffusion test tube).
to Jarrod: I strongly derecommend using cotton to seal a home made distiller if nitric and sulphuric acid are in the distilling
bulb. If vapours come into contact with it, it will turn into a nasty black mush. There is a very slight chance it turns into gun
cotton and you do not want that. I know gun cotton has to be very dry and have a neutral ph but after all it is near a heat
source and water which could increase the ph and dry it (very unlikely though).
beez21 March 19th, 2007, 02:12 PM

Hello,
I was just wondering if it would be possible to concentrate Nitric acid by freezing it in a normal home freezer, because the water
would freeze allowing the nitric acid to, just be poured out. Would this work or am I missing something? Please tell me if this
is a stupid question, but I did a quick search that didn't return anything useful!
Nitric-producer March 19th, 2007, 05:01 PM

I doubt it otherwise why would we all bother with Distillation etc. ;) Im pretty sure it would just freeze into a big large chunk.
beez21 March 19th, 2007, 05:09 PM

Yes I did think that but I was just making sure. With the freezing points being so different -42 degrees and 0 degrees, I
thought it might have worked. Looks like I'm going to have to splash out on a Distillation set. bye bye money :(
nbk2000 March 19th, 2007, 06:07 PM

UTFSE will show a thread where I posted about my experience with freezing out nitric acid from DMC (methylene chloride).
You don't need a distillation setup if you extract/freeze, though you'll still want a setup for purifying the DCM for reuse.
beez21 March 19th, 2007, 07:38 PM

Oh, really sorry I'll search more Thoroughly next time! it wont happen again :o
ultma March 19th, 2007, 09:31 PM

I f you want to get technical JFK(i thought you were dead) 100% H2SO4(unless in a perfect vacuum) will have at least 1 H2O
molecule as H2SO4 is hygroscopic, there is no such thing as 100% pure anything.
I take it you have not heard of 110% sulfuric acid

you add 10% water you still have 100%
I think its made by bubling SO2 through 100% H2SO4
nbk2000 March 20th, 2007, 12:53 AM

It's called 'oleum', and is sulphuric acid with an excess of Sulfur Trioxide dissolved in it. Any additional water added to oleum
results in additional Sulphuric Acid, until all excess SO3 is consumed, making it a very effective dehydrating agent.
xenon24 March 27th, 2007, 08:55 PM

A little OT, but since you brought it up...
NBK (or anyone else), do you know where to buy oleum, or how to make it? Based on the research I've conducted it's very
hard to make sulfur trioxide (whereas sulfur dioxide is made by simply burning sulfur) I've done searches on oleum before
and never found much.
I'd like to make 2,4,6 - trinitrotoluene, but I don't have the resources to make/haven't found a place to buy oleum.
It is also a solid if you add enough Sulfur Trioxide, and this is how it is transported...makes for a nice desiccator.
nbk2000 March 28th, 2007, 01:16 AM

Roasting iron pyrites in a furnace will form crude oleum, or crystallline SO3, depending on reaction conditions.
Buying it? Not too likely.
Besides which, you don't need oleum for making TNT.
akinrog March 28th, 2007, 03:57 AM

Roasting iron pyrites in a furnace will form crude oleum, or crystallline SO3, depending on reaction conditions.
Sorry to interject Sir, but AFAIR, burning pyrite gives SO2 which was further oxidized into SO3 either by means of a catalyst
(Vanadium oxide?) or contact process. Regards.
nbk2000 March 28th, 2007, 06:28 AM

You're not burning them in air, you are destructively distilling them (roasting).
I read this in an old book, maybe Dicks or Ullman, so perhaps it was incomplete or just plain wrong. Go to primary sources.
I also found this:
Sulfur trioxide can be prepared by the two-stage pyrolysis of sodium bisulfate:
2NaHSO4 > Na2S2O7 + H2O

Na2S2O7 > Na2SO4 + SO3
This method will work for other metal bisulfates, the controlling factor being the stability of the intermediate pyrosulfate salt.
Source (http://en.allexperts.com/e/s/su/sulfur_trioxide.htm)
So roast sodium bisulfate until all steam evolution is done, then crank up the heat to cook off the trioxide.
I wonder if you could do this with super-cheap ag. grade ammonium bisulfate?
megalomania March 28th, 2007, 02:32 PM

Oi! Isn't this a thread about nitric acid? I was spending (actually wasting) no small amount of time yesterday researching the
preparation of SO3. I decided to stick to nitric acid this summer, so no goodies for sulfuric will be forthcoming for now.
Oleum consists of sulfur trioxide dissolved in sulfuric acid, not sulfur dioxide, ultma. It is true that a common industrial route
to sulfuric acid is the roasting of iron pyrites in open air to form sulfur dioxide. I can't vouch for the anaerobic method, but it
sounds reasonable. It probably requires more heat energy (read that as $$$ wasted to industrial types), which is why it is not
used commercially.
Squizzy March 31st, 2007, 11:47 PM

Hi my first post bear with me.
I went a different tack in equipment to make nitric acid.
Instead of using a glass vessel i bought a camp oven around 2 litres and drilled a hole to make a tight fit on a distillation
head. I then added the potassium nitrate prills and went to the luteshop and bought some lute (clay).
I smeared this liberally around the rim and the distillation head hole after assembling it all. Attached a condensor and a 3 litre
flask to hold the condensed nitric acid. This receiver had a extra small neck for a thermometer to which i attached a rubber
tube which i laid out to lead fumes off. Then i added sulfuric acid through the distillation head and sealed it afterwards with a
stopper to fit. Then i actually used a gas flame to heat the mixture. Id seen this idea of using iron vessels in a old chemistry
book from the 1850s in a google book search.
Some of the old chem books on googlebook have some gems for home experimenters
After use and rinsing its only got a medium coating of surface rust on it and would seem to be able to be used many times.
Getting the clay lute to seal can be problematic. but if it leaks slap some more on. Even go around the outside with more They
used coal fires to heat similar iron vessels so a gas flame set for a nice mild distillation should be safe. The only problem was
you cant see the end point of the distillation. I didnt boil it dry to the evolution of red fumes , instead I judged the output but
I found on dismantling there was still much liquid in the iron vessel. I was erring on the side of caution though.
The acid performed well in making Aqua regia I didnt triturate for strength of the acid
I also heated the iron camp oven to extreme heat. The aim to burn of any oils and paraffin used as a rust preventitive on the
assumption it might nitrate into a explosive in a nitrating environment like that.
In hindsight glass would have served as well but for making red fuming acid RFNA iron would possibly save your glass
James April 2nd, 2007, 12:04 AM

Just a quick crazy thought, why not use an old fashioned pressure cooker with the stem removed. Then you could attach a
tube (and ultimately the condensor etc.) where the stem was. I have a pressure cooker that I could use for something like
that.
Frunk April 3rd, 2007, 07:05 PM

Just a quick crazy thought, why not use an old fashioned pressure cooker with the stem removed. Then you could attach a
tube (and ultimately the condensor etc.) where the stem was. I have a pressure cooker that I could use for something like
that.
What makes you think the stainless steel that the pressure cooker is made out would resist boiling nitric acid? That's an old
trick for distilling water or alcohol, but acids are another beast.
megalomania April 3rd, 2007, 10:43 PM

It would work for awhile, but eventually corrosion would become an issue. Actually highly concentrated nitric acid passivates
many metals, whereas dilute nitric acid will attack them. Maybe the steel container will last for a time. Certain steel alloys exist
that will resist acidic environments, but I doubt the steel in a pressure cooker would be made of such an alloy.
If you were distilling large amounts of nitric acid on a regular basis I would suggest going with a glass setup, but for the casual
distiller in a pinch there would be nothing wrong with using a pressure cooker. Distilling nitric acid once in a steel pot should not
go wrong. Even a corroded pot should not affect the overall purity of nitric acid, but structurally it would be dangerous with each
use. Spilling hot nitric acid all over your work area does not a fun day make.
Bluebanshee April 6th, 2007, 06:49 PM

I came across a good way to produce concentrated sulphuric acid while reading through an old Encyclopaedia Britannica (1938
edition or thereabouts) it details the method by which it used to be made in industry in the good old days and before the
contact process was invented. it uses hydrated Iron II Sulphate, also known in those days as "green vitriol" (FeSO4.7H2O). to
produce sulphuric acid, which also used to be known as "oil of vitriol".
The iron II sulphate is a green solid (the green colour is due to the H2O ligands), and it can be purchased from garden
centres (in the UK at least) as a soil treatment.
i have checked out the thermochemical data on iron II sulphate in my "Nuffield advanced science book of data" it gives the
decomposition temperatures listed below.
The method is as follows: Put the iron sulphate in some kind of vessel and heat gently. At a temperature of 363 K, the
material will lose 6 of the water of crystallisation molecules. FeSO4.7H2O -----> FeSO4.H20. this new material is white, hence
the process can be monitored visually by colour change.
Put the white solid in a distillation apparatus and heat strongly. At a temperature of 573 K the material decomposes into
sulphur trioxide and iron oxide and the remaining water of crystallisation molecule is given off.
FeSO4.H2O ------> FeO + SO3 + H2O. This reaction can again be monitored visually as the FeO has a very characteristic red
brown rust colour (funny that)
note that 1 mole of SO3 plus 1 mole of H2O will react to give 1 mole of H2SO4 (sulphuric acid) and this will be distilled over
and can be condensed to give very concentrated sulphuric acid.
I have tried this and it does work, main points to note are, ensure that you only heat gently at first otherwise you fully
decompose the material too early and waste it. also make sure that all traces of green have dissapeared before collecting the
distillate, otherwise you will contaminate your acid with excess water, (best to heat it just until the first signs of red/brown
appear)
At the risk of teaching people to suck eggs, this sulphuric acid can be used to produce nitric acid, by distillation with sodium or
potassium nitrate. :)
Frunk April 7th, 2007, 05:10 PM

Besides, everybody has access to a glass distillation setup.
Beer bottles. For a 60*C distillation, thermal dilation is hardly a problem.
Some plastics take nitric well, but you can use three beer bottles, a drill press, a set of taps (the threading stuff kind, not the
sink kind) and teflon tape to make a distillation setup.
One beer bottle acts as the condenser, while the other two are the distilling/recieving flasks. There's a variant that uses the
larger wine bottes.
If you have a torch capable of melting glass, blow those beer bottles into glass pipes.
Emil October 6th, 2007, 07:21 AM

I was just browsing through the net last night, and came across something I hadn't noticed before. The Hydroponics shops
supply Nitric acid at a 38% concentration as a pH down product for use in areas with really hard water.
It's pretty cheap as well, the cheapest I found was 4.50 for a liter.
This could be a really handy source. To get the HNO3 to around a 68% concentration you can literally just distill it away from
the water.
And then if you wanted to take it further, (90 - 98%) just distill it with some
HS2O4, or other dehydrating agent.
The second method on a large scale may not be so profitable in the long run, as you could probably synthesize via the xNO3
and HS2O4 method which would be more economic. However, if you can make plenty of use out of the 68%, which we all
should be able to (HDN, NG etc), then it could be a handy little source.
Some of you guys may have come across it, but just thought I'd share for the ones who haven't. I won't bother giving a link
for it. All you have to do is just go onto the Hydroponics page that you use and just search it.
Charles Owlen Picket October 6th, 2007, 09:50 AM

Personally I don't think that all that cheap....but you are correct - it would work. But from my perspective if you have proper
distillation equipment; proper glassware - using H2SO4 and a solid nitrate would be a less expensive route, no? Now, if you
can't get any sulfuric at all I could see it but only if you were to knock out a large batch at once and save the labour.
Emil October 6th, 2007, 06:47 PM

Well personally you probably wouldn't, but don't forget, I live in the UK. That price is actually pretty good for me. I imagine
you are a USA resident, and therefore get decent and reasonable prices. However, in the UK we get ripped off with pretty much
everything haha. Just have to put up with it I suppose.
But sometimes it's best to disregard price right..???

I mean only to a certain extent, beings as we are home experimenters and aren't planning any major usage, at least I hope
not?
But of course on a bigger outlook, price is very much important.
I just thought this could be a handy source for 70% nitric acid, as for alot of experiments there is no need to go wasting
90%+.
Next on my list is to invest in a glass distillation kit from united glass tech.
Charles Owlen Picket October 6th, 2007, 09:23 PM

It -=IS=- cheaper in the States but even though I would have no intention of hoarding some voluminous amount the lower
cost makes the experiments a more ready, less pressured past-time. Where I am going with that is that if I think I learned
what I could, I would just use the material for drain cleaner - with no feeling of monetary loss.
However, if all I could get would be lower concentration I would still distill it down as 90% + HNO3 is so damn flexible
experimentally. Being realistic I suppose it's not THAT expensive (4.50) but I wouldn't think I paid 4.50 per liter but 4.50 for
200+ ml....
I know that the UK has a metal plating industry, does it not? THAT'S where acids (technical grade) are used in abundance!
Perhaps you could check that out and get the deals we get here. After all the raw materials can't be THAT inflated (no?)
Emil October 7th, 2007, 07:17 AM

Yes this is a very good point, maybe I should take a look round some companies and try and obtain some acids in decent
quality and strength.
I've tried before just buying from a chemical supplier I use occasionally, however, they didn't want to supply acids to a
domestic customer.
If I had a business to buy products through they wouldn't blink an eye.
But chemical suppliers are always going to be more careful than a lot of other suppliers, so maybe I'll just have to try some
metal plating companies.
If not just have to do things the hard way with the good quality drain cleaner.
The only thing that puts me off trying to obtain some fuming nitric acid is that it is pretty renowned for making explosives, and
could leave an all to suspicious trail.
Charles Owlen Picket October 7th, 2007, 10:36 AM

I have spoken with many people (mostly younger fellows at university, locally) and from my understanding unless one does
something quite "attention getting" the idea of having or leaving a "trail" is a fear one need not have.
A few years back in the US the Consumer Products Safety Commission (CPSC) got a hold of lists of buyers that had
frequented pyro suppliers and sent them all a letter. It was written on Justice Dept. stationary and warned of not making large
exploding fireworks. A low trick, meant to frighten: which it did!
Many people promptly got out of the hobby. But more of them banded together and gave monies to law firms protecting the
companies from CPSC harassment. The result was that the larger companies are still in business (albeit with strong
stipulations of what they may sell to the unlicensed public).
There are ways to enjoy hobbies such as energetic chemistry without breaking any laws. One simply needs to be creative and
careful. I personally, go to a local university and have an individual who is enrolled, do some research while I am in
attendance. I enjoy the lab, maybe take some pics and the material is promptly flushed. I live in books on the subject and
that fulfills a lot of my wanton desire for "hands on" experimentation.
Reading the law carefully; I am generally safe from harassment as research allows some small level of synthesis if certain
provisions are met. The material is not used for noise making or attention getting maneuvers :-) I'm confident you can do the
same if you study the issues involved. If you wanted to experiment further, make sure you don't disturb the public with noise
or fire. Think safety and no one will be angered.
Lewis July 9th, 2008, 06:53 AM

This may seem like a relatively simple concept, but I haven't run material covering it here.
I recently bought a full 24/40 ground glass setup, and I'm eager to create some HNO3 with it. I have everything I need, save
a vacuum source. This is the last hurdle and it's proving challenging.
I originally thought of an aspirator solution, with the water from the cooling circuit also going through the aspirator. I then
began to wonder if a simple hand pump system would be adequate to create a vacuum.
Is it necessary to apply constant suction to the distillation rig? I don't see why it would be, as once the vapors begin to
condense, they will counteract the rise in pressure from the initial boiling.
Of course, no system is perfect, and even discounting leakage, there will probably be some compounds (NOx?) that will build
up in gas phase, and increasing the pressure. Still, could I simply give it a few manual pumps every once in a while to
maintain the vacuum?
If this idea is not workable, I'd like to hear why. Perhaps someone would be able to fill me in on exactly how an aspirator
system works as well.
ChippedHammer July 9th, 2008, 07:27 AM

Your manual hand pump will not last long, I am told that aspirators are second to a proper teflon vacuum pump.
Emil July 9th, 2008, 05:50 PM

A vacuum on your HNO3 rig, is probably the biggest pain you will come across. A vacuum pump, possibly teflon for chemical
resistance, is really the best way forward. However these are expensive.
I bought a chemicaly resistant vacuum pump, and already am having problems. Regardless of what vacuum pump you have,
the HNO3 reisdue is still a pain for most pumps. If it doesn't corrode it, is usually makes parts stick. The way forward is to
build yourself a filter for your vacuum pump. This way the fumes that go through your pump, are not half as nasty as they are
before the filter.
I can't say how well a hand pump will hold up, maybe if you have a good filter it might not be such a problem.
Personally I would choose an aspirator over an expensive pump anyday. Why?? It does exactly the same job only at a fraction
of the price. An aspirator works by simply creating a vacuum from the resistance of the liquid or air flowing through it. The
water comes in at the top of the aspirator, which then hits a narrower exhaust port which is at the bottom of it. This resistance
causes a vacuum which comes off from the side of it. You simply connect this to your rig via a tube.
There is no maintenece needed with them and nothing which can really go wrong. The HNO3 fumes are just washed down the
drain with the water.
Of course you need a mains pressured feed to attain a decent vacuum which could be a pain, depending on your location of
your lab. If you have a mains pressured tap near by... Excellent!
There can be a slight drawback with these aspirators though. If you water pressure from your tap or feed drops whilst in mid
lab, it can sometimes cause for water to be spat out through your vacuum tube, diluting your nicely distilled fuming nitric. This
isn't a worry as long as your pressure is pretty consistant, which it should be.
Lewis July 9th, 2008, 06:40 PM

Ah! So the aspirator needs a taper. Having only seen the outside of them, I attempted to use a regular "T" of tubing for mine.
:p
I'm planning on simply recirculating the water with a bilge pump and reservoir. Hopefully any fumes will be sufficiently diluted
so as not to wreck my equipment.
I suppose the higher the speed of the water aspirator, the better the vacuum up to a certain point? If this is the case, then my
crappy little pump probably won't do it.

This is indeed true, for the cost of an aspirator they just aren't worth trying to improvise and build yourself. A guy sells them
on eBay, who is based in the US. I think he sells them for around $20, although you could probably pick one up for cheaper.
Yes, this would probably be the best way to go about things, recirculating the water is ideal, as you will be amazed how much
water you are wasting otherwise. Wasting it isn't the problem, it's mainly the cost. The higher the water pressure, the better
the vacuum will be up to a certain point yes. So if you can create a loop system with a pump, and pressurise it to a decent
pressure, you will be well away. I can't give any exact figures, all I know that mains pressure is usually 3-4 bar, some areas
may be more or less. This allows you to easily pull a sufficient vacuum for this type of distilllation. Even half of this pressure
would be enough for a decent vacuum. Remember with HNO3 we only really need to lower the boiling point a smallish fraction
to avoid decomposition.
Make your system large enough, in the sense of the amount of water it can hold, and the fumes will not be able to
concentrate the water enough to cause any harm to components
I was bummed a few months ago. I had a lovely all glass aspirator, which I accidentally snapped at the stem where it thins. I
was not impressed.
megalomania July 10th, 2008, 07:49 PM

Eek, you need a trap for your vac pumps to avoid this. At the very least pull your nitric acid through some water, and then pull
that moist air through a drying trap. You can use many materials to DIY a washing and drying trap, flasks, mason jars, beer
bottles, PVC pipe. Choose your material depending on how strong your vacuum is.
Dissolve some baking soda in your water trap to avoid it becoming acidic as well. The base will neutralize the nitric fumes as
the air is drawn through.
I used to have a problem running distillations with my aspirator since both the water line and vacuum line had to run from the
same device. I needed the water to circulate through a condenser, which can only take so much pressure, which in turn means
weak vacuum.

Ahh yes Mega I was just about to say about the water having to feed two devices. It has to feed your aspirator and your
condenser, thus lowering your flow to the aspirator giving you a weaker vacuum. Here's the trick though for anyone who might
be having this problem. Put an inline isolation valve before the condenser flow tube. You can purchase one from any plumbing
store. I made my water tubing rig out of 15mm copper tubing and then used tubing to transfer from the copper to the rig. This
way you can regulate the pressure on the condenser and turn the valve almost fully off. Just allowing a slight trickle of water
through the condenser still keeps it ice cold, but doesn't kill off your pressure to the aspirator. This way you can keep your
vacuum pull high.
I am currently making a trap for my pump, this way it saves the sticky residue clogging the bits on your pump up. Luckily mine
is a chemical resistant pump, so it doesn't damage anything, just makes an annoying cleaning job after every distillation.

How many people here have heating mantles? I'm leaning towards getting one due to the sheer simplicity (no annoying oil
baths) of them.
I know there are two diffrent types, thermowells and Unimantles. So far I'm leaning towards a thermowell as you can directly
pour sand into them and they seem to last longer (or so I'm told).

I went for an electric hot plate to start with, it has a built in magnetic stirrer aswell, which isn't the most powerful, but it can
help alot. I never really thought much of the hotplate.
Personally I prefer using a flame. It's quick to ignite, fast to ajust, and can be done very cheaply. A bunsen burner fed off LPG
would be good enough. I personally lack space so do not need a huge cannister of LPG gas laying around, so I chose to go
with a camping stove fed by small gas bottles. You just change your gas bottle over when it runs out. They last for a fair while
too. Dont about 4 distillations and am still on the same bottle.
An oil bath is completely unnecessary if you ask me. I Don't see the advantages of using such a system. More hassle than is
needed.

Using a open flame is bad for your flasks, hot spots form which stresses the glass and results in uneven heating. The only
glassware that should be exposed to a flame is a test tube and then its passed in and out of the flame.
Setharier July 13th, 2008, 01:14 PM

I have an lab torch which fire emitting holes are drilled around the head so they spread around evenly, making no single hot
spot but heating about the whle bottom except the very center.
Althrough I am able to obtain pure new 2kW heating plate only for 20 and attempting of purchasing it very soon, is it "much"
better than the lab torch? Only cons I can find might be the relative high energy drain and ability of elevating the distilling
flask directly in contact with it.

With a bunsen burner yes. But I use a camping stove, which has a wide ring and spreads the flame out nice and evenly.
Besides the heating for the distillation of nitric acid is relitively mild. Especially under vacuum as it should be. It's not a
problem for this task.
Combustable Wishes July 19th, 2008, 11:01 PM

As true as this is, and the viable solution of distributing the flame via a splitter, iIbelieve the use of a ceramic material
between the flame and the glass is almost a better solution as it evenly disperses the heat everywhere it touches. I am by no
means an expert, but that is what my AP chem teach trusted us with to heat beakers, and if I managed not to break
something that way (natrual klutz) it seems pretty viable.
jarynth August 3rd, 2008, 03:41 PM

Hey all, this link provides a concise diagram of the azeotropic properties of the HNO3/H2O mixture depending on the amount
of H2S04 added:
http://www.qvf.com/en/processsystems_3/mineral%20acids/ConcentrationingofNitricAcid.shtml
The data probably refers to standard pressure. I'm still looking for a graph detailing the concentration of NA vapor at low
pressure, when I find it I'll let you know. Many older handbooks report some data in table form, and the missing info can be
obtained by clever interpolation, but an easy-to-use reference for the impatient amateur chemist is advantageous. =)
DetaDude August 6th, 2008, 07:06 PM

General info. Lab depot sells a Nalgene aspirator (plastic) for around $12.00. I have three of them on my distillation set up
and can select 1, 2, or all three. They are fed by a clear water pump from Harbor Freight and with all three opened up and
pulling vacuum the pump is making 40psi and the vac. is 29.5 in.hg., if I bleed off a small amount for the condenser, I still
have 30 psi and a vacuum of 28 in.hg..The pump draws from two 5 gal. buckets , and when distilling I put a 10 lb block of ice
in each bucket. I do not have running water in my lab at this time but its coming soon.
I recently added a third bucket and a submersible aquarium pump to handle the condenser chores.
A quick note on some glass aspirators sold by Pellet Labs (AKA Mt. Home Biological) I have tried these ( I have three of them)
seems the problem with them is that when the vacuum get above 16 or so in. hg. the drain water starts to back up in the
venturi and cuts off the vacuum, they are nice units if you keep th water pressure low and are willing to accept a lower vacuum.
I also use a teflon hose for the vac. outlet from the still to the first stage filter/trap in the vac. circuit , be sure to add a bleed
down valve between the still and the first trap, so when you shut down operation you don't suck neutralizer back into your
receiving flask.
I do hope all of this is of help.
If I can help further please contact me via PM.
Lewis August 7th, 2008, 09:44 PM

Deta: Thanks for the advice! I'm nearly set up to do my first run at HNO3. It's been a long time in the making, but I'm taking
my time, with the intention of doing it spot-on, the first time around.
I'm not too concerned with pulling a torrential vacuum for this project, as even a mild one will do wonders on eliminating NOx
fumes when distilling.
With something like nitric distillation under vacuum, the home experimenter would probably do well to go the extra mile with
preparation and safety. While I'm almost ready to begin (still waiting on a glass aspirator), I'm still divided on a few things,
namely:
-What sort of tubing to use for vacuum gauge and aspirator lines
-How to stop moisture from entering the still
-Finding a good storage solution for high concentration HNO3
-Sealing my ground glass joints properly
Whatever I decide to do, you can bet I'll document the process, who knows, maybe someone will even find it useful!
fractional distiller August 8th, 2008, 10:17 AM

Hey Lewis I have a Few suggestions for your process. You do not need to follow any I am just spouting a few out.
What you are aware of is that the Nitric acid is going to attack many kinds of tubing. My best guess would be to use a Nitrile
type tubing that will be somewhat acid resistant.
There are also special purpose vacuum tubing that can be purchased from any chemical supply shop. That being said you will
most likely have to purchase it online or grab a bit from your local chem lab.
What you should do for your ground glass is just get yourself a acid resistant grease for the joints then pull your vacuum with
your aspirator via the sink try an venturi valve if your need a higher fluid speed.
Attach the venturi to the sink. Attach aspirator to venturi use a glass tubing that can be bought @ www.unitednuclear.com for
the glass simple bunsen burner can be used to bend the glass then needle nose pliers can be used to attack the glass to the
aspirator once the glass tubing has been heated just flare it with the tip of plier place over it and then clamp down. Flame
polish it as cooling to deal with thermal shock (glass will still be brittle due to lack of proper annealing, will work in your favor
for removal). Your aspirator will take the NOx fumes with it down the sink.
As for the the moisture use a simple cold trap. Set one up using a large test tube or other device by attaching a glass tube to
it and seal it and then place inside a larger container fill with any Hydrocarbon and dry ice. (any contact with dry-ice
hydrocarbon will cause instant frost bite) but this will deal with the moisture by freezing it. Instead of using the aspirator to rid
yourself of Nox also vent it through cold trap as well.
If not use Higher concentration H2SO4 to take care of moisture because it will be diluted into the acid creating a little heat as
dilution of H2SO4 is exothermic.
Storing your acid is easy buy or (come by) a large brown 2 liter bottle (aids in protection of UV) fill it with your acid and keep in
fridge of freezer.
hope it helps
Fractional, I'm a little confused by what you are referring to when you say a water aspirator connected to a venturi. I was under
the impression that they were the same thing.:confused:
I read mention of needing grease/tape on ground glass to make a decent seal constantly, but I still have a hard time
believing it! The joints just seem to fit together so perfectly, not to mention the fact that a decent vacuum would pull them
together even tighter.
I'm a firm believer in using the proper equipment for the job, but I still hate spending a fortune and waiting for things to come
in the mail. I'm wondering how fast stray nitric/NOx fumes are going to destroy conventional aquarium tubing (I'm assuming
quite fast).
I also would love to avoid dry ice whenever possible, as I don't think it stores well even at freezer temperatures. I've been
leaning more towards a trap filled with dessicant.
Alexires August 9th, 2008, 01:22 AM

Lewis - You could always try PTFE (Teflon) tape on your joins. Just a small amount (a couple of layers) should help hold the
vacuum as well as be resistant to the acid.
totenkov August 9th, 2008, 01:39 AM

Yes most recommend some kind of Teflon grease for the joints. In most distillations, I have never bothered. When you are
going to distill Nitric just connect all the joints in the sequence that you want (I have tested a few different connections in the
glass, to develop efficiency). Then wrap the connections with generous amounts of Teflon tape, from the hardware store.
Not only will this rig avoid leaks but the tape will hold firm the joints, should loosening occur, which it does. Some ill fated glass
of my own has met its demise that way, double and triple check every time!
Emil August 9th, 2008, 05:37 PM

Lewis.
Like the others said, teflon (PTFE) tape is definately the way to go with sealing the joints. It is necessary to seal the joints
either by means of tape of a vacuum grease. Not only does it properly seal your rig, the most important thing is that is allows
your glass to come apart alot better after you have finished the lab. You'd be suprised how well those glass joints hold
together at times, and you don't want to risk damaging the glass when just simply taking it apart.
Dow corning sell a vacuum grease which is deisgned for this application, however is it resistant to nitric acid vapour? Absolutely
not.
This is where teflon tape comes in handy as it is also dead cheap. The problem with vacuum grease is you also risk the chance
of slightly contaminating your nitric acid as it will most likely attack it and then end up being carried over with your distilled
acid.
The tubing question debatable. Depending on what specific material it is made from depends how it copes. My tubing I use
does not resist the nitric vapours either, but it only turns the clear tubing yellow, it doesn't really deteriorate the tubing itself. I
would just use the aquarium tubing and then inspect what happens. If it is only discolouration then I wouldn't worry. The
correct tubing can be very expensive to buy aswell so unless really needed, I would try and work around that.
All that is needed is an aspirator for your vacuum source. A glass aspirator is great. I have a metal "chapman" aspirator. The
spec states that with a water pressure of 2 bar (30 psi), a vacuum of 29.5 in/hg can be expected. That is pretty damn
respectable as 2 bar isn't much at all. You can guarentee any mains water is going to be more than that.

Well, the aspirator is in, and as luck would have it, when attached to the bilge pump I've been using, it won't create even a
weak vacuum with it.:(
It definitely works like a charm with enough water pressure, I just don't have the means to create it as I don't have a water
line out to the lab. I'm going to have to get inventive...
I did notice is an old air compressor sitting in the corner. I wonder if it could be used to move water somehow...
Cobalt.45 August 12th, 2008, 08:07 PM

I did notice is an old air compressor sitting in the corner. I wonder if it could be used to move water somehow...
FWIW, Harbor Freight sells a cheap (~ $13 + S&H) air vacuum "pump" that will pull a vacuum w/your compressor.
More: http://www.harborfreight.com/cpi/ctaf/displayitem.taf?Itemnumber=96677

It seems like a good deal, but I already have the venturi so I'd rather improvise something myself. Also note my location. If
I'm outsourcing my supplies anyway I might as well stick with a system I know is going to stand up to the most corrosive of
fumes.
I'd be curious to know what's inside that device. For that price it seems like it could be easily improvised, but I've been wrong
before...
Cobalt.45 August 12th, 2008, 11:08 PM

I'd be curious to know what's inside that device.
Think of a simple venturi w/a tap near the narrowest portion of the "throat".
On closer inspection, it has a zinc casting as the main portion of the device, so would be impractical if exposed to HNO3
fumes, etc.
Lewis August 13th, 2008, 01:31 AM

I spent most of the night trying in vain to get a decent vacuum for my distillation setup. Simply put, the fancy glass venturi I
bought can't create a vacuum worth shit.
I built the still in the back yard so I could access the water hose. Even at full blast (I was almost afraid the fragile looking
aspirator was going to explode), it created only a meager amount of suction. Not enough for my gauge to read anything
above 0 in. Hg.
Below are the pictures of my failed attempt at distilling some water under vacuum:
http://i282.photobucket.com/albums/kk278/orbital_Saucer/DSCN1497.jpg?t=1218602070

Lewis here is an idea. You may have tried already so if you have then please forget this.
Just connect your aspirator up to the water hose and then where the vacuum take off is on the aspirator, place a hose and
connect it directly to your vacuum gauge. This doesn't include any other part of your still. Now turn the water on and inspect
what happens. Does it pull any vacuum now?? I say this because incorporated in your rig, is plenty of joints and possibilities of
leaks for the vacuum. Maybe the reason you are not seeing any vacuum is because your still is not holding it???
Just do this as a basic check, this then eliminates any worry about problems with the rig. If you still recieve no vacuum then
you have a problem. It is either your vacuum gauge isn't working right, or your aspirator isn't.
Later on this evening I am actually going to test my new metal aspirator via the same means that you have. It will be hooked
up to my outside water hose and then a vacuum gauge placed on the off take to measure the vacuum it produces. I already
know the water pressure of the outside hose is 2.2 bar. It would be more however the connection from the mains system
incorporates a flexi hose which is somewhat restrictive to water pressure. After I have checked it and recorded the results, I will
post again and let you know.
I did have a glass aspirator, it looked the part, but it was pretty useless in the fact is was so fragile. When disconnecting the
quite tight tubing one afternoon, the stem of the aspirator cleanly snapped. It was right where it thinned down. I choose from
that point never to get a glass one again and go for something ruggid. I will be checking this later and report back.

Well I have done those small tests now and have some answers. I would of edited my previous post rather than repost but it
wont let me?
Anyway, after my putting my new aspirator to the test I was happily suprised. The unit pulled a really good vacuum at just
below 30 in/hg.
Take a look. This is what I recommend you to do with your unit Lewis.
Here you can see the Aspirator connected up to the mains, and the vacuum gauge connected to give me the reading.
http://i250.photobucket.com/albums/gg256/emil2008_2008/P1000130.jpg
A close up on the gauge. Note the in/hg at the top in white measuring anti clockwise. Ignore the fact the needle is reading off
the meter. The gauge for some reason sits at 3 in/hg when disconnected. It is merley a fault, so with this gauge I just take off
3 in/hg to get the actual figure.
Now time to look at my actual vacuum pump. This is a chemical resistant one. Quite a nifty bit of kit. Here is the same,
connected up to the gauge for a nice reading.
Close up showing 26 in/hg (take away 3 and this is 23 which is actually listed in the specification documents).
This just shows you that the aspirator actually out performs the vacuum pump. Obviously for most people the consumption of
water with an aspirator is enough to cause a problem.
If you are still having a problem after you check your aspirator, then I recommend to take the item back from where you
brought it for a refund. Then buy one of these. A chapman aspirator from a lab shop on eBay. Nice price. Heres the link.
http://stores.ebay.co.uk/AVOGADROS-LAB-SUPPLY_FILTRATION_Aspirators-Vacuum-
Pumps_W0QQcolZ2QQdirZ1QQfsubZ3452369QQftidZ2QQtZkm
See how you get on!

Turns out the aspirator works after all. I was having difficulties last night for a couple reasons. Firstly, the check valve on the
unit tends to stick in place once it closes off from positive pressure. Secondly, the aspirator seems to not work when the water
flow is turned on, and THEN the vacuum line is attached. The whole thing needs to be assembled before the water is turned
on.

On another note, I set everything up again and distilled some water the other night, but still could only get about 5" Hg out of
the rig. Might be fine for nitric but I'll probably look for a better water pump soon.
I tested my stored H2SO4 today and it only had a density of about 1.7, which I calculate to be about 80% concentrated.
Boiling is a complete bitch because it:

-takes a lot of energy
-inevitably fumes up the shop, even if I carefully suck the fumes off the beaker
-gets organic matter in the acid when done outside
What does this forum think about distilling at this concentration? Obviously water is bad in the system, which is why we use
drying tubes, etc. to remove moisture from the still, but I'd assume the 20% or so of water would be clung on to by the
sulfuric, and thus not be a problem. I would assume that (especially under vacuum) the BP of water and nitric would be
sufficiently different to not cause a problem, but this is total speculation.

Concentrating Sulfuric acid is a nasty job, unless you have the correct equipment, like a fume hood.
However, it all depends what kind of distillation you are doing, from your question I find it hard to tell. If you are going to be
doing the Sulfuric/Nitrate route to distill off nitric acid, then 80% is not really going to be ideal. It will work but you will end up
with a weaker nitric acid which will need further distillation to remove water.
If you are concentrating nitric acid you already have, (which is around 70%) and thus using the sulfuric acid to steal the water
then 80% would be fine, You would just have to regulate the amount you add. In both circumstances 95%+ sulfuric is really
the best.
Loveofchaos August 19th, 2008, 08:15 PM

I know this is a bit belated but to me, getting the wax off of the Potassium Nitrate "prills" is too much work for what you get.
Where I live in CA you can go the pharmacy and buy pure Potassium Nitrate, US$2.37 for 6 oz. Even though I am not sure it is
100% pure, I know it is very pure. Makes good smoke bombs too =]
Alexires August 21st, 2008, 02:32 AM

Loveofchaos - Yep, it is so damn belated that I have no idea what you are replying to. Keep your posts on topic and in a nitric
acid thread, we don't really care that you can't be bothered doing something because you can just walk down to the store and
buy it.
First and last warning.
Lewis August 23rd, 2008, 08:19 PM

My first crack at HNO3 was only very mildly successful, but achieved a result nonetheless. It went like this:
140 KNO3 grams were added in portions to 153 (87mL) room temperature H2SO4. A small amount of red-brown fumes
evolved, and temperature rose. The mixture was left to its own devices for maybe an hour, before being heated slowly in a
water bath under vacuum.
The rig stayed at a pretty constant 18" Hg throughout. Initially, a fair amount of NO2 evolved, but this tapered off as the nitric
began to come over, which occurred at ~74C and at a peak rate of about 1 drop per 2 seconds. The water bath stayed
between 90 and 95C, until it boiled off, at which point the flask's temperature began to drop, and the experiment was ended.
I originally tried to use a dry ice/methanol cold trap, but the stopper on the flask continually leaked air, so I opted to connect
the vacuum adapter directly to the aspirator. This undoubtedly lead to an inferior product, but it was a trial run anyway.
A better way of heating the flask will have to be used in the future, as well as leaks fixed, etc. Still, I did receive a small (~100
mL) amount of insidious looking yellowish nitric that gave off red-brown fumes readily.
Alexires August 23rd, 2008, 11:57 PM

Lewis - An option for you to use may be to make your own custom heating mantle. If I remember correctly, there is a thread/
post around here that mentions it, but basically it involves pouring plaster of paris into a container, sitting the flask that you
are going to be heating in it until it starts to hold its own shape, then press some wire into the plaster of paris.
When it dries, apply current and work out what setting you need for various temperatures (try it on water first). Make sure the
wires don't touch, etc.
Your leaking joints problem could be solved with a liberal application of Teflon tape. Since the pressure is from the outside, it
should push the Teflon into the holes, sealing them up and holding a vacuum better.
Perhaps try rigging some kind of water condenser up to your water bath (just a metal "cover" with a fan blowing on it should
do). It will help keep the water in the bath without you having to constantly top it up with boiling water.

Sounds good, maybe just a couple of points though.
Prior to mixing your Sulfuric acid with your nitrate, make sure you always cool your H2SO4 in the fridge for an hour or two. It is
always a good idea using acids when they have been cooled. Doing this would of prevented the red/brown fumes that were
given off at the beginning. There should only be white fumes given off not red ones. Also, especially with KNO3, you really
have to make sure it has been mixed well. I personally hate using KNO3 for Nitric production, but I am well aware of its
advantages with being cheap and easily available. I have always found AN to be the best and also Sodium nitrate. You actually
have a reasonable liquid to distill rather than a disgusting sludgey almost solid slop which the KNO3 gives you.
Not having a cold trap will not give you an inferior product. This is merley to protect your vacuum device from harmful Nitric acid
fumes. Using an aspirator there is no worry as there is nothing to damage inside. A piece of tube straight from your aspirator
to your vacuum adaptor is all that is needed.

As always, thanks for the feedback. Perhaps my leaking joint problem just needs more tape. In the past I've made a very thin
layer of tape, never overlapping it more than 2 layers in any one spot. My logic was that the entire joint will contact the teflon
better if it is in a consistent thin layer, but next time I may just go nuts with the stuff.
I thought a cold trap helped to condense/freeze any water vapor coming off the aspirator. Regardless, I use an empty flask
between the rig and vacuum source now because I got some backflow from the aspirator once I turned it off the first time,
diluting my fresh nitric with a few drops of water.
As far as nitrate goes, I have easy access to KNO3 and Ca(NO3)2. Calcium nitrate is dirt cheap, which I like, but I'm not sure
about its tendency to from hydrates, so I decided to play it safe.
I think my next purchase might be a nice heating mantle from labX or the like. Maybe an overhead stirrer too. :)

Ah yes the backflow from the aspirator can be a killer. The last thing you want after an hour of hard work is to have it ruined
by some damn water.
The mere fact that your rig if under a vacuum is enough to keep any vapour entering it what so ever, so this is never a
problem from your aspirator. The problem can arise obviously when you turn it off and suddenly you get the backflow, like you
said. Luckily I think my aspirator is an anti backflow one which may be handy. Either this or just keep the vacuum running
however remove the tube from your rig before you turn it off.
An over head stirrer could be a very good investment. I have used a couple of magnetic stirrers in the past, always being quite
dissapointed with their overall performance. At first I find they seem to work a treat, but as your mixture starts thickening they
slowly but surely give up their will to stir. Even with AN, which stays alot thinner than KNO3, it still will not perform after you get
so far through it. Stirring it by hand is an absolute nightmaire. Every muscle in your hand and entire arm start to ache by the
time you have finished lol. Only problem with the over head stirrers is they seem to be reasonably expensive, and I'm not
sure how well they work??? Do you have any idea?
fluoroantimonic August 27th, 2008, 03:09 AM

I really don't think there is much of a need to bother with a vacuum when distilling nitric acid. As far as I know it has been
conclusively determined that using a vacuum when distilling nitric acid from XNO3+H2SO4 is usually useless if not harmful. It
will only slightly reduce decomposition, while it lowers the boiling point making condensers less efficient and pulling more water
from the sulfuric acid. As far as I know the only reason you ever really need a vacuum for nitric acid it to remove the last
traces of NOx from 99% nitric. Don't believe me? Read these threads (especially posts by garage chemist):
http://www.sciencemadness.org/talk/viewthread.php?tid=9450#pid109960
an interesting alternative idea

Hope this helps clear things up a little.

I don't use Sci madness, I might browse through there every few months, but I have actually read those threads on nitric acid.
He does have some good points however he seems to think it is not possible to obtain anhydrous Nitric acid from a single
distillation which in fact not true. If you are using high quality enough H2SO4 (98%), and you make sure that your nitrate is
completely dry (dried in oven prior to use), then you can obtain anhydrous nitric from a single distillation. If this is the case
then there isn't any water to draw from the H2SO4, only extremely minimal which in this case doesn't matter.
But it is a good idea though, if you are using slightly lower quality products where more water is present, you are not going to
be able to produce anhydrous nitric in one hit. The best thing you can do is to produce the highest concentration nitric in your
first distillation, then if you are striving for a really pure product which is only really needed in RDX manufacture, resdistill it
with the equal volume of Sulfurc acid to steal the last water. A vacuum certainly is needed for the second and last distillation,
otherwise you end up with a fairly strong yellow HNO3. Believe me. A slight yellow tint is ok, but really as clear as possible is
always the desired product.
RDX really is that fussy, water or nOX is a no no, and nOX is always going to be produced at atmospheric pressure no matter
how careful the distillation is carried out.

Interesting points. I distill under vacuum because I can. I have a few reasons for this, namely:
-I don't use a very powerful vacuum, so the change in H2SO4's tendency to trap water is minimal.
-The aspirator prevents toxic and corrosive fumes from entering my poorly ventilated workspace.
-The vacuum lowers the amount of heat needed to distill, which saves time, energy, and unnecessarily heating the shop in
these hot summer months.
Emil: On the topic of overhead stirrers, I admit to knowing next to nothing about them. I assume one would come in very
handy, knowing that not many heating mantles have a magnetic stirrer in them.
fluoroantimonic August 28th, 2008, 02:16 AM

Of course you can get anhydrous HNO3 from a single distillation, it just takes tons of conc. sulfuric. I think he's saying that its
a waste of high quality sulfuric acid, when you can use low quality dilute acid and save your concentrated stuff for a second
distillation to dehydrate the nitric acid. Or not use conc. sulfuric at all and break the azeotrope with something else. In any
case I know garage chemist knows what he's talking about, I don't believe I've ever seen anything be very high quality
information from him.
I have to admit using a light vacuum to keep the vapors at bay is a good idea. Even so it seems like a lot of screwing around
for such a benefit. What are you using the condense the nitric? I would imagine the extra effort and cost of more effective
condensation means (not to mention the vacuum itself) would out way the (very small) energy cost.
Lewis August 28th, 2008, 04:49 AM

I use a ~45cm Liebig condenser, and believe me, the vapors are in no danger of passing through it without condensing. They
are eliminated completely in the first 8th of the condenser length!
It could well be that the vacuum is worthless in many regards, but frankly until I get a better heat source it really helps. My
nitric distills painfully slowly even at my kitchen hot plate's maximum setting when I use a sand bath. :( This really is the only
reason I'm not pumping out tons of high quality nitric for many fun-filled energetic experiments. I simply do not have the
many hours necessary to make nitric by distillation at the current rate.
Insulating the flask and adapter with Al foil helps somewhat, but it's still such a tedious process, not to mention one that I feel
for the safety of my property I should be watching constantly.

Do what I did and turn to the direction of the sinister yet friendly flame. You can't beat it. So much more control over heating,
and you can kick it up as high as you need. I can distill quite rapidly when it is all set up right. I haven't timed it (yet) so I
cannot give an accurate number, but with the prior mixing and messing around aside, in an hour or two, I could distill a litre of
fuming nitric acid. I'm not sure on heating plates and such.
Mine never used to really satisfy me. My first test use with it was a 500 ml beaker filled with tap water. I turned it on, it was
baking hot, and yet the temperature of the water was hardly rising much. It took ages and ages to start to get the water to
any "hot" tempterature and even then it wasn't boiling. I was put off by this and decided to buy a portable camping stove
which has a wide ring on it for the flame. This way, no cracked glass, and plenty of fast reliable heat. Besides with the price of
electricity so high, I believe it is much cheaper to use a gas based fuel.
I use a 2000ml boiling flask and a 500ml recieving flask, which is soon to be upgraded for another 2000ml. A 600mm
condenser and the necessary adapters to connect the rig up. A Vacuum pump or an aspirator feeds the vacuum needs.
To me the distillation with a vacuum, even if it is just slight, makes the process run a whole lot better. Like stated your fumes
are just disposed of, and it seems to speed things up with a nicer margin for decomposition. I have distilled without vacuum
before, and I can tell you, it is alot slower, you have to regulate and mess around with the flame settings a great deal more,
and you end up with dark yellow acid.
I can understand the economical drawbacks with introducing the vacuum. Let's face it, you add a water aspirator, you use alot
more water which costs. You buy a pump and you have obviously used a fair amount of money for that. Unless you ghetto rig
yourself something out of some old bit of junk kicking around the garage (which will probably end up just breaking anyway), it
is going to cost you. However it is an investment which is based upon your personal situation. Planning on making nitric acid
insmall amounts a couple of times??? Forget it. Plan on making high quality nitric acid more often, absolutely.
bloodhound125 September 9th, 2008, 04:13 AM

Does anybody know where I can find a HNO3 concentration chart like the one used by the ragheads in that famous HNO3 video
where they make the acid in a stainless pot with nothing but latex gloves, I think someone said its on the FTP. I basically want
to know what the concentration of my acids are according to weight and temperature if this is indeed possible. Thank you
Moderator Note: I have approved this post because it was posted in The Watercooler originally and I could not find the answer
to his question.
Emil September 9th, 2008, 07:52 AM

Most people will usually just say UTFSE, but in this case the charts are actually quite hard to find. Not sure why, but I'm more
than happy to post them up for that reason.
Nitric acid concentration chart.

http://i250.photobucket.com/albums/gg256/emil2008_2008/hno3.png
Even though this is a Nitric acid thread, I feel that it's equally as useful to have the Sulfuric acid chart aswell.
http://i250.photobucket.com/albums/gg256/emil2008_2008/h2so4.png
Very handy charts, no matter what type of units you work in, the chart gives details for all. Don't have a hydrometer?? Not a
problem either because you can simply just weigh your nitric using the "grams per litre." Even if you only have 250ml of
product, just do the necessary maths.
Lewis September 9th, 2008, 02:51 PM

Those are indeed handy charts, Emil. Still, one thing about them confuses me. What does 20C/4C mean?

Those temperatures correspond to the density of water. The two temperatures are, more or less, room temperature in the
case of 20, and the maximum density of water at 4 (water occupies less and less space to just under 4 degrees, after which it
expands). I am not positive what the scale in the chart means exactly, but I suspect it may be the density of the mixed acid
at 20 degrees factoring in water density at 4 degrees. I see there is an asterisk after the entry, maybe it explains it there, but
the meaning of the asterisk is not in the pictures Emil gave.
Emil September 9th, 2008, 08:52 PM

Yeh I think Mega is correct, I would like to be able to confirm but am unable to do so due to not being able to find the source
where the damn charts came from. I think I got them from a site which I see mentioned here at RS. All I can seem to
remember is that the guys name began with F, and had his own site which is where these charts are from. I seem to
remember he was fairly well known to certain members.
Anyway I would go ahead and measure your density at 20c. This seems to be the default temperature for most measurements
including viscosity.
stupid939 September 25th, 2008, 06:54 PM

Yeah, that was Frogfot and his site was frogfot.com, but its down now. I was going to see if someone here had a backup of his
site, but I will get to that sometime else. I had a backup, but my external crashed.
I did find another list which will work:
http://img523.imageshack.us/img523/7554/nitricbm3.png
Its at imageshack, so I would download it and store it somewhere before it is taken down.
Alexires September 25th, 2008, 09:20 PM

stupid939 - Thanks for that, it will be very helpful.
DetaDude October 5th, 2008, 03:35 PM

Both charts appear to be from the Chemistry/Physics Handbook quite likely an older version, both charts look very much like
the ones in my older version of this publication.
Lewis November 14th, 2008, 05:50 PM

I feel it's time to come back and show everyone where I'm at with this project, after all the helpful advice I've gotten from this
thread. Last night approximately 50mL of HNO3 was distilled in an experiment to get the maximum concentration possible in
one pass.
A large excess of H2SO4 (140 mL) was used in an attempt to trap as much water as possible. The nitrate salts used were
120g KNO3, and 20g Ca(NO3)2.
The H2SO4 was pre-chilled before the salts were dissolved. Some heat was generated, but no noticeable NOx fumes. An
apparatus for vacuum distillation was set up, but it was discovered too late that the untested PTFE thermometer adapter
fabricated earlier leaked badly. As a result, only a feeble 5" Hg could be maintained in the system. (just enough to safely pull
off nitrogen oxides for dilution)
The reaction flask was heated gently for just under 2h, with the majority of the distillate coming over at 71C. Eventually, the
temperature began to rise again, until the heat was removed at 78C.
While a preliminary assessment of density placed the HNO3 in the ballpark of 1.5g/cm3, the volume measurements used in
the calculation were not accurate enough to determine the concentration of the acid. (It could in reality be anywhere from 80%
to 100%)
Here are the pictures:
Prepping the rig.
Dissolving the nitrates.
Heating reaction flask.
Close up of vacuum inlet and trap. The rubber stopper didn't stand up well to nitric acid vapours.
Reaction flask.
The pumps supplying water to the aspirator and condenser. The aspirator pump is a big electric waterfall supply, while the
condenser uses a small bilge pump.
Storing the new HNO3.
This is inconclusive as I obviously cannot determine the concentration without better volumetric measurement or different
equipment/diluting the acid. Perhaps the next experiment will be to try RDX out for size.
Emil November 15th, 2008, 10:25 AM

Very nice Lewis. I like the set up you have there. I also invested in one of the vacuum gauges that are meant for cars as well,
handy little things to just keep an eye on your vac throughout.
Good idea on the PTFE thermometer adapter, it's just a shame it was letting by. It is handy having the thermometer but really
not mandatory. If this is giving you problems I suggest investing in a proper adapter or just doing away with the thermometer
and plugging it off/changing the fitting. I don't use a thermometer on my setup. I don't really see any need in this instance.
The nitric will boil when it wants to boil, according to vacuum etc. So regardless whether it boils at 50c or 75c it just seems
unimportant info. What I do is heat the mixture up slowly and then just leave it at a slow boil. Adjusting the temperature very
slightly to get my preferred rate. I can distil quite fast because I have a vacuum source which pulls 25-30 In/hg. This means
breakdown of the nitric is very small. I don't have an exact rate at which I distil but I would say at least 3 drops a second.
One thing I did note is that you seem to be mixing your HNO3/Nitrate mixture in your round bottom distillation flask. This
would lead me to believe that stirring is minimal unless you arer using a magnetic stirrer??
Mixing of your initial mixture is very important I find for a decent result. Make sure as much nitrate as possible is dissolved
and this is why I tend to mix mine in a normal flask which allows me to really stir it well.
I find the magnetic stirrer to be of use about 2/3's the way through the mixing, after that is seems to just come to a stop as
the mixture really thickens up. I don't imagine a magnetic stirrer working if your using KNO3. The couple of times I used KNO3
as my nitrate, I had trouble stirring it by hand! It really got that thick. AN is my preferred choice now.
I notice you have an extraction duct. This is the next thing on my list. Can I ask whether it is hooked up to a fan to withdraw
the fumes, or is it merely just acting as a guide to let the fumed float out of the window??
This is just a tip as for the RDX comment you suggested. I once thought I'd give my 80-90% Nitric a go for making it. It was
yellow in colour and had only been distilled once. Let me tell you it was a waste of time. Don't get me wrong you will get some
RDX, but the yield suffered so bad. I think I used Mega's route (330ml Nitric and 75g Hexamine). From this I got about 10-
15g of RDX after washing and filtering and drying. I followed all instructions to a perfection, and the obvious flaw in the whole
thing was the quality of acid. So, Unless your Nitric acid is clear, and 98%+, don't bother wasting your precious acid and
Hexamine.
However it is very simple to acquire such a fine grade acid. Take your 80-100%yellow nitric and add to an equal mass of
concentrated Sulfuric acid. (both acids cooled in the fridge may I add). You may find a temperature increase so use a light
cooling bath to keep them under control if necessary. Distil this in your rig, However you are now looking for a decent
distillation which produces next to no NOx, so this calls for your 20" Hg + vacuum now which your aspirator is quite easily
capable of. You want basically no breakdown or colour change. A slight tinge of yellow is acceptable, as this can be removed.
Now your acid is ready for RDX.

Improvised Manufacture of Nitric Acid > HNO3 byAgNO 3
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knowledgehungry Novem ber 5th, 2002, 07:58 PM

I cam e across this formula in a chemistry book AgNO3+H2->Ag2+HNO3 I do not know if a catalyst is needed and I do not know wh at the conditions are for the reaction to occur. Just was letting
you guys know if anyone has any more info on this topic id be happy to hear it.
Sparky Novem ber 6th, 2002, 12:18 AM

This price is from <a href="http://www.clayartce nter.com /chem _raw_s.htm ." target="_blank">http://www.clayartcenter.com /
chem_raw_s.htm.</a>
Silver nitrate: $24 per ounce.
I think this m a k e s t h i s m ethod too expensive. Though I suppose it wouldn't have any water in it.
"Silver metal also dissolves in dilute or concentrated nitric acid, HNO3." - from <a href="http://
www.webelem ents.com/webele m e n t s / e l e m e n t s / t e x t / A g / c h e m .htm l" targe t="_blank">http://www.webelemen ts.com /
w e b e l e m e n t s / e l e m e n ts/text/Ag/chem .htm l</a>
W hich m eans you would have to distill it anyway I guess.
<sm all>[ Novem b e r 0 5 , 2 0 0 2 , 1 1 : 2 1 P M : M e s s a g e e d i t e d b y : S p a r k y ] < / s m a l l >
nbk2000 Novem ber 6th, 2002, 03:54 AM

$400/pound...real good "recip e" you've got the re. :rolle yes:
Isn't like you'd have to scrim p on using fertilizer and drain opener to make it for 25/ounce.
NOW USE THE FUCKING SEAR CH ENGINE BEFORE POSTING C RAP LIKE THIS AGAIN! :mad:
I'm o f t h e m i n d t o b a n b o t h o f you, one for posting this shit, the other for even responding to such shit.

Improvised Manufacture of Nitric Acid > Nitric Acid - Archive T h r e a d
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atropine
Freq uent Poster
Posts: 129
From : wales
Registered: OC T 2000
posted January 27, 2001 07:34 AM
--------------------------------------------------------------------------------
Usin g h2so4 @ 70% and kno3 at ~100% what will the yield of of nitric be using th e vapourising m ethod. Th e one with the 2
bottles and the heat and stuff.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
From : Brussels,Belgium,Europe
Registered: SEP 2000
--------------------------------------------------------------------------------
You should get something like 80% HNO3!
ALENGOSVIG1
Moderator
Posts: 766
From : V a n c o u v e r , C a n a d a
Registered: NOV 2000
posted February 07, 2001 03:17 AM
--------------------------------------------------------------------------------
why dont you concentrate the H2SO4 b y boiling and get highter percentage.
------------------
Explosives Archive
MacCleod
Freq uent Poster
Posts: 215
From :
Registered: DEC 2000
--------------------------------------------------------------------------------
Atropine,did you mea n the m ethod in 'Im p. Mu nitions Manual'?.There wa s a c o n d e n s e r d e sign in P M J B # 1 t h a t ' s e a s y t o m a k e
and works better.Just get a long sectio n of clea r flexible 1/4 or 3/8th. tubing and a large coffee can.Punch two holes through
the sides of the can,one at the top,another at the botto m . R u n y o u r h o s e through the top hole,looping it se veral tim e s a r o u n d
the inside,then run the other end out through the bottom hole;seal the holes up with silicone.Connect the top end to your
r e a c t i o n v e s s e l , a n d h a v e a s e c o n d c o n tainer below the bottom h ose.Then fill the can with ice,water and you 're set!.
------------------
"That which does not kill us,m a k e s u s s t r o n g e r "
Mr C ool
Freq uent Poster
Posts: 991
From : None of your bloody business!
--------------------------------------------------------------------------------
I get good results by using a leibig condenser and running ice cold water through the cooling jacket, but the coffee can idea
sounds very good, and cheaper.
atropine
Freq uent Poster
Posts: 129
From : wales
posted February 07, 2001 01:27 PM
--------------------------------------------------------------------------------
thanks room. I will try the beer can m e t h o d . G o d d a m i t i h a v e e n o u g h o f e m .

Purification
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stanfield December 4th, 2002, 04:51 PM

The nitric acid I obtain at the end of my distillation is red. I know there is a w ay to "remove" the NOx by adding urea, but w hat I want today is measurement !
How many grams of urea/how much mL of nitric acid.
Furthermore, do I need to heat the acid w hile adding the urea ?
this "recipe" is very imprecise, inaccurate all over the net...
thanx !
mongo blongo December 4th, 2002, 05:25 PM

Well the amount of urea used depends on how much decomposition has occurred. I think you also have to bubble a dry stream of oxygen through it. If you can find out how
much NOx is in your HNO3 then it would be easy to work out molar quantities.
kingspaz December 4th, 2002, 06:34 PM

wouldn't it be a fair approximation to place a flask of the acid over a white tile and then slowly stir urea into it until it becomes clear?

the problem w ith homemade nitric acid is that it's still yellow-red after purification, there isn't very much differences betw een the "pure" and the "contaminated" product :)
it's could be possible on w hite industrial nitric acid.
Otherw ise, I never got a problem making PETN but one day, runaway will occur due to this shitty NOx...

If your homemade HNO3 is still red/yellow after purification then it needs more urea. It doesn't matter if it is homemade or not. It is still HNO3 and a red colour indicates that
there is still NOx present.
If on the other hand, the HNO3 is still yellow after excess amounts urea have been added, it could be due to sunlight decomposing the HNO3 but this happens quite slowly.

After "purification", he's yellow (with light red coloration :) ) but during PETN manufacture, red fumes are given off... so this must be NOx ! And I've added many grams of urea
! I don't w ant to add too much urea because it decreases acid concentration...
see ya !

the NOx coming off from the PETN nitration is because its oxidising the PE/PETN. did you get a shitty yield? the oxidation could be a couple of things, too higher temperature or
too dilute nitric acid.
mongo blongo December 6th, 2002, 12:05 AM

Just a thought. If you just added a few drops of w ater, wouldn't the H20 react w ith NO2 to form some HNO3? But if that was so then it wouldn't make sense to re-distill the
HNO3 with H2SO4 because if there was any water in the HNO3 to begin w ith it w ould just react w ith the NOx to form HNO3 (assuming that there w as decomposition in the first
distillation).
I think I must have gone wrong somewhere.
stanfield December 6th, 2002, 05:31 AM

nonono, with PETN, I always got a FUCKING AMAZING yield... I'm just worried about the NOx released.
thanx !
Marvin December 6th, 2002, 05:17 PM

NO2 forms nitric and nitrous acid w hen you add water. Adding water wont force the reaction the other way until you only have a very dilute solution. Bubbling oxygen through it
does a mixture of oxidising the solution to nitric, and driving off NO2 and NO.
megalomania December 8th, 2002, 05:08 PM

The bubbeling of air through the nitric acid is quite important. It is meant to be done with the addition of urea, both, together... I forget the exact amount of urea to be added,
but I believe it to be quite small per unit volume of acid. I have seen the reference several times, but one would think I would have written it down by now ...
I should also add that it is possible to remove the redness by bubbling air into the acid while distilling with sulfuric acid (no urea needed, although it is more effective).
Another note just so nobody gets the wrong idea, while oxygen is the necessary component here to be bubbled in, one does not need pure oxygen, plain old air is sufficient,
although in all cases it should be DRY air.
[ December 08, 2002, 04:40 PM: Message edited by: megalomania ]
jarrod February 3rd, 2003, 05:54 AM

How can normal air be dried before entering a pump (a little fish tank one)
Is it possible to have the air pass through a couple of cigarette filters to adsorb the moisture, or cotton w ool?
____________________________
[/////][/////][//////] to pump
"""""""""""""""""""""""""""""""""""""""
inlet hose
air flow--->
I am really not sure so any input would be appreciated, w ould I decreases acid concentration more than 1% using moist air?
Thanx
[ February 03, 2003, 05:01 AM: Message edited by: jarrod ]
nbk2000 February 3rd, 2003, 07:10 AM

Search the internet with Google using the search term:
"drying air" desiccant
That'll give you a good start. I could tell you how to do it, but that'd be giving you the fish, rather than teaching you how to catch them yourself. < img border= "0" title=""
alt="[Wink]" src= "wink.gif" />
jarrod February 3rd, 2003, 10:07 AM

Well w ise fisherman w hy we are fishing <img border="0" title="" alt="[Wink]" src="wink.gif" />
Do you have a method (w ith some sort of measurements) for adding the urea w hile the desiccanted (if thats the w ord :confused: ) air is being bubbled through the impure
acid?
I searched the net and found no actual urea/acid ratios or close to.
I found out from searching the form that it is very little urea to acid. :rolleyes:
I was thinking maybe around 2g to 500ml for a ball park figure

This is based on my 0 experience and 3.5 hours of searching/reading
So any input is very w elcome
Thanx
nbk2000 February 3rd, 2003, 10:52 AM

1 gram urea to 100 grams acid.

For how long should air be bubbled through the acid?
IPN February 16th, 2003, 08:38 AM

Why wont you try it your self.
Test it and then you will know what is the correct time.
Not asking others to do the job for you.
Mic February 16th, 2003, 11:34 AM

Hey,
Today something that I think was impossible happens ! I found some HNO3 here in Canada !! It's a small hydroponic store that sell some pipe for smoking weed and some
drugs that are legal (salvia, legal mushrooms, natural ecstacy, legal peyote, etc...) and they sell stuff for growing w eed.. I was there because I wanna buy some salvia and I
found HNO3 ! it's a PH-.. Do someone know what is the concentration of this stuff ? They also sell some H3PO4 and some H2O2 35%.
Thank You.
Mic
rikkitikkitavi February 16th, 2003, 03:23 PM

nitric acid for fertilizer use is usually around 50-53 %, it should be listed on the package according to IATA,ADR,UN e t c transport rules.
/rickard
Dave Angel September 11th, 2004, 05:41 PM

I think I've finally found a way to get concentrated nitric acid clean of NOx, that I am happy with.
Start w ith 500mL of 97% technical H2SO4 in a 1L jug, adding as much KNO3 as is feasible before the mixture becomes too pasty to handle, which usually amounts to 800-900g.
The slurry is poured into a 2L rb flask mounted in a heating mantle. The upper part of the flask is clad in ceramic wool and the still head wrapped in an old thermal glove.
I'm afraid I have no temperatures to report as I have no thermometer pocket or ground glass thermometer. As the temperature is increased there is some awkw ard bubbling as
the HNO3 makes it way through the slurry and the atmosphere initially becomes very dark red with NOx. After a while, the colour clears and the nitric acid comes over steadily
(2-3 drops per second). The result is usually about 320mL of orange HNO3, density 1.57(2)g/cm3.
This is all very common know ledge but I feel it is important to include a full guide to what I do. The important bit is the purification step:
The contaminated HNO3 is placed in a 500mL pyrex jug on a hotplate/stirrer with stir bar. The output of a small fish tank air pump (capacity 0.75L/min) is led to the bottom of a
small glass vial (tincture of iodine bottle, 100mL) via a silicone tube and glass tube. The vial is filled with CaCl2 and a length of output tubing is placed at the top of the vial, the
whole array sealed with blu-tac. The output tube is connected to a length of glass tubing (which happens to have a capillary end) mounted in the acid. A thermometer is
clamped in place and the temperature is brought up to 40-45C with stirring, and air being bubbled through, (temperature according to Microtek's work).
After about 3 to 4 hours of bubbling, and much off-gassing, the nitric acid is almost colourless, a slight yellow remains. Left to cool, this becomes absolutely colourless at room
temperature. Density was calculated from the mass of 100mL of this acid to be 1.52(7)g/cm3. No urea w as used at any point to rid the acid of NOx, as per Microtek's
suggestion in his quantitative report!
Now, the density suggests 100% HNO3 w hich will clearly not be the case. Possible reasons for this? The ever present errors in measurements, possibly a little remaining NOx
raising density. I have a slight worry that some sulphuric acid may have been carried across. As I am being quite intensive with my production of HNO3 - using up as much
H2SO4 as possible, the heated flask in the distillation becomes filled with a great, irregular mass of solid sulphates towards the end. My fear is that these allow local heating of
the remaining H2SO4 to boiling temperature, which I know is very high, but still I am paranoid to some extent about it, now I have it in my mind.
I'm probably just worrying about nothing, and I'm sure someone will set me straight. Besides, even if this were the case the acid could be re-distilled to leave the traces of
H2SO4 behind, before removal of NOx.
Anyway, with a few concerns put aside: I have made highly concentrated nitric acid, free from NOx, with one distillation, no need for vacuum, no use of urea or DCM/dry ice
extraction methods. I intend to improve the method with a stronger pump to power a glass gas diffuser, working in a multiple necked flask with reflux condenser to process
larger volumes faster and capture escaping HNO3 vapor.
penguin6636 January 6th, 2008, 06:09 PM

The first time I distilled nitric acid I had placed a fan at the base of my condenser to blow aw ay all the NO2 that was fuming in the air. It also kept my end product clear. I tried
the same concept with a batch I just made and dripped it through a separatory funnel about 6 times. My initial product had a strong yellow color to it, but after dripping it past
the fan several times it cleared up. I did this outside so the temperature was 5-10C and the air was fairly dry. The amount of acid that evaporated was negligible. Does this
method sound practical?
http://img201.imageshack.us/img201/2292/nitricno2dc9.jpg http://img201.imageshack.us/img201/4662/nitricclearun7.jpg
DetaDude March 19th, 2008, 02:56 PM

I recently found myself browsing through a used book store and ran across an old publication, circa 1923 published in the U.K. "Absorption of Nitrous Gases"
by H.W.Webb MS, F.I.C.. This book is just full of helpful info on our favorite acid
and w ays to make, concentrate, and purify it along w ith pit falls (allbeit aimed at an industrial operation) but adaptable to small scale.
One item that this book mentions is the use of ozone for purification and concentration of the acid by use of ozone. It does state that it is to expensive to use in industrial
settings but performed well during experimentation (1923).
I have long been intrested in using ozone in conjunction with HNO3 production and after reading this publication I think I'll tinker around with it in my lab. If
anyone out there has some info or background they don't mind sharing I would be deeply appreciative. As soon as I can set up some tests I'll report back on my findings.
I realize that this is long out of publication but poss. may find an old copy in a school/public library, used book store etc.

Improvised Manufacture of Nitric Acid > what a conc. of H2SO 4 would work for HNO 3 dist? - Archive file
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zaibatsu March 15th, 2003, 03:12 PM

n o _ n a m e_available
A new voice
Posts: 25
From : germ any (?)
Registered: JAN 2001
posted January 20, 2001 06:46 PM
--------------------------------------------------------------------------------
hi guys,
first i have to say -as new born mem ber- a big hello to your great board.
s o n ow:
i want to distill HNO 3 from a KNO 3 a n d H 2 S O 4 s o l u t i o n .
a) would car-battery conc. of H2SO4 (~65%)work ?
b) i read in an serious "m a k i n g of nitric acid" that u sho u l d a d d s o m e AgNO 3. anybody heard about this ?
Mr C ool
Freq uent Poster
Posts: 991
From : None of your bloody business!
--------------------------------------------------------------------------------
You need 98% to get pure nitric acid, but you could just boil the acid you have un til very thick fum es com e off to concentrate it.
65% will m ake nitric acid I think, but it will have quite a lot of m oisture in it.
I don't know about silver nitrate. it'll probably cost too much to be worth it.

Improvised Manufacture of Nitric Acid > Acid recovery after RDX pption - WAR NING!!!
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Mr Cool April 12th, 2003, 03:41 PM

Maybe you wouldn't b e stupid enough to try this, but I was :o .
I had read that residual organics (form aldehyde etc) hindered acid recovery from the spent acid after m a k i n g R D X o n a n
indu strial scale, and therefore the spent acid was com m only used to m ake fertilisers instead.
I thought that m aybe the problem was how to deal with the form a l d e h y d e f u m es on such a large scale, and I was willing to
g i v e i t a g o o n a s m a ll scale.
So anyway, 180g of d istilled acid, 60g of HDN, gave me slightly over 41g of crude RDX which is awaiting recrystalisation. I
haven't had a chance to do this yet, m y lab sm ells too bad still...
Obviously, if the residual acid in the solution after dum ping it into water could be recovered, as it can for PETN etc, then the
p r o c e s s w o u l d b e c o m e m u c h m o r e e c o n o m ical. So I tried it...
T h e r e w a s a p p r o x 4 0 0 m L of solution in total. My plan was to reflux it for a while to drive out/destroy m ost of the remaining
organic com pouns, before distilling off azeotropic nitric acid, then concentrating this with sulphuric acid and m a k i n g a n o t h e r
batch of RDX.
The strange thing was, it refluxed happily for almost 15 m inutes, then in the space of around 5 seconds it turned in t o a n
erupting volcano of nitrogen o xides, nitric acid and form a l d e h y d e .
T h i s e x p e r i m ent cost me about 30 for a quickfit leibeg condenser, 7 for a quickfit reduction adapter, and a few hours
clearing up a cidic formaldehyde solution from all over m y lab and the ceiling :( :(.
So, I thought I would warn you about it, just in case anyone was thinking of doing the sam e !

Poor glasswa re, lab, chemicals, hum an! <im g border="0" title="" alt="[W ink]" src="wink.gif" /> Qu ite freak story, at least fire
didn 't start up. I think what happened here is the reaction betwe e n a m m o n i a ( f r o m a m m onium nitrate/water equilibrium) and
form aldehyde in acidic media to give methylam ine, ethylam ine, formic acid, HEAT, etc... (this reaction is quite known).
Am m o n i u m n i t r a t e a n d f o r m a l d e h y d e a r e b y p r o d u c t s o f t h e h y d r o l y s i s o f H M T A ( I a s s u m e d HDN = HMTA,
h e x a m ethylenetetratem i n e , H e x a m i n e , U r o t r o p i n e ? ) C ould well be something else like a radicalar chain reaction though, that
would explain the 15 minutes peacefull reflux.
If one is really in the mood of recycling nitric from RDX m ixture, he could probably neutralize the residual liquor (with say,
s o d i u m bicarbonate), evapora te the solution, then add sulfuric acid until all sodium nitrate has rea cted and finally d istill out
t h e a c i d ( a m m onia wouldn't com plicate things as it would have been rem oved during the evaporation step). I'm not certain
about this, but it does seems possible to do. In any case, I would rather purchase KNO3 from the drugstore rather than losing
a couple of hours recycling the acid, that's my 2 cents. Hoping your lungs will reco ver properly from this experience :D
rikkitikkitavi April 12th, 2003, 06:33 PM

a m monia cant exist in a acidic environm ent, it will all react to am m onium ions...
but the rem aining nitric acid plus the a m m onium nitrate formed probably started a runaway oxidation of the organic residue in
solution, when it was heated enough beoynd a certain threshold.
Fortunately you had a dilute solution which prevented a even m ore feriocous reaction, possible explosion and fire!
m aybe by distilling under reduced pressure, the majority of the organic can be stripped of , and the rem ain ing carefully
o x i d ized ...
but it is probably very difficult to control this reaction and get a good separation since it is difficult to judge at what temperature
a n d p r e s s u r e m a x i m u m organic/minim um nitric acid is done.
on an industrial scale this is probably one of the secrets of each manufacturer , since recovery of strong nitric is determinal for
the cost of product.
/rick ard

The reaction I was referring to can be found here : <a href="http://www.rhodium.ws/chem istry/m ethylamine.htm l"
target="_blank">http://www.rhodium .ws/chemistry/m ethylam ine.htm l</a>. If one does the study of this reactions, he find out
that it proceeds throu gh this equilibrium :
NH4<su p>+ + H2O -> NH3 + H3O +
I agree there's not m uch free amm onia in a su ch acidic solution (a couple m icrogram s, maybe), but there is enough to start
this reaction. HCl is a stronger acid than HNO 3, thus there should be even m ore free NH3 in Mr.
Cool's acidic solution than in the actual reaction I quoted. Quantitativly :
NH4<su p>+ + H2O -> NH3 + H3O +
KA = [NH3][H3O+]/[NH4+] =
6,31x10-10
If we set the activity in hydron ium cations to be of 0,1M (just for the purpose of the calculation, this means pH = 1,0) we find :
[NH3]/[NH4+]= 6,31x10-9
T h i s m eans that in th is solution, if there are, for exam p l e , 1 , 0 M i n a m m onium ca tions, there will always be 6,31x10 -9 </
s u p > M i n a m m o n i a , t h i s s e e m s sm all but this is enough molecu les to start a reaction. To convince yourself, use Avogadro's
n u m ber and find out that in 400m L of this hypothetical solution, there is 1,5x1015 free am m o n i a m olecules
fooling around. That's 1,5 million of billion of a m m o n i a m o l e c u l e s ! .
<sm all>[ April 13, 2003, 05:32 AM: Message edited by: Einstein ium ]
Mr Cool April 13th, 2003, 08:55 AM

Einsteinium, HDN = hexam eth ylenetetramine dinitrate. In my experience (and others), it gives better yields with less acid than
f r e e b a s e h e x a m ine.
Next tim e I'll probably recover the acid as HDN, by adding some hexamine, cooling, filtering etc, then using this in subsequent
batches (although if I recover it all this way I'll soon end up with a lot of HDN!). If I recove r it as NaNO3,
NH4NO 3 etc, then I will actually be losing m oney that way since the prices for the hydroxides from
the sources I have would mak e the resulting nitrates significantly more e xpensive than fertiliser nitrates, plus it'd be a lot
m ore effort to recover them .
W hat a pitty it can't b e purified like I was trying to do :(. Maybe under reduced pressure it could be done safely, but now I am
reluctant to try it!!
I know it's re ally cheap just to m a k e s o m e m ore acid, b ut it seem ed senseless to throw away 80% of the acid that you m a d e !
If th at rem aining 80% could b e recovered, giving 100% efficiency based on acid (I know that wouldn't be possible, it's just to
m ake it sim pler to work out!), then the 200m L of 70% HNO3 that I started with could have made well over 200 g
of RDX!
W ell, from now on I'll only recover the acid afte r making PETN or MHN. I've been doing this safely for a while now, and there
aren't really any organic by-products so I'm sure it's safe. But first I'll have to find another 40 to replace my glaswear :(.
Microtek April 14th, 2003, 10:22 AM

I rem ember seeing a patent for HNO3 recovery from waste flows after RDX production. I'm not com pletely sure, but I think
H2SO 4 was added before heating the waste. At least that way was used for recovering acids from HMX production via DADN.
Another way was to use Mg(NO3)2 to b reak the azeotropic coupling between water and HNO3 which could then be distilled off.
Anyway, the m e c h a n i s m in the m ethod with H2SO4 was IIRC, that the byproducts from the R DX synthesis were destroyed by
the hot sulfuric acid ( as in the nitrom eter ) and volatilized.

Manufacture
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stanfield June 5th, 2002, 04:48 AM

What are all the distillation possible to produce nitric acid ? (with added sulfuric acid, huh !)
I know : - Sodium nitrate (the one I use !)
- Potassium nitrate
- Calcium nitrate if I remember correctly...
what's the suite ?
I posted this because I hope founding a cheaper nitrate than sodium nitrate !
thanx !
Synthetically Hopeful June 5th, 2002, 05:09 AM

I seem to remember calcium nitrate being the best, but that was a long time ago, IIRC it dosent act as bad when adding it.
inferno June 5th, 2002, 05:34 AM

A possible way of synthesising HNO3:
Chemicals needed
Sodium bisulphate (NaHSO4)
Nitrate ion source (KNO3, Ca(NO3)2, NaNO3, Ba(NO3)2 etc)
Equipment needed (improvised, as not many people have good glassware)

Glass bottle/flask (wine bottle or something)
cork/stopper with hose or tube coming out
Acid-resistant container, with (salt) ice water in or around, if around it must have some water in it too
(Pyrex beakers are good, and, if youre at school, fit easily into your pocket)
Method
(I havent actually tried this, i only learnt of it in the last few days and have no nitrates atm nor sodium bisulphate. I read about it in an article about a 17 year old who made
his own nuclear reactor, he used the acid to purify some uranium he obtained)
Put the sodium bisulphate and NO3 donor in the bottle, flask or whatever youre using. Im not sure if you should put water in, but i think it *may* help. The
container has to be heated, with an open flame (may crack though) or in an oil bath/hot water bath or something. A bunsen burner under a flask would work well. The gas
resulting will go up through the tube, and the end of the tube must be secured into the ice bathed water. The gases escaping from the chemicals should condense in the cold
water to make HNO3, though it will be very impure, and a purification method probably needs to be found, im sure theres a few, simple distillation might work.
I havent done this but im pretty sure it works. Anyway its a start for this board, arr so many new boards since yesterday!
da man June 5th, 2002, 06:08 AM

Inferno, as some other members said, that reaction would happen at high temperatures, which would decompose the nitric acid into NO2, H2O, and O2.
Ammonium nitrate also works, 80g of ammonium nitrate + 90g of sulphuric acid works well. This was worked out by mongo blongo, so all credit goes to him :) This methods
good for me, because i get my ammonium nitrate for $1.50 a Kilo!

Many people said to me that ammonium nitrate method doesn't work !?

If you want to make HNO3 from H2SO4 (or NaHSO4) and Ca(NO3)2 you will have to make the Ca(NO3)2 in a solution, otherwise the solid gets coated with insoluble CaSO4,
preventing further reaction.
Eventually, some CaSO4 dissolves and lets the underneath Ca(NO3)2 react but this is a much slower reaction.
(parallell to Na2CO3(aq) + Ca(OH)2(s) => CaCO3(s) + 2 NaOH (aq) , a very old way of making lye from boiling soda and lime together for many hours, and eventually the
reaction completes )
I used a aprox. 4 M solution of Ca(NO3)2 and added eqimolar amount of

sulfuric acid. Cooling and ventilation!
Any higher concentration of Ca(NO3)2 and I found that the precitpated
CaSO4 made the whole into a sludge that wouldnt settle. But this is probably depending upon how fast you mix them. A slower mixing time gives larger CaSO4 crystals and
easier settling time, because of lower oversaturation of CaSO4 in solution.
Anyway , after finishing the reaction, I let the CaSO4 settle and decanted of the top liqiud (8 M HNO3)- This I distilled until I got
aezotropic HNO3.
Unfortunately I only had access to non-vaccum proof glasware during this, but later I made > 68 % acid with NaNO3 and H2SO4.
/rickard

calcium nitrate in insoluble in sulfuric ? damn...
Even by heating the mix ? I hate the idea of adding water !
da man June 5th, 2002, 06:41 AM

Stanfield, who said thet the Ammonium nitrate method didn't work, it worked for me (the distilling didn't work, but i know it made nitric, from the fumes, and i used it to make
PETN, even without distilling it)?

Da man - H2O+NO2 would reform to HNO3 (might need some compression though):
2H2O + 2NO2 ==> 2HNO3
And the gases would be going into a salt ice cooled container.
Mr Cool June 5th, 2002, 08:27 AM

Inferno: not without oxygen it won't, check your equation...
It should be:
H2O + 2 NO2 + 1/2 O2 --> 2 HNO3

I read in the book "Nitrogen and Phosphorus" a way to synthesise NO2, by adding an extra step to this process you could easily turn this into HNO3.
I dont have the book on hand, (I will have to borrow it from the libary) but I can remember the process invloved. A glass U tube in an ice bath connected to a test tube at one
end. The test tube contained a small amount of Lead Nitrate (Pb(NO3)2) which was used in the demonstration. The other end of the U tube had a glass pipe that went into a
beaker full of water. The beaker also contained a test tube full of water, that would displace some of the water in order to collect the NO2.
The PB(NO3)2 was heated at one end, as it decomposed into PbO it released NO2 gas. The NO2 gas then travelled into the U where the Ice bath could condense some
impurities like N2O5. NO2 was then collected in the Test tube at the other end.
This method could work quite well if you have the equipment needed for this process.
This post will be edited when I have the book

Ca(NO3)2 isnt insoluble in H2SO4, but CaSO4 is formed on the surface of the Ca(NO3)2 crystals, preventing a further reaction.
that said, solubility of CaSO4 is larger in H2SO4 than water due to

CaSO4 + H+ = Ca2+ + HSO4- but not much.
/rickard

The equation I use to distill is :
3NaNO3 + 2H2SO4-->3HNO3 + NaSO4 + NaHSO4
So, If I use Calcium nitrate, is this equation different ?
DBSP June 5th, 2002, 01:49 PM

I belive you rection is wrong.
NaNO3 + H2SO4----> HNO3 + NaHSO4. You can't get more than one mole of HNO3 from 1 mole of H2SO4 since the second release of the H+ is performed at such high
temperatures that the HNO3 formed would emmediately be decomposed.
mongo blongo June 5th, 2002, 03:01 PM

Yes DBSP is right and I think it should be the same for Calcium Nitrate but I would stick to NaNO3.

Ca(NO3)2 available as a fertilizer is many times a double salt:
Ca5(NH4)(NO3)11*10H2O Nitrogen content 15,6 %
Pure Ca(NO32) is usually available as Ca(NO3)2*4H2O

Nitrogen content 11,8 %
so you can separate them by reading at the package.
you have to dry it before making any HNO3 if you want to make high-conc. Dried CaNO3 is very very hygroscopic, like NH4NO3
Even if the NH4NO4 doesnt interfer I removed with GENTLY heating to
180-190 C (tried small batches at first) when the NH4NO3 decomposes into laughing gas:
NH4NO3 = N2O + 2 H2O
(technical method of making laughing gas)
Anyway, I never succeded making HNO3 from solid Ca(NO3)2 and H2SO4, some HNO3 was formed (heavy ,irritating white smoke) but later I realized that I probably have to
crush or grind the salt into a extremely fine powder to increase reaction surface, which I didnt-
In solution it worked much better :)
/rickard
stanfield June 5th, 2002, 04:22 PM

so, I must make a saturated solution of calcium nitrate then add sulfuric then distill... ok, but what about the concentration of final nitric acid ?

check my other posts at the toppic : HNO3 from NaHSO4 and NaNO3...
/rickard
cspotdie June 11th, 2002, 07:22 PM

Is the Sulfuric Acid used in Drain opener strong enough to use in the production of HNO3 ?
thanks
Lifes a bitch then you pay

Sort of. It's diluted most of the time but you can just boil it to purify it. Boil it until you see white fumes and then you should have somewhere around 98% sulphuric IIRC.

The concentration sold for drain opening use varies, but it is typicially in excess of 96%. You will not have any luck just boiling it to get fumes, that trick is for battery acid. At
this concentration it is quite useful in distilling nitric acid, up to about 96%. After you have used the sulfuric acid, it will contain water (the more water in the nitric the more the
sulfuric will have), so you may then try the boil.
Sparky June 23rd, 2002, 11:28 AM

This is a bit off topic but: Can you use molecular sieves to dry nitric acid? I can assume you can't because nobody seems to but why not?
Sparky June 25th, 2002, 08:33 PM

I was reading rec.pyrotechnics and I found a post that was dealing with nitrating cellulose.
<a href="http://groups.google.com/groups?hl=en&lr=&ie=UTF-8&oe=UTF8&safe=off&threadm=AtIQ8.52922%24s82.4103635%40news1.calgary. shaw.ca&rnum=1&prev=/
groups%3Fq%3Dnitration%2Bof%2Bcommon%2Bce" target="_blank">http://groups.google.com/groups?hl=en&lr=&ie=UTF-
8&oe=UTF8&safe=off&threadm=AtIQ8.52922%24s82.4103635%40news1.calgary. shaw.ca&rnum=1&prev=/groups%3Fq%3Dnitration%2Bof%2Bcommon%2Bce</a>
llulose%2Bgroup:rec.pyrotechnics%26hl%3Den%26lr%3D %26ie%3DUTF-8%26oe%3DUTF8%26safe%3Doff%26selm%3DAtIQ8.52922%25
24s82.4103635%2540news1.calgary.shaw.ca%26rnum%3D1
It states that magnesium nitrate can be used to concentrate nitric acid. Does anyone know a procedure for this? If you have say 50% nitric acid can you add magnesium,
forming magnesium nitrate and drying the acid? What kind of concentration can be reached?
vulture July 5th, 2002, 05:03 PM

I assume you can better use MgSO4 for this, which is a strong dessicant. It is freely available as epsom salt in the form of it's heptahydrate, MgSO4.7H2O. You just need to
heat that till all the water comes off.
It won't react with the nitric acid because that would require the formation of H2SO4, which is a much stronger and less volatile acid, so that won't happen.

Concentrating nitric acid report
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View Full Version : Concentrating nitric acid report

I bought 1 Liter of 58% nitric acid several weeks ago and today I decided to (try to) concentrate it...
(Usually, I made my nitric acid by distillation of sodium nitrate and sulfuric acid)
So, I put the entire bottle of nitric acid in the boiling flask then I added 1 Liter of 92% sulfuric acid (yes, I know this must be 2 L but I didn't have an another liter on(under?) the
hand...)
Then I began the distillate but after 2 hours, I got the same nitric acid (58%)
So, I have 3 questions :

- Must I boil down the acid to 68% before ?
- When w ill I know that my acid is at 68% ?
- Must I only add 2 Liter of sulfuric acid ?
thanx for all !
[ July 09, 2002, 02:15 PM: Message edited by: stanfield ]
DBSP July 9th, 2002, 03:23 PM

Most likely the H2SO4 got to diluted by all the water and didn't function properly. Kepp the acid as it is and add a nother liter as soon as you get it, and then distill it. If you
decide to do anything before that you are risking to loose lots of acid.

ok, thanx
Theoriticaly, w hen you finished distilling your mixture, there's only diluted sulfuric acid who's remaining in the boiling flask ? right ? So, if you boild it dow n, you could recover it's
original concentration, no ?
In other w ords : you get back you sulfuric acid and lot of concentrated nitric acid ? life is wonderful ! (chemistry too ! :) )
see ya !
ALENGOSVIG1 July 9th, 2002, 05:43 PM

Yes you can reuse the H2SO4 if you heat it to drive off the w ater content.

That's what I though :)
So, I think this method is better than nitrate+sulfuric :
- lesser time
- you can get back you sulfuric acid
- I think there are less nitrogen oxides produced during the process...
What about the temperature ? I have this one (dunno how to say in english!):
<img src="http://stanfield.150m.com/tete.jpg" alt=" - " />
and not a Vigreux column :
<img src="http://stanfield.150m.com/vigreux.jpg" alt=" - " />
see ya !
EDIT : I haven't yet any vacuum pump < img border= "0" title="" alt= "[Frow n]" src= "frown.gif" />
Mr Cool July 10th, 2002, 10:09 AM

If I were you I'd do it in a few smaller batches: boil down your litre of H2SO4 to get it very strong, add a few hundred mL of 58% HNO3, distil, boil dow n the H2SO4 again, add
more HNO3, distil...

Is there a way to calculate how much sulfuric acid you need ?
this method is too long, Mr cool...
Microtek July 11th, 2002, 05:39 AM

I use equal volumes of 62 % HNO3 and 96 % H2SO4, and it works excellently even without vacuum. You have to make sure that the temp doesn't get too high though, or the
water will come over as well.

you're lucky ! I use a bit less concentrated nitric acid and it didn't work ! (my sulfuric acid too was a bit less concentrated...)
Microtek July 13th, 2002, 05:18 AM

I think the reason is that the water was boiled off of the H2SO4. As you said yourself: Once you're done distilling, you could concentrate the sulfuric acid by boiling the w ater off.
At low er concentrations H2SO4 will give off the w ater at lower temp, so if you leave the setup you need to be sure the heating isn't too much, or you'll just end up with your
original nitric acid in the receiving flask.

I just tested out making HNO3 by distillation of ammonium nitrate + sulfuric acid = it didn't work !
By the way, w hat's the equation of distillation of calcium nitrate + sulfuric acid ? I know the one which involve sodium nitrate (The one I alw ays use) but calcium nitrate seems
to be cheaper than sodium nitrate...
thanx !

H2SO4 + Ca(NO3)2.4H2O ---> CuSO4.2H2O + 2HNO3 + 2H2O
i included w ater of crystilisation in the equation to show that w ater w ill be produced as a by product of the conversion. i think KNO3 is prefered because (as far as i know which
isn't very <img border="0" title= "" alt="[Wink]" src= "w ink.gif" /> ) it has no w ater of crystilisation.

damn... NaNO3 too hasn't water ? (Here NaNO3 is really cheaper than KNO3 !)
rikkitikkitavi July 19th, 2002, 08:31 AM
NaNO3 is hygroscopic, which KNO3 isnt. However even KNO3 contains
water to some extent so for maximum yield , dry it.
I have tried distilling with CaNO3, however with negative results.
First, Ca(NO3)2 is extremely hygroscopic and is hard to dry properly.

I dried it in a oven at 150 C. Even after that one or two hours of exposure to air lead to moisture being absorbed into a sticky mess.
quick mixing after the drying, thus.
The Ca(NO3)2 sold as 15.5 % N-content is a double salt:

Ca5(NO3)10*NH4NO3*10 H2O. I separated the NH4NO3 by adding Ca(OH)2 and boiling it for several hours. (NH4 + OH => NH3 + H2O)
more important is that the reason why it failed w as probably

a insoluble layer of CaSO4 formes on the surface of the Ca(NO3)2 preventing furhter reaction. Some CaSO4 dissolves in H2SO4 forming
CaHSO4 though, but not much. The reaction progresses slowly.
I could feel a clear scent of nitric acid thoug, and w hen heated it gave of HNO3-vapour.
( Pure sulfuric mixed with CaSO4 ,and later filtered of to a clear solution clearly preciptates CaCO3 when neutralized with Na2CO3. But not much though. Some CaSO4 goes into
solution with H2SO4. A more dilute H2SO4 preciptates more CaCO3. I havent been able to collect the preciptate though, since the crystals where extremely fine and simply
wouldnt settle or be filtered. )
/rickard

I always distill my HNO3 with CaNO3. For me, CaNO3 is the cheapest and most easily availible nitrate. It is how ever VERY hygroscopic. Luckily the plastic buckets it comes in
seals very well and the CaNO3 doesnt seem to absorb any (very little anyhow ) water. But, if i leave the prills out, they w ill abosrb so much water it becoms liquid!
Also, i get better yeilds (after being tripple distilled with H2SO4) when using CaNO3 w hen compared to KN03 or NH4NO3.
rikkitikkitavi July 19th, 2002, 05:05 PM

Alensovig, what ratios Ca(NO3)2:H2SO4 do you use?
Do you know your temperature in the flask when the HNO3 starts to come over?
/rickard

so, the calcium nitrate method work ! For me too, this is the cheapest nitrate !
Does it have an effect on nitrogen oxides formed during the reaction ? less or more ?
thanx !

Wait a minute ! I made some calculation last night and I found that for 1000 mL of sulfuric acid, you get about 400 mL of nitric acid...
With sodium nitrate, I get more than 1 Liter of nitric acid !!
But this w as last night and I w as tired so I maybe made a fault...
xoo1246 July 20th, 2002, 04:53 AM

Could people take pictures of their distillation setup and post them, w ould be interesting. If you w ant to, that is.
I was planning to buy a setup, but then again, I have never used one. I know how they work, what parts there are etc, but tips would be nice. What heat sources are you
using, electrical, flame, oilbath, etc?
I'll soon attent a chemistry education, hopefully I'll learn something there.

I taked photos of my distillation apparatus but I haven't them yet ! As soon as possible I will post them here !
I personaly use a sand bath...
stanfield July 22nd, 2002, 04:45 AM

What a luc k ! I just found a res eller near me who sell 25Kg bag of potassium nitrate for 12 !
So, what's the equation of the distillation w ith potasium nitrate ?
3KNO3 + 2H2SO4 => 3 HNO3 + ... ???
thanx !
DBSP July 22nd, 2002, 09:20 AM

KNO3 + H2SO4 --> HNO3 + KHSO4

thanx,...
At this moment, I'm distilling and the distillation with potassium nitrate take more time than the one with sodium nitrate !
I used 3KNO3 + 2H2SO4 => 3 HNO3 + ... so the sulfuric acid is in little excess which I like.
I used 500 mL of sulfuric (96%) and 1400g of KNO3
I'm really pissed off ! I hope this distillation w ill finish before going to bed :mad: !
thanx elsewhere :)

argh ! I justed finished my distillation and I ONLY GET 300 mL of NITRIC ACID !!! (theory : 587,5 mL !!!!) This method really sucks ! I really prefer sodium nitrate ! Furthermore,
the nitric acid looks really red so I have to purify it with urea ! With sodium nitrate, the final nitric acid is pale yellow and no purification is needed !
shit !
DBSP July 22nd, 2002, 02:54 PM

Stanfield, I don't thik that your equation is right. As I posted before; KNO3 + H2SO4 --> HNO3 + KHSO4, this means that:
3KNO3 + 2H2SO4 --> 2HNO3 + 2KHSO4 + KNO3, which means no excess H2SO4.
What ammounts of chems did you use?

I used 3KNO3 + 2H2SO4 --> 2HNO3 + 2KHSO4 + KNO3
so, 500 mL of H2SO4 and 1415g of KNO3.
mongo blongo July 22nd, 2002, 11:50 PM

I agree with stanfield that NaNO3 is the best. I have tried KNO3 and NH4NO3 with shitty yields.
EDIT-WTF? You have KNO3 on both sides of the equation? It's:

KNO3 + H2SO4 --> HNO3 + KHSO4
[ July 22, 2002, 10:55 PM: Message edited by: mongo blongo ]
stanfield July 23rd, 2002, 03:49 AM

I have a friend who said that the correct equation is :
2 KNO3 + H2SO4 => 2 HNO3 + K2SO4
He saw it in a chemistry book ! So this must be right ? what do you think about it ?
[ July 23, 2002, 02:50 AM: Message edited by: stanfield ]
rikkitikkitavi July 23rd, 2002, 05:04 AM

this has been covered before in older topics...
first reaction
H2SO4 + KNO3 => HNO3 + KHSO4 takes place at about 100-150 C.(bp HNO3 84C) @ 1 atm.
second reaction
KHSO4 + KNO3 = > K2SO4 + HNO3 takes place at much higher temperature so much of the HNO3 decomposes:
2HNO3 => H2O + 2NO2 + 1/2 O2
In the old days, NaNO3 was used, probably becaues it is much cheaper and the KNO3 w as used for black powder.
(there is very little KNO3 in nature but NaNO3 exist in chile fex)
The reaction was stopped after the first reaction, and the NaHSO4 formed was sold as "niter cake" , since the yield of the second reaction w as so low that it wasnt economically
feasible drive it that far.
/rickard
mongo blongo July 23rd, 2002, 03:42 PM

Yes so Stanfield , if you use your equation then you are not using enough H2SO4 and you will be wasting your KNO3 unless you heat it way over the decomposition temp of
HNO3 which of course is bad. Try the other equation that takes place at the lower temps and you will see a better yield. <img border="0" title="" alt="[Wink]" src="wink.gif" /
>
stanfield July 23rd, 2002, 05:08 PM

in brief : H2SO4 + KNO3 => HNO3 + KHSO4 if I understood...
mongo blongo July 26th, 2002, 10:17 PM

Yes, that w ill be the equation for distillation if you want the least amount of NOx at the normal temps used in this procedure.
Good luck dude <img border="0" title="" alt="[Wink]" src="wink.gif" />

During my (wrong) distillation the temp was always betw een 90 and 100C (with a sand bath), is this fine ?
thanx...

Today I made a distillation with sodium nitrate :
- 500 mL of 96% sulfuric acid
- 1200g of NaNO3
I obtained 460 mL of nitric acid instead of 583 mL theoriticaly...
Since I have my 5 Liter distillation apparatus, all the nitric acid I made is really RED ! Before, with my 1 L distillation apparatus, it was yellow, I didn't have to purify it ! why ?
I think to obtain a maximal yield, I should buy a vacuum pump... Today I only tried with my mum's aspiratory during 5 min and the nitric acid really pissed !
see ya !
woo-jong August 3rd, 2002, 04:59 AM

Does 1 mole of sulfuric acid absorbs 1 mole of water?
mongo blongo August 3rd, 2002, 12:24 PM

I'm not sure how to work it out but it would be using "ligans" (sp?). Water ligans will be attracted around the molecule and it depends on the shape and size of the molecule. I
did this a while back in chem class but I have the memory of a goldfish so I'm not sure if that is all right.
firebreether August 6th, 2002, 04:58 PM

woo, H2SO4 and H2O are infinitely miscible(sp).
mongo blongo - i think you mean ligands. Like [Cu(NH3)4]2+.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > HNO3
with NaHSO4+KNO3
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inferno June 2nd, 2002, 07:32 AM

"..David pulverized the ores with a hammer, thinking that he could then use nitric acid to isolate uranium. Unable to find a commercial source for nitric acid--probably because it
is used in the manufacture of explosives and thus is tightly controlled--David made his own by heating saltpeter and sodium bisulfate, then bubbling the gas that was released
through a container of water, producing nitric acid..."
That last part is what im looking at. Would this work? This is taken from an article in the Miscellaneous forum about a 17 year old who made his own nuclear reactor in his back
yard.
Anyway, its easier for me to get those two chems than to get nitric acid, what i imagined was putting the chems in a stopped flask with a piece of hose going up into an
elevated container of water, and heating the flask either with a flame or placing it in boiling water.
I first assumed that the NO3 ion joined the H in the water and made the acid, but after a little more research, im assuming the NaHSO4 is evolved
to HNO3, leaving maybe sodium and potassium sulphate. The vapours must form into the liquid in the water, which would probably have to be an ice bath to give instant
cooling to the vapour.
And one more question, a 1% solution of sodium bisulphate in water has pH 1.3. Could it be used as a catalyst for AP?
Any help would be appreciated.
[ June 02, 2002, 06:39 AM: Message edited by: inferno ]
Mr Cool June 2nd, 2002, 09:33 AM

NaHSO4 + KNO3 will not be a good way to make HNO3 for RDX or PETN. This is because you will have to get it very hot for it to react (probably a few hundred *C), and the
HNO3 will therefore decompose when formed into NO2, O2 and H2O. This will form an equilibrium with HNO3 (more HNO3 at low temperatures since the decomposition of
HNO3 is endothermic), but it will not totally re-react. Therefore, the HNO3 formed will contain a lot of NO2, and a lot of H2O. Both are bad.
DBSP June 2nd, 2002, 09:34 AM

I'm not shure about this method it sound kinda wierd. If it would work would the reaction look something like this?:
NaHSO4 + KNO3 ---> HNO3 + NaSO4- + K+. Or would the K+ ion liberate the Na+ thus giving (KSO4-) + Na+
It all seemes wrong, but I don't know!
Pu239 Stuchtiger June 2nd, 2002, 03:07 PM

NaHSO4 + KNO3 --> NaKSO4 + HNO3
4HNO3 + heat --> 2H2O + 4NO2 + O2
inferno June 3rd, 2002, 05:51 AM

This is what i would do:
<pre>
______
/.-----.\
// \\
// | |||
|| | ||| H2O
||
/__\
/____\
KNO3+NaHSO4
</pre>
The KNO3+NaHSO4 would be heated, possibly in a slightly aqueous solution to help the reaction. The H2O would be in an ice bath, or maybe straight into an ice
bath, so hopefully the vapours would condense upon entering the water. I dont have any proper glassware so itd be a pretty simple setup.
What i want to know is if this would work, Pu's reaction looks about right, thanks for any suggestions.
[ June 03, 2002, 04:51 AM: Message edited by: inferno ]
rikkitikkitavi June 3rd, 2002, 09:53 AM

Why not
Ca(NO3)2(aq) + NaHSO4 (aq) => CaSO4(s) + HNO3(aq) + NaNO3(aq) ?
Probably easier to find Ca(NO3)2 and cheaper to.

Filter out the CaSO4 ,and simple distillation removes the HNO3
from the NaNO3. Some NaNO3 is probably preciptated to, since the HNO3 will "push" it out of solution.
4 HNO3 = 2H2O + 4 NO2 + O2 is a equilbirium. Condensing the H2O and simultaneously absorb the NO2 in the water would give HNO3 again.
3 NO2 + H2O => 2 HNO3 + NO (net reaction, many intermediate steps )
It is similar to the real industrial process of making HNO3 where NO2 is lead through large absorbing towers with packed columns . You probably need some sort of packed
column so the gas/water mixture has a large cntact area to react on. Only bubbling NO2 through the water probably leads to to short contact time/to small contact area and
exessive losses of NO2. Unless ypu lead the gases through repeteaded absorbing flasks.
Maybe some sort of recirculation of the condensed water/acid from the bottom to the top to, so you wont get a to diluted acid?
I could make a simple schematic, but I dont know how to attach pictures?
It is very difficult to say how good it will work, but it will work to some extent. It seems like a simple setup , so why dont give it a try? And please let us know :)
The absorbtions process slows down when the HNO3 concentration goes up to, this is why commercial HNO3 usually comes as 53 %. Stronger acids (up to 68 %) are made
trough distillation, and above 68 % extractive distillation with H2SO4 or Mg(NO3)2. There is new processes developed where O2, NO2 and H2O is reacted at very high pressures
, giving > 95 acid directly.
/rickard
/rickard
DBSP June 3rd, 2002, 10:24 AM

When I heard NaHSO4 it sounded familiar, now I'vre found out why.
A while ago I found a bottle of NaHSO4 prills at home, used for some toilet washing. And I have 24kg of Ca(NO3)2. I've been thinking about buying a dest. setup but I haven't
been shure of that I could get enaugh sulfuric acid, now if this workes as well then I might buy one.
I'll try a small quantity and see if it colors my skin.

I didn't make any calculations regarding this thing, I just took a pinch of NaHSO4 and a pinch of Ca(NO3)2 and poured it into a small ammount of water. When most of it had
dissolved i poured some of it on a newspaper(this was yesterday). Today it had all dried out when I had a look at it. At the same time as I poured the mix onto the paper I
allso poured a small ammount of water on the paper to have something to compare with. The paper was brown where the mix had been poured out and at the place the water
had been poured there wasn't a trace left of it. The conclusion is that it workes, I wonder what conc you could get this to in the first step. That must depend on how much
water is which is needed to dissolve the reactants. Calcium nitrate is very soluble in water but I haven't got any solubility data on the NaHSO4, has anyone got anything?
I haven't got merck installed right now since I formatted not so long ago, could anyone with it installed check that please.
If one would distill this mixture the HNO3 obtained would probably be low conc, perhaps 40-50%(has anyone any idea of conc? ).
After that it's easy to concentrate it the normal way. This method is perhaps more work demanding but worth it if it workes.

solubilty of NaHSO4 / 100 gr H2O
25 C 29 grams
100 C 49,7 grams
solubility of Ca(NO3)2 /100 gr H2O (

25 C 100 grams
100 C 354 grams
from my Lange, handbook of Chemistry
/rickard

Cool, it does work <img border="0" title="" alt="[Wink]" src="wink.gif" />
The way i was thinking though was to heat the NaHSO4 and KNO3, hopefully the resulting gases would condense when lead into an ice bath and
form diluted HNO3, otherwise they could be lead into a salt-ice cooled closed flask to condense in there, but it would have to be closed or too much gas would be lost.

Improvised Manufacture of Nitric Acid > Purifying and concentrating sulfuric acid.
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Hvoroba July 11th, 20 02, 10:1 2 AM

This is a sum m ary of an industrial process for recycling sulfuric acid which I found somewhere on the internet:
Concentration-Sulfuric acid is heated at 100C at norm al atm ospheric pressure until all m oisture (water) is vaporized and
c o n d e n s e d s e p e r a t e l y . W hen the concentration reaches < 98% thick white fume s a p p e a r .
Purification-The concentrated impure a cid is then distilled at 340 C at norm al atm ospheric pressure. The result should be <
98% pure sulfuric acid. During both procedures an oil bath is used to prevent steam explo sions.
A. Are these procedures correct?

B. If yes, what details should I insist on when operating such a procedure?
Thank you.
zaibatsu July 11th, 20 02, 02:2 3 PM

T h i s h a s b e e n covered already, and your last post was locked. DO NO T P O ST THIS AGAIN, unless you are told that you can.
megalomania July 12th, 20 02, 03:2 1 PM

This section is only for nitric acid! Not sulfuric, phosphoric, acetic, hydroch loric, or any other acid, ch emical, solvent, topic, issue,
or anything else under the sun period.

concentrating nitric?
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S. Toppholzer June 5th, 2002, 03:48 PM

There is the commonly available 75% nitric acid - could it be concentrated like sulfuric acid?

Once nitric acid reaches a concentration of 68% it cannot be further concentrated by heating to drive off water. It forms an azetrope at this level. To further concentrate it must
be distilled from conc. H2SO4. There are other ways to do it but this is probably the easiest.
Einstein July 29th, 2002, 11:57 AM

If I have gotten it right, you have to add strong (98% should do right?) H2SO4 to your nitric acid, then distillate the nitric, boil remaining H2SO4 until you have 98% again and
do this whole thing couple of times. This should give you 90+ % HNO3, IF Im correct.
PYRO500 July 29th, 2002, 02:26 PM

Yes that will w ork.

It should actually give you 100% nitric acid if you use strong enough sulfuric acid to begin with.
knowledgehungry October 10th, 2002, 04:37 PM

in terms of concentrating hno3 from h20 might it be possible to use electrolylosis to break down the h20 in the solution of nitric??
i know that even if it w as theorytically possible i know that it would most likely be too dufficult and risky to do but i was just wondering if it has been tried or if there is no way
that it would w ork. Is it likely that the hno3 w ould decompose too?
Just for you all to think about...
kingspaz October 10th, 2002, 07:02 PM

knowledgehungry, i know you mean w ell but by saying 'i know that it would most likely be too dufficult and risky' it makes you look silly.
HNO 3(aq) + H2 O (l) <=> H3O+ (aq) + NO3-(aq)
this shows that solutions of nitric acid are ionised. so w hen you put current through it the NO3 - ion will go to the cathode and the H 3O+ w ill go to the anode so not only the water will be destroyed. good thoguht though.
also look in forum matters under new features to see how to use the proper format for w riting chemicals instead of h2o and the like.
[ October 10, 2002, 06:04 PM: Message edited by: kingspaz ]

You can electrolyse nitric acid to make it more concentrated, but its more complex than simply sticking 2 electrodes in and away you go. The method you are hoping it will work
by is flawed for reasons other than have been mentioned already. H3O+ being positive moves towards the cathode where it is reduced, which normally results in the production
of nascent hydrogen. Every process however, that would normally produce hydrogen in acids fails in conc nitric acid oweing to its agressive oxidising action with the production
of NO2 gas. NO3- moves towards the anode, where its oxidised. The solution eventually ends up giving half an oxygen atom per electron regardless of the actual species
oxidised by the anode, any NO3 produced ending up back as NO3-. The failiar of this to liberate hydrogen effectivly makes simple electrolytic concentration impossible. A more
complicated cell w ith seperate anolyte and catholyte compartments can be used, the NO2 produced at the cathode is fed into the anolyte to be reoxidised and concentration
effectivly proceeds by ion migration rather than actual electrolysis of the anolyte at the expense of the catholyte. You dilute as much acid as you concentrate, and the anolyte
needs replenishing to keep the process going. Over 99% nitric acid can be achieved eventually....
NO2 is extremely toxic. Fear it.
Richy October 12th, 2002, 07:56 AM

how concentrated is the nitric acid from the H2SO4 + KNO3 reaction?
i am using concentrated battery acid (boiled at 100c till no more steam then boiled at 130c for 20 mins) and 98% potassium nitrate. the final HNO3 product is orangy and
fuming.
vulture October 12th, 2002, 01:46 PM

Theoretically the concentration is 99% , but everytime your HNO3 sees air, it will decrease in concentration because it will evaporate and decompose partially,
that's why it's called fuming. If you leave your HNO 3 exposed to air it will autodilute to 68%. Use as soon as possible.
You'll notice that alot of nitration recipes use a nitrate salt with concentrated H2 SO4 because then almost 99% HNO3 will be created
in the reaction vessel which is often superior to earlier prepared HNO3.

The decomposition of nitric acid has virtually nothing to do with air. Pure nitric acid decomposes into water, oxygen gas and NO2, which colours the solution brow n. Its
accelerated by heat and light, as usual. Dont assume that decomposition will stop at the azeotropic point of the acid, thats just w hen the vapour pressure of the liquids is in the
same proportion of the constitution of the acid at boiling point. Although I say 'virtually nothing', the eventual equilibrium depends on the concentration of oxygen (its partial
pressure), and the amount of NO2 in solution, as well as the amount of water.
Acid mixtures prepaired by dissolving nitrates are never 'superior' to equivalent mixtures of acids. The only time such mixtures are used industrially is w hen nitric acid cannot be
obtained. While nitration mixtures are generally expressed as a mixture of absolute nitric, sulphuric and w ater content, its accepted that they will almost never be made in any
scale by mixing pure nitric and sulphuric acids. The industrial cost of pure nitric acid is too great for this to make sense, instead they are usually made by mixing the calculated
amounts of azeotropic nitric acid, oleum and if needed water to result in an identical mixture than if pure nitric and sulphuric had been used. The only reason anyone would see
'alot' of directions using nitrate salts, would be if they restricted themselves to fringe literature, while some of these methods may w ork, they arnt accepted in reliable texts.
Anyone w ho is serios about this sort of chemistry should buy the pyrex bits for a still, quickfit works w ell, and vacuum distillation under it results in less decomposition, as other
members have also reported. Anyone that isnt serios, shouldnt be doing any of this at all.
One of the big problems w ith dissolving nitrate salts in sulphuric acid, is a rather complex equilibrium results that keeps quantities of nitrate and sulphate and hydrogensulphate
undissolved. Its the specific application of Le Chatelier's principle usually taught as 'The common ion effect'. The stronger the concentration of nitric acid in solution, the lower the
solubility of the alkali nitrate in it. The other problems are more obvios.
There are several good methods of making pure nitric acid without distilling from NO2, but owing to its toxicity, none of these are suitable for home production. If you add liquid,
or concentrated NO2 gas to w ater a rather violent reaction is produced w here the liquid apears to 'boil'. NO2 reacts with the water to produce nitric and nitrous acids as in the
expected dilute system, but in the concentrated acid, the nitrous acid decomposes releasing NO gas. Its the reoxidation of the NO to NO2 in the gas phase that plays the
dominant role in the oxidation. Industrially the correct amounts of liquid NO2 and water with oxygen gas at 50atmospheres is sealed into containers and eventually produces
over 99% nitric acid solution.
The reason conc nitric acid fumes in air is exactly the same reason as HCl gas fumes in air. They are good enough dehydrating agents that they cause the water vapour in the
air to precipitate as acid solution, the solution having a lower vapour pressure than the ambient concentration of water. Nitric acid is only decomposing if it turns brown.

excellent, thanks guys. i have had it stored in an airtight container for 3 days now . ill use it in some NG today. w ish me and my fingers luck.
vulture October 13th, 2002, 06:42 AM

<blockquote>quote:< hr /> The decomposition of nitric acid
has virtually nothing to do with air. <hr /> </blockquote> What I meant is that in an open container the nitric acid will
decompose quickly because the NO2 gas can escape. In a closed vessel the partial NO2 pressure builds up and stops the equilibrium from moving further to the right. Also,
unless you work in a dry room it's going to attract water from the air.
Hmm, I wonder if adding conc. H2 SO4 or conc. H3PO 4 to the nitric for storage would improve storage life. Also I
wonder If one could drain the H 2SO4 /w ater or H 3PO4 /water layer or does this mix w ith the HNO3?
<blockquote>quote:< hr /> Acid mixtures prepaired by
dissolving nitrates are never 'superior' to equivalent mixtures of acids. < hr /></blockquote>From the perspective of
the home experimenter they are. If you use enough H2 SO4, you'll get better nitrating than with 70% nitric acid.
Ofcourse 70% nitric acid also nitrates better w ith an excess of sulfuric acid, but then w hy go through the hassle of preparing the nitric acid?
<blockquote>quote:< hr /> Nitric acid is only decomposing if
it turns brown. <hr /> </blockquote> Green (yes green! Had it once myself after distilling), Yellow and colors between
yellow-brown are signs of decomposition.
Deep red HNO3 isn't necessarily a bad thing as long as there isn't much w ater in it.
<blockquote>quote:< hr /> Dont assume that decomposition
will stop at the azeotropic point of the acid < hr /></blockquote>At the azeotropic point the decomposition will
decrease significantly because dissociated acid won't decompose that easily. Also at the azeotrope w ater and nitric acid w ill decompose at the same rate, so the solution will stay
at 68%, but the volume w ill decrease.
<blockquote>quote:< hr /> NO2 is extremely toxic. Fear it.
<hr /> </blockquote> Very true! It's a silent killer. I once breathed a significant amount of NO2 /
HNO 3 gas w hen opening a distilling setup. Besides a scorched feeling in my throat and nose, I felt no other effects for half an hour. But then I got a terrible
headache, high hearthbeat, a feeling of anxiety and stress and severe nausea. This lasted an entire night. <img border="0" title="" alt="[Frown]" src="frown.gif" />
[ October 13, 2002, 05:54 AM: Message edited by: vulture ]
aster December 23rd, 2002, 01:37 AM

i am making my mercury fulminate following the mega recipe, when the mercury react with the nitric acid (68% )they released the nitrogen dioxide gas, and the product
coloured green, (settle dow n in the lower layer of the container/glass). if i use more volume of acid than recommended, and closed the open end of the beaker or erlenmeyer
by placed a mica sheet, then will the nitrrogen dioxide gas that trapped in will react with the water in the nitric acid (68%)and increasing the concentration of the nitric acid left?
(so i can get more concentrated acid) then i can simply separate them carefuly by decant the upper layer, am i right? is there any danger to use this left nitric acid that i
assumed became more concentrated than before for syntesis another recipe that require more concentrated acid?
aster December 30th, 2002, 04:23 AM

humm .......i realize something w rong with my idea above, so from the reaction of the mercury and HNO3 the left acid w ill be more dilute than concentrated, because when NO2
gas formed, then the H2O will left and dilute the remaining acid, maybe using separated glass, the one for reacting mercury with HNO3 and the other just fill with HNO3 (and
keep closed and w rapped dark), so the stream of the NO2 gas can react with the water in the glass fill only with HNO3 and increasing the concentration. being closed and
wrapped dark so the HNO3 won't decompose upon influence of light, ...any one ever try this? i am wonder how much this (idea) can concentrated the acid ?
Marvin December 30th, 2002, 09:18 PM

<blockquote>quote:< hr /> What I meant is that in an open
container the nitric acid w ill decompose quickly because the NO2 gas can escape. In a closed vessel the partial NO2 pressure builds up and stops the equilibrium from moving
further to the right. Also, unless you work in a dry room it's going to attract water from the air. < hr /></blockquote> In fact exposure to air does play a part w hich is why I said 'virtually', but not becuase of loss of NO2 which is very soluable in the conc acid, loss of NO2 in normal
storage w ill be much less than loss of the acid itself by simple evaporation even in an open container. In an ordinary partially sealed container, ie effectivly sealed, but pressure
can vent, the atmosphere will push out all the air, ending up as mostly oxygen. Anyone who stores nitric in an open container deserves everything they get, and it will be a lot
more serious than the nitric absorbing water. The other main product apart from the diluting water is oxygen, and this is the real problem becuase of its low solubility and the
resultent high pressure of oxygen that forms if you try to prevent its escape. Making containers resistant to nitric acid/NOx at several 10's of atmospheres is certainly possible
industrially, but for home chemists is not recommended. What matter for home storage, are kinetic factors, mainly heat and light, rather than equilibrium conditions that are
never really aproached and impractical to alter.
<blockquote>quote:< hr /> Hmm, I wonder if adding conc.
H2SO4 or conc. H3PO4 to the nitric for storage would improve storage life. Also I wonder If one could drain the H2SO4/water or H3PO4/water layer or does this mix with the
HNO3? <hr /> </blockquote> The decomposition turns acid into NOx/O2/H2O, so adding a strong acid, or a dehydrating
agent will tip the balence in the favour of more decomposition, not less, with or w ithout a means for removing the water continually. The more agressive particualy the
dehydrating action, will increase the speed as well as affect the equilibrium result. Both phosphoric and sulphuric are miscable w ith nitric acid or w e w ouldnt be using mixed acids
for nitrations. Nitric acid and phosphorous oxide forms mixed layers of mainly nitrogen pentoxide and some form of phosphoric acid, but I havnt seen a way to exploit this
without using P2O5. Maybe HPO3 could be made to dehydrate the acid and form a decantable pyrophosphoric layer, but I suspect this w ouldnt work well.
Nitrate salts in a nitrating mixture produce hydrogen sulphate, reducing acidity, wasting acid, the ppt causes problems of its own but for some reason the mixture behaves much
worse than that of pure nitric acid in the same total volume. Ive tried nitrating mixtures w ith mixed acids, and nitrate salts and for want of a better explanation the salts seem to
kill the dehydrating properties of the sulphuric acid. Adding additional sulphuric acid counters this, but at the same time dilutes the nitric in the mixture and the best comprimise
performs much less w ell than ordinary mixed acid and at considerable extra waste of sulphuric. Some people may be desperate enough to try this but the results are never
superior to distilling the acid yourself and saving on resources. Ive used 70% nitric much less, simply becuase I cant buy it here but the dinitrations on an unactivated benzene
ring w ith 70% nitric/sulphuric went much better with a relativly low excess of nitric acid than any of my experiments with sulphuric/nitrate mixtures did. As a secondary point
mixed acid can be recycled a number of ways if its been prepared from acids rather than salts (cf the TNT synth in Davis for the most elegent), Id go as far as to suggest
recycling nitrate salt mixtures is completly unfeasable without using the sort of distillation that would have better been used to prepare the nitric acid in the first place.
Ive had greenish acid before and I confess I assumed it w as an external contaminent like copper. Looking at it logically it could be an affect of dissolved N2O3 which is blue, and
the yellow /red colour of dissolved NO2 resulting in a green hue, but I'm speculating. Brown nitric acid is a real problem as its a much more agressive oxidising agent than nitric
acid is, and this is certainly one factor in runaw ay reactions. Getting rid of the NO2 often involves effectivly adding w ater, eg use of urea. Storing brown nitric acid is only an
advantage over long periods of time with pressurised oxygen so I see no reason not to get rid of as much of the NO2 as possible prior to cool storage.
<blockquote>quote:< hr /> At the azeotropic point the
decomposition will decrease significantly because dissociated acid won't decompose that easily. Also at the azeotrope water and nitric acid w ill decompose at the same rate, so
the solution w ill stay at 68%, but the volume will decrease. <hr />< /blockquote>I dont follow your reasoning here,
there is no sudden point at which the acid becomes dissociated, only a smooth curve that has nothing to do with the Az point at all. The Az point is simply the point at w hich the
partial pressure of the gas is in the same ratio as the liquid its above. Theres a tendency to ascribe a 'molecular formula' to this, particulaly in older textbooks, but the points
change with temperature and pressure and often bear little relation to the mixtures that crystalise out on freezing for example. There is how ever a gut feeling that tends to
creep up when thiking about these ideas, that the molecules 'prefer' to be in these ratios and that the composition w ill tend to form the 'prefered' mixture. I'm not accusing you
of this, just suggesting this might be a gut impulse that is misleading the logic. If there was a massive great Az discontinuety in Water/peroxide mixtures would this affect its
decomposition? Rather more obviosly not, and Id expect nitric acid decomposition to depend smoothly on the temperature and the concentration of the acid and each product.
Pure nitric acid, isnt pure nitric acid when its liquid, its a mixture of nitric acid, water and nitrogen pentoxide. If its the nitrogen pentoxide that is the major kinetic factor in
decomposition, then the concentration of w ater might have nothing directly to do with it at all.
aster, Whats missing is oxygen, the oxygen converted to water by the dissolving metal. Pure nitric acid has been made industrially, and probably still is, by mixing the right
proportion of NO2, water, and oxygen at 50 atmospheres and results in 99%+ acid. NO2 is very nasty however, and making nitric, or increasing the concentration of nitric acid
this way isnt w orth the health problems in my opinion. If you think you can setup a draft cabinet good enough to avoid health problems, and pure oxygen, preferably at
pressure safely without anything corroding, or splatting nitric acid everywhere, then I'm sure small amounts of higher concentration acid can be produced, slowly.
NO2 has an unpaired electron, which is w hat makes it so reactive, paramagnetic, and brown. It destroys lung tissue very fast, so much so it makes your body think it has a lung
infection, its your bodies reponse to this that makes you feel ill, or die. The effects of which vary between 'mild infection' symptoms all the way to fatal puminery edema as
much as several days after the exposure, when of course no infection was ever actually present. There is also cumulative long term damage which can be symptomless apart
from the impaired lung function.
If you choose to play with NO2, you w ill need much more than luck, and much more information that anyone w ould be able to find on the internet or should expect to find at a
forum.
aster December 31st, 2002, 08:34 AM

ok, your explanation is very helpful, thanks. another idea is making more concentrating nitric acid by adding few H2SO4 98% then using calcium nitrate to convert the H2SO4
into HNO3 and Calcium sulfate that w ill precipitate upon forming, what is the plus minus of using this method? it will be more safe than disolving NO2 gas into HNO3 solution i
think...
jarrod January 2nd, 2003, 06:37 AM

A bit off topic :rolleyes:
But I have a really good site w ith pics and detailed info on distillation, but its in GERMAN. If any one out there can translate this for me I would be grateful. I have already tried
the free translators and they get general idea but are shotty overall.
In den Destillationskolben links fllt man 25 ml konz. Schwefelsure. Vorsichtig, in Portionen und unter guter Khlung mit Eiswasser schttet man 30 g gut getrocknetes, fein
gepulvertes Kaliumnitrat durch einen Trichter hinein. Dazu gibt man noch ein wenig Silbernitrat (AgNO3). Bei dieser Prozedur bilden sich bereits stechend riechende Dmpfe, nicht
einatmen! Nach etwa einstndigem Stehen im verschlossenen Kolben wird die Mischung vorsichtig erwrmt; die zuerst bergehenden Tropfen (erkennbar an der gelb-braunen
Farbe) werden gesondert aufgefangen.
Der als Vorlage dienende Rundkolben mu (am besten durch Einstellen in ein Becherglas mit kaltem Wasser) ebenfalls gut gekhlt w erden. Bei dem Versuch destilliert fast reine
Salpetersure ber (im Temperaturbereich von 83 bis 85 C bei Atmosphrendruck). Sobald sich grere Mengen brauner Stickoxide bilden und sich das abtropfende Destillat
brunlich verfrbt, wird die Reaktion abgebrochen.
Sind prparativ grere Mengen reiner Salpetersure darzustellen, so arbeitet man auf jeden Fall mit einer Schliffapparatur und destilliert wiederholt im Wasserstrahl-Vakuum
(Siedekapillare verwenden). Der Siedepunkt der Sure liegt bei einem Druck von 26 mbar nur noch zwischen 36 und 38 C!. Hier reicht zur Erwrmung des Destillierkolbens ein
Wasserbad aus
<a href="http://www .chemikalienlexikon.de/cheminfo/1248-lex.htm" target="_blank"> the site</a>
thanx
:confused:
vulture January 2nd, 2003, 08:41 AM

<blockquote>quote:< hr /> I dont follow your reasoning
here, there is no sudden point at which the acid becomes dissociated <hr /></blockquote>That is not what I said.
Nitric acid of 68% is fully dissociated into H+ and NO3 -. Above that concentration, there will be HNO 3 molecules
present w hich can decompose easily into NO2, water and oxygen.
Dissociated acid decomposes much slower.
Rhadon January 2nd, 2003, 08:53 PM

jarrod: The procedure you pasted here is a w ell-known one. The only thing that could be new to some persons might be the addition of small amounts of silver nitrate. Yet, I'll
do a very crude translation:
<blockquote>quote:< hr />
The distillation flask which is shown on the left side is filled w ith 25 ml of conc. H2SO4. Then there are, cautiously and in small portions, added 30 g of w ell dried and finely
ground KNO3 by means of a funnel. Then there is added a small amount of AgNO3. At this point there w ill be evolved vapour with pungent odour. Do not breathe them! After
standing for about an hour in the closed flask, the mixture is heated cautiously. The first drops of the distillate (which can be recognized by their yellow -brownish colour) are
collected a separate vessel.
The round bottom flask which is used for collecting the distillate has to be cooled well, e.g. by placing it in a beaker which is filled w ith cold water. In the experiment the nitric
acid that distills is almost pure (@83 - 85 C). As soon as larger amounts of brown NO2 are formed and the distillate has a brow nish colour, the reaction is stopped.
Are larger amounts of HNO3 to be prepared, one should use a ground distillation apparatus and distill multiple times under vacuum in any case. The boiling point of the acid is
about 36 - 38 C @26 mbar, so a water bath is sufficient for heating.
<hr /> </blockquote> 
Marvin January 9th, 2003, 09:12 PM

That is not what I said. Nitric acid of 68% is fully dissociated into H+ and NO3-
<hr /> </blockquote> A finite point in the nitric acid equilibrium at which you could say one species w as not present
would qualify as 'Sudden' in physical chemistry. An acid is is only assumed to be completely dissociated at infinite dilution. Its also not clear to me w hy you chose the azeotropic
point to be the point at w hich HNO3 stopped existing.
Dissociated acid decomposes much slower.
<hr /> </blockquote> H+(aq) cant decompose, and if nitrate decomposed detectably (From a chemical point of view )
then we'd expect a RT solution of sodium nitrate w hich w ill also generate free nitrate ions to visibly evolve oxygen.
Above that concentration, there w ill be HNO3 molecules present which can decompose easily into NO2, w ater and oxygen.
<hr /> </blockquote> You are making the assumption that its HNO3 molecules that decompose, something I thought
Id made clear in my last post may not be the case and probably isnt. It seems much more likly that its the nitrogen pentoxide that decomposes, certainly in the high
concentration acid and this is supported by the observation that solid pure nitric acid does not seem to decompose at all of its own accord.

Improvised Manufacture of Nitric Acid > Methylene Chloride
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View Full Version : Methylene Chloride
Alchemist July 24th, 2002, 10:57 AM

Hello all,
does anyone know of a good OTC source for Methylene Chloride? Thanks!!!!
mongo blongo July 24th, 2002, 12:12 PM

It's also called Dichloromethane and is easily found in hardware stores used as a paint remover and cleaning up epoxy resin.
It will also be found in paint and varnish stores. It usually contains a small amount of methanol (about 10%) which can be
removed by distillation. Are you thinking about HNO3 solvent extraction?
nbk2000 July 24th, 2002, 01:32 PM

The more expensive "pro grade" paint strippers are mostly MC. Also, it's mixed in with toluene and acetone. I don't know the
percentages, but an MSDS would tell you. I can by it neat for $20 a gallon here. Though I'd have to pick it up at the factory
since they can't ship it. :(
Since it's boils at 40C, and around 30 degrees C lower than the next highest Bp solvent (acetone 70C), and way less than
toluene, it'll be easy to distill. You'll need a very cold condenser to collect it though since it's nearly boiling at warm room
temperature.
I've been studying the solvent HNO3 extraction process for the DVD. I'd go with freezing out the anhydrous nitric acid if I had
access to dry ice (which I do). Though I wouldn't bother with distilling off the dilute nitric in the first place.
Rather, use the NO3/H2SO4 mix, add an excess of acid, and do multiple extractions with MC. Freeze the combined extracts to
-60C and collect via filtration the anhydrous crystalline HNO3. Let thaw and you've got it.
How simple is that? :D No distilling required at all, everything available cheaply without suspicion, and it's pure anhydrous to
boot.
spydamonkee July 24th, 2002, 06:03 PM

MC can also be found in spray cans of Belt Grip for softening big conveyor belts to make em grip better. it also contains
toluene
dunno how oyu would go about seperating the two since its in a spray can, prolly not the best source :D
SATANIC July 24th, 2002, 10:01 PM

IIRC, the best source is the cheap brands of paint stripper. it contains only 10% methanol.
look in supermarkets rather than hardware stores,you'll usually find it, otherwise, try a cheapass looking hardware place.
da man July 25th, 2002, 06:38 AM

I think i remember reading a while ago in the patent for this that the nitric acid with the methylene chloride still present in the
acid, can be used for the nitrations without the methylene chloride interfering. Would this work for the prodcution of RDX? All
you would need to do is mix the nitric and sulphuric acid, add the methylene chloride, suck off the sulphuric/water layer, and
PRESTO! Acid for RDX manufacture!
[ July 25, 2002, 05:39 AM: Message edited by: da man ]
kingspaz July 25th, 2002, 08:04 AM

just like to point out acetone actually boils at 55.5*C not 70 <img border="0" title="" alt="[Wink]" src="wink.gif" />
[ July 25, 2002, 07:05 AM: Message edited by: kingspaz ]
nbk2000 July 25th, 2002, 08:39 AM

Excuse me for not installing the Merck Index. :rolleyes:
Anyways, the patent says it's a "gentle" oxidizer. You're not going to use it for trinitro-anything synths. Though you could
easily use it for making MNT or dinitrophenol for conversion to PA.
I like how you can simply freeze out pure anhydrous acid without all the distilling crap and NOx fumes to hassle with.
Alchemist July 25th, 2002, 10:36 AM

Hello all,
Thanks a million everyone! This went over so good I should give ya all my entire list of 18 chemicals I am looking for!!!
Again thanks, byeee......

Microtek July 25th, 2002, 12:17 PM
As it happens, I'm currently trying to establish whether this is a viable method for producing very pure nitric acid.
I have a feeling that the reason I get poor yields from my HMX procedure is too much water or NO2 or both in my distilled
HNO3 ( which works fine for making RDX ).
I can buy CH2Cl2 from my supplier, but I wanted to try extracting it from paint remover to avoid the shipping costs. Over here
all paint removers contain some sort of colloidal material as a thickening agent for easy of use on vertical surfaces. I don't
know what it is, but previous attempts have shown that it is pretty inert.
I found a brand that was reasonably cheap, and contained from 60 to 100% CH2Cl2 ( that's what it said on the label - pretty
wide margins ), 1-5 % xylene and then that gelling agent.
I found that simply mixing the product with some xylene ( 20-30% ) and distilling the mix worked fine; much of the CH2Cl2
came over and left a cake of xylene and gelling agent that was easily poured out.
Condensing the vapour was much easier than I had anticipated; I just made sure that the condenser tube ( glass ) extended
well into the receiving bottle. The vapours can be seen as a diffraction because they are so much more dense than air and
when I looked across the mouth of the receiving bottle, no spill could be seen.
The distilled methylene chloride still contains some kind of aromatic substance, probably xylene which is nitrated when the
CH2Cl2 is used to extract HNO3 from mixed acids, causing the solvent to turn red or black. However, the nitroaromatic that is
produced is easily separated from the CH2Cl2 by a second distillation.
When I do this, I employ a sandbath and monitor both the temperature of the bath and of the vapour in the distillation flask.
I keep the sand bath at 70 C. Surprisingly little CH2Cl2 is lost.

Methylene chloride can also be found in auto shops and hardware stores as "acrylic solvent". Its usually pure methylene
chloride.
Also, i have a procedure fot TNT that uses methylene chloride/nitric acid extracted from KNO3/H2SO4. The only problem is that
you need tons of methylene chloride. But you can distill it off so you can reuse it. You could make a makeshift distillation
apparatus to distill methylene chloride easier than nitric acid.
nbk2000 July 25th, 2002, 04:07 PM

Well, since acetone and MC Bp's are within 15C of each other, there will be some carrying over of acetone into the distilled MC.
But, fortunately, MC is insoluble in water, while acetone is freely soluble. Thus, a simple washing with cool water (several
times) will remove the acetone contaminant.
You could make a spiral condensor from PTFE tubing wrapped around a dowel, and insert it in a straight length of PVC piping
with a T fitting at the lower end. The PTFE tube connects to a glass tube that passes through the stopper at the bottom.
The reason for the T fitting is so that the water that results from the melting of the ice chips that you pour in the open top of
the condenser can drain out. A small screen keeps the ice in, of course,. :) and a stopper connected to another tube carries off
the melt.
Ice is a much more efficient means of condensing the MC than just plain water. Also, your receiver should be ice packed too.
Reason for the PTFE tubing is because you might need to use the condenser (in normal water cooled mode) for distilling the
nitric if you run out of MC. Two birds, one stone. <img border="0" title="" alt="[Wink]" src="wink.gif" />
nbk2000 July 26th, 2002, 02:10 PM

(I've moved this to the special project section since it's now mostly about nitric acid purification than about finding MC.)
I'm wondering...would it be OK to add the dry ice directly to the MC/HNO3 mix?
Reason I'm asking is because this would greatly simplify the process since you wouldn't need a seperate cooling bath, just do
it all in one pot. :)
I don't think it would react since both CO2 and HNO3 are acidic.
Naturally you'd want to be very careful to add the dry ice in very small pieces till the raffinate is cold, otherwise you'll get acid
splattering everywhere. Ouch!
I'll have to see if I can find some straight MC at the auto suppliers since I already have everything else, or can get it within a
few minutes. Only thing I don't have is the equipment (or inclination) for a distilling setup.
Mr Cool July 29th, 2002, 08:31 AM

Dry ice wouldn't react with HNO3 or MeCl2, but you might get clouds of HNO3 and MeCl2 vapour before the liquid was cold, like
when you put dry ice in water.
nbk2000 July 29th, 2002, 09:05 AM

I figured that might be the case. If one has a deep freezer, it be advisable to use that to pre-cool the raffinate as much as
possible. At -20, that'd only require another 30 degrees of cooling by the dry ice to freeze out the anhydrous nitric, conserving
the amount needed.

The dry ice should actually a freezing mixture with DCM that may get quite cold by simply mixing them. In chloroform at least
you can get to 77 C.
In my chemical survey I came across a few brands for painting. Some of these are gelled with crap, and can be quite
expensive. The first brand I found is 84% DCM, with the other stuff being isopropanol 6.5%, methanol 3.5%, and other. It was
$7.95 a quart, and $20.95 a gallon (3.8 L). The second brand included isopropanol, ethylene glycol monobutyl ether, and
methanol. It was $28.50 a gallon with no listed %s. The third included acetone, toluene, methanol, and other. There were
actually two similar brands here (one was gelled I suspect) which cost $17.99 and $16.99 a gallon. The fourth included
methanol, toluene, and acetone. It was only $9.99 a gallon.
I suspect there is much data on obtaining pure OTC dichloromethane at The Hive.
DBSP July 30th, 2002, 05:30 PM

I've made some searches on metylenechloride and found out that it is banned in sweden not even chem companies can buy it
without a special permission. To bad, is it the same in other companies?
All chlorinated solvent are banned here.
My chem supplier has is at the prize of about 75$(x1,25=~94$) per 4l(pure).
Mr Cool July 30th, 2002, 06:38 PM

Mega: I've been playing with "Nitromors" brand paint stripper recently (the only listed ingredients are DCM and methanol), it's
very thick and cloudy white. BUT: if you pour it into an equal volume of water and stir it well for a minute, then let it settle, the
DCM settles to the bottom (clear and colourless), the methanol mixes with the water at the top, and the thickener pptes and
settles between the two liquids. So if all brands contain this thickener, it's very easy to seperate. The DCM layer is roughly 70%
(v/v) of the paint stripper that you used.
megalomania July 31st, 2002, 01:13 AM

Ahh yes, I forgot to mention two things: that DCM is only slightly soluable in water (hence easy to seperate the alcohols and
acetone), and that pure DCM is illegal in the US (to the best of my knowledge).
I am unfamiliar with the method of nitric acid purification using DCM, is there a patent or another source I can check this?
nbk2000 July 31st, 2002, 08:52 AM

Damn newbies! Always asking for people to spoon feed them information! Search!
<img border="0" title="" alt="[Wink]" src="wink.gif" />
US#3981975 Preparation of anhydrous nitric acid
It's listed in the "patents" topic by me in the links section, in wantsomfets' post.
[ July 31, 2002, 08:52 AM: Message edited by: nbk2000 ]
Microtek August 6th, 2002, 11:30 AM

Mr Cool: The Nitromors brand is also sold in Denmark and I used it some time ago as a source for DCM. I settled on the
same extraction method that you did, but found that the DCM obtained still contains some sort of dissolved plastic, which can
be separated by distillation.
PrimoPyro August 7th, 2002, 02:45 AM

Megalomania, what exactly do you mean by "pure" DCM being "illegal" in the USA??
Illegal how? To buy? Or to makret in _______ product? Anyone can purchase it from a supplier without scrutiny. I may be
unaware of domestic laws in your area however, that may prevent it's usage in certain applications in pure form.
But I know for a fact that it is considered to be a benign chemical in the eyes of the organic chemist. It is my favorite solvent,
as is common for many an o-chemist.
For those of you in the USA having troubles finding it OTC, stop looking there altogether. Buy it from a chemical supply
company, just call them up and outright ask them, "Hi. I'm interested in purchasing a solvent. Do you do business with
individuals, or only companies?"
A)Yes they do business with individuals, then you say, "Ok, I would like to order 2 liters of dichloromethane solvent. I have
the CAS Registry Number if that would help. (Have this number ready for every compound you ever wish to order, it makes
their job ten times easier and helps them believe you know what you are doing with this solvent.) What am I using it for? I am
a general contractor and painter, and its the best solvent for cleaning pigments from brushes and equipment without
damaging them.
Bla bla bla.
B)They don't sell to individuals, only businesses, you ask: "Oh really? That's a shame. Do you happen to have the name and
number of a company that does sell to individuals? Thank you, have a wonderful day, ma'am." (click)
It's easy as pie. Heh, or you can bee a little nerd funny and tell them you use it as colone because you love the smell, and
then ask if they have ether as well. :D
[EDIT] I also forgot to add that dichloromethane forms an azeotrope with water, and other azeotropes with many other
solvents. Simple distillation will not fix this.
PrimoPyro
[ August 07, 2002, 05:08 AM: Message edited by: PrimoPyro ]
nbk2000 August 7th, 2002, 09:02 AM

Since the MC would be used for nitric manufacture, a little water wouldn't have any real effect since it'll either be removed by
the H2SO4, frozen out, or passed over into the HNO3. You may not get 100% anhydrous HNO3, but 98% ain't nothing to
sneeze at. :)
But a dryer like anhydrous magnesium or potassium sulphate would remove combined water after the distillation.

Microtek: Yeah, the specific Nitromors I'm using (they have paint stripper, paint brush cleaner, varnish cleaner, varnish
remover, etc etc etc etc etc etc) has some petroleum distillate of some sort, which stays in the DCM. I've found it can be
frozen out quite easily.
megalomania August 8th, 2002, 01:21 AM

In regards to the illegal reference, I meant that to apply only to OTC products for household use. The chemical must be
adulterated in some way before it can be sold to the public; this is more of an environmental thing, and certainly may not
apply everywhere.
nbk2000 August 16th, 2002, 11:14 AM

Something glaringly obvious (in hindsight) just occured to me.
The reason why the patent specifies methlyene chloride ISN'T because it's the most effective but, rather, the most convenient
solvent to use.
By looking at the table listing the extracting power of various chlorinated solvents, we see that the more fully halogenated the
solvent, the less effective it is.
Thus, carbon tetrachloride is less effective than chloroform which is less so than methylene chloride.
But I think that, if we continue with this line of thought, that we'd see that methyl chloride would be most effective of all.
Methyl chloride is a gas above (IIRC) 4*C, thus requiring refigeration to keep liquified. This would complicate industrial scale
processes which require maximum economy. But, to the HH (Home Hobbiest), maximum EFFICIENCY is the goal.
Methyl chloride is (IIRC <img border="0" title="" alt="[Wink]" src="wink.gif" /> ) easier to make than DCM, requiring simply
passing HCl through MeOH, and condensing the gaseous product.
Since the easiest way to seperate out the raffinate in the patent is to freeze it out with CO2, you'd already have CO2 on hand
for liquifying the MC gas. And, once seperated, the MC could be allowed to evaporate off, or be recycled.
Feasible?
PrimoPyro August 17th, 2002, 07:53 PM

It will be contaminated with hydrogen chloride and water vapor that will need to be removed.
nbk2000 August 17th, 2002, 11:02 PM

I'm assuming that a person would have the good sense to purify their solvents prior to use.
The question is, would methyl chloride be more efficient than DCM for extraction of HNO3?
nbk2000 August 21st, 2002, 09:04 AM

The methyl chloride generator consists of a 5-l. flask resting on a sand bath and fitted with a reflux condenser, with a delivery
tube running from the top of the condenser to a train of wash bottles, two containing water and two containing concentrated
sulfuric acid, with three safety bottles, one at each end of the train, and one between the water and sulfuric acid bottles.
To charge for about 45 moles (theoretical) of methyl chloride:

200 g. of water and 2.2 kg. (1.2 l.) of concentrated sulfuric acid are placed in the flask, and 1.4 kg. (1760 cc.) of methyl
alcohol is added, with cooling, at such a rate that the temperature does not rise above 70.
Then 2.4 kg. of sodium chloride is added, the apparatus is tightly connected, and the flask is heated on the sand bath so that
the gas is evolved at a fairly rapid rate.
It has been found in practice that, using materials of the commercial grade, the yield of methyl chloride is about 55 to 65 per
cent of the theoretical amount, so that about double the calculated quantities must be used.
rikkitikkitavi August 21st, 2002, 03:06 PM

Or you can use Lukas- reagense ZnCl2+HCl+MeOH and reflux it.
ZnCl2 acts as the catalyst/nucleophilic agent.
Unfortunately I dont have a link, I just read it in my Organic chemistry book, but it is a standard nucleophilic substitution.
It is also described in Vogels (chapter Alkyd halides, p272 for n-butyl chloride) but with larger carbon-chains and both primary
and secondary alcohols. Nevertheless , it is appliable to MeOH.
It also works in reverse (MeCl+ H2O => MeOH + HCl) but due to the volatility of MeCl yield is probably not so low.
/rickard
nbk2000 August 21st, 2002, 06:08 PM

I just got back from Wal-Mart where I picked up the stuff to try the process.
I got a can of DCM in a product called "Aircraft Remover" (made by Klean-Strip), 18oz (weight), for $4. It's DCM with less than
4% methanol. That's it...straight DCM in a can. :)
It was in the automotive section near the body filler stuff called "Bond-o".
Got the stump remover, the gloves...only thing missing is the acid. That's next week, along with the dry ice to freeze out the
raffinate.
Should I bother with washing out the methanol? Or just use it straight? Only side effect I see of not removing the MeOH would
be possible methyl nitrate contamination. But that'd be such miniscule amounts...
Pu239 Stuchtiger August 22nd, 2002, 02:54 AM

I must say that the difficulty of building an HNO3 still is being greatly exaggerated. It would take me less than an hour to
rebuild mine. It's simply two flasks, a glass tube, a propane burner, and a sheet of fused teflon tape. The yellow HNO3 that is
the result of NaNO3/H2SO4 distillation has a density of 1.51g/cm3. NO2 is easily removed with CO(NH2)2; H2O is easily
removed by placing a beaker of the HNO3 in a tightly sealed aluminum pot with a beaker of 98% H2SO4 for a few days (keep
the pot in a warm, but not hot, area if possible).
Much easier than toying around with dry ice, methylene chloride, etceteras... and a lot cheaper. Each milliliter of 100% HNO3
costs me about $0.02 to prepare.
nbk2000 August 22nd, 2002, 06:18 AM

And anyone can make a still from 2 beer bottles. Your point?
This topic isn't "Distilling is better than...", it's about using DCM for preparing anhydrous HNO3. Keep it on topic.
And who needs dry ice? You can simply boil off the DCM, or distill it at low temperatures and recycle it forever.
Here's a (possible) nitric synth so simple it's practically k3\/\/l. <img border="0" title="" alt="[Wink]" src="wink.gif" />
NITRIC ACID...the 3@%Y way
Stump remover, acid, 2 glass jars, can of DCM, and a can opener.
1. Mix stump remover and acid in jar. Let sit while you view your Sailor Moon H collection. :p
2. Turn can of DCM upside down and hold down nozzle till all pressure is released. Open end with churchkey can-opener.
3. Pour 1/4 can of DCM into jar. Put on lid and shake a minute. Let settle. Pour off DCM into other jar.
Repeat #3 till out of DCM.
Leave jar of DCM/nitric in sun till all DCM evaporates off. Cap off jar of remaining 98%+ HNO3.
No boiling hot acid splattering everywhere, no fire, no broken glass, no NOx fumes, nada.
Simple or what? :D
Use dry ice and you can get 100% ANHYDROUS CRYSTALLINE nitric. You CAN'T get that by distillation.
Cost? Same as the method you mentioned, only without the added expense of urea to remove the NOx impurities you get by
doing it that way.
Pu239 Stuchtiger August 22nd, 2002, 01:23 PM

You wouldn't want to leave HNO3 in the sun, because the concentration will go down as it yellows due to being broken down by
light.
Unless CH2Cl2 is free, distilling is cheaper. :-p
42mL of HNO3 would theoretically take $0.27 of H2SO4 and $0.20 of NaNO3 to prepare. Factor in a slight loss of yield, the cost
of propane (I get around eight hours of burn time for a $2 canister; it takes about thirty minutes to distill 60mL of HNO3), and
the next to nothing cost of a tiny amount of urea - the cost of 100% HNO3 is going to be around $0.02 per milliliter.
I'm saying just because earlier on this thread this CH2Cl2 method of extracting HNO3 was being spoken of as being cheaper,
easier, etceteras... which I disagree with.
vulture August 22nd, 2002, 02:59 PM

This might not be entirely on topic..
How about preparing anhydrous HNO3 by adding anhydrous MgSO4 to your nitric acid? The MgSO4 hydrates to MgSO4.12H2O
which falls out of the solution if you do not stir it. The HNO3 can then simply be poured off.
Drying nitric acid in a dessicator with 85%+ H3PO4 might also be interesting since conc. H3PO4 is insanely hygroscopic.
[ August 22, 2002, 02:02 PM: Message edited by: vulture ]
nbk2000 August 23rd, 2002, 08:49 AM

Well, I got some acid yesterday and was prepared to try the process. After spraying out some of the paint stripper into a jar of
cool water (to remove the methanol), I noticed this foamy shit and a lot of off-gassing as the cleaner sank to the bottom.
The stuff burned like acid when it touched my skin and formed a solid cake at the bottome of the jar on cooling in ice water.
Soo....there's obviously more than just DCM and methanol in the cleaner. I'm pissed that the full ingredients weren't listed on
the can like they're supposed to be. So I'll have to call the manufacturer monday and get a listing of the ingredients. Maybe
I'll just have to distill of the DCM first. *sigh*
Guess I'll just have to occupy myself with an NG synth.
mongo blongo August 23rd, 2002, 12:32 PM

I have just tried that with some more strange results. When I poured the DCM/Methanol into water it settled at the bottom and
turned into a jelly like substance with bubbles in it. The DCM I had was very old, possibly 5-6 years. When I have some more
cash I will get some more fresh DCM and try again.
nbk2000 August 23rd, 2002, 02:23 PM

I called their technical support section and got ahold of someone.
It turns out the ingredients are (In order):
DCM
Ammonia (gas dissolve in DCM)
Paraffin Wax
Methanol
I'll have the exact ratios within the hour since he's e-mailing me the MSDS.
The concentrated ammonia would certainly explain the burning, and the wax the foaming.
So, it seems some work will have to be applied to purify. Distillation to remove the wax, nuetralization to destroy the
ammonia, and washing to remove the methanol. Bummer.
If I had a car I could just pick up a gallon of pure DCM from the plant for $25. :( It sucks being broke.
Does DCM or ammonia destroy rubber? I could easily enough make a still from a bottle with a copper tube going...oops...can't
use copper with ammmonia gas. SS tubing then, with the spout going into acidified ice water to neutralize the ammonia and
condense the DCM.
+++++++++++++++++++++++++++++++++++++++++
Just got the MSDS:
METHYLENE CHLORIDE 75-80

PROPELLANT 15- 20
**
ABOVE INGREDIENT CONSISTS OF THE FOLLOWING:
PROPANE 70- 75
BUTANE 15- 20
ISOBUTANE 10- 15
**
METHANOL 1- 4
NONYLPHENOXYPOLYETHOXYETHANOL 1- 5
No ammonia or wax listed, so either he got the wrong product, or they've changed the formulation since the MSDS was printed.
But the 75%+ DCM content is encouraging.
+++++++++++++++++++++++++++++++++++++++++++
I've done some testing on the product.
I added an excess of 10% sulphuric acid to the product to neutralize the ammonia. After the fizzing ceased, I decanted off the
water layer, and washed the yellow layer several times with tepid tap water (shaking and letting seperate) to remove excess
acid and methanol.
The remaining yellow "blob" form a clear (piss yellow) layer with a foamy layer on top. When cooled in ice water, both sections
would solidify into a thick mass that wouldn't pour out. On warming again, it would regain its liquidity.
I sniffed it and it reminded me of chloroform. This explains the "blob" behavior, since chloroform does the same thing in water
(except the foam and solidifying part).
I noticed a waxy residue floating on top of the ice water when I poured the blob into it. The yellow blob at the bottom
remained fluid, but thick and opaque, while waxy bits floated on top.
Determining the Bp of the "blob" will show if it's DCM or not.
[ August 23, 2002, 03:21 PM: Message edited by: nbk2000 ]
mongo blongo August 27th, 2002, 10:51 PM

<a href="http://216.239.37.100/search?q=cache:ZnamOjuEhroC:ehis.niehs.nih.gov/roc/ninth/rahc/
dichloromethane.pdf+Dichloromethane&hl=en&ie=UTF-8" target="_blank">http://216.239.37.100/search?
q=cache:ZnamOjuEhroC:ehis.niehs.nih.gov/roc/ninth/rahc/dichloromethane.pdf+Dichloromethane&hl=en&ie=UTF-8</a>
Under the Properties part it says that is has a sweet chloroform-like odor.
nbk2000 August 28th, 2002, 09:18 AM
I boiled some in a test tube and it did so at 40*C, so it's definitely DCM. After boiling for a bit at 40*C, the residue started to
get hotter after it stopped boiling, thus being the wax.
I tried iceing the can down before spraying it out to minimize DCM volatilization but, as expect, the shit wouldn't spray out.
Likely because the stuff solidified in the can.
So it seems the way to clean up the product is to wash with acidified water to neutralize the ammonia, wash with water to
remove the salt, than distill to seperate the DCM from the wax.
Carbon tetrachloride also has a chloroformish smell. I sniffed it (once) just to know what it smelled like. I guess that series all
smells the same.
Now, according to the patent, chloroform will also work, but with only about a quarter of the efficiency. But that may be
acceptable since making chloroform requires only a bucket, ice, bleach, and acetone. I know the process works because I've
done it. Compared to finding pure DCM, it might be easier to just make mass quantities of chloroform.

If DCM works, how about using trichloroethylene? I don't know in which purity, but it's certainly OTC.
Rhadon August 28th, 2002, 07:43 PM

But both trichloromethane and trichloroethylene have a significant disadvantage: Their boiling points are higher than that of
dichloromethane.
<blockquote>code:<hr /><pre style="font-size:x-small; font-

family: monospace;"> BP
dichloromethane........40 C
trichloromethane.......61 C
trichloroethylene......87 C</pre><hr /></blockquote>I think that this could
be a reason why trichloromethane works worse than dichloromethane does, because when distilling off solvents with higher
boiling points some of the nitric acid will decompose. At least if it is done at atmospheric pressure. If vacuum distillation is
applied, this is not the case, obviously, but being able to get pure nitric acid without having to distill under vacuum is the only
advantage of the CH2Cl2 method in comparance to the directly distilling H2SO4/HNO3.
mongo blongo September 4th, 2002, 11:26 PM

Right, I have got some DCM (paint and varnish stripper) from B&Q (UK chain store). It is the B&Q brand which was next to the
"Nitromors" brand which was more expensive, hence more lightly to have other shit in it to help remove paint.
This stuff is a thick, colorless,transparent gel which made me think- Fuck!!! WTF is in this shit!!!??? :mad:
I didn't have access to the MSDS data so I don't have a clue!
I sat down and thought that since DCM is quite dense, it may settle down to the bottom when added to water. I think I was
right!
I added the thick gel to some cool water and the gel settled to the bottom. I mixed it up with the water with a glass rod very
well. The gel started to turn white and congeal. This told me that the DCM was probably being "sucked out" of the gel leaving
just the other components of the paint stripper which congealed because of the absence of the solvent (DCM).The DCM(?)
settled to the bottom!
I now had three separate layers. The top one was water, the middle was the white congealed shit and the bottom was a
transparent/milky liquid of what I believed to be DCM (uncleaned).
I have now filtered out the white shit and I have two distinct layers of water and DCM. There is still a very thin layer of the
white shit which got through the filter paper. This shit now seems to be clumping together and should be removed with another
filter.
What I plan next is to filter and add some water and shake it to wash out any methanol that I suspect is still present in the
DCM.
I also know that DCM is slightly soluble in water so there may be some water present in the bottom layer of DCM.
Of course this is BAD for HNO3 solvent extraction!
I have two ideas of removing water.
1) To freeze out the water in my freezer and filter out the crystals.
2) To wash it with H2SO4 to dehydrate it and it should separate into a different layer which can be separated prior to use with
HNO3 or XNO3/H2SO4.
In respect to my second idea, the DCM could alternatively be stored under water to prevent any evaporation of the solvent.
When you want to use it, you could wash it with H2SO4 to dehydrate it and use both layers for the solvent extraction (extra
H2SO4 to concentrate the HNO3).
It depends on which you prefer. <img border="0" title="" alt="[Wink]" src="wink.gif" />
From the amount of gel used I think I have obtained a very generous amount of DCM.(no exact measurements yet sorry)
When I have washed it and dehydrated it, I will do a boiling point experiment to confirm that it is pure DCM (as NBK did).
I also have some problems extracting the HNO3 from the DCM!
I could boil off/distill the DCM from the HNO3 at 40-50 deg C, BUT how will I know when all the DCM is gone?(I ain't going to
sniff it) :)
AND the HNO3 will still evaporate off when doing this which could leave you with a more dilute acid than anticipated in the
patent!(I don't want to do nitrations with the DCM still present because I can't be sure how much acid I am using)
NBK's idea of freezing out the HNO3 is MUCH better but dry ice is a pain in the ass to get and impossible to store at home(?).
I am very interested in this because I FUCKING HATE DISTILLING HNO3!!! AAARRRHHHH!!! :mad:
Has anyone got any better ideas of extracting the HNO3 from the DCM? :(
Boiling pt experiment coming soon!

HNO3 solvent extraction from XNO3/H2SO4 experiment as soon as I receive some new electronic scales (other scales disposed
of in a runaway nitration :( )
So has any got any comments on this?

Any magical solutions to removing HNO3 from DCM? :)
C-Ya
kingspaz September 5th, 2002, 05:33 PM

to purify the DCM from water add dehydrated calcium sulphate, mix it up then filter out the newly hydrated calcium sulphate.
i beleive a possible problem overlooked so far in extraction is that in CH2Cl2, as opposed to CCl4, the chlorine atoms are
open to attack by H2O molecules. thus hyrdrolising, CH2Cl2 + 2H2O <=> CH(OH)2 + 2HCl
HCl is gaseous so removed from the equilibrium and according to la chateliers principle the equilibrium will move to the right
therefore hydrolising more DCM :(
at what rate this occurs i am unsure bu i imagine daylight would speed this up somewhat by breaking the C-Cl bond.
mongo, for removing the DCM from the HNO3 read one of NBK's posts above.
also i have bought 500ml of nitromers paint and varnish remover but i got the stuff in the yellow can as it states 'free flowing
formula' so i thought i'll get this as it won't have that gel shit in it and therefore volume for volume more DCM :) ....haven't
had chance to experiment though.
[ September 05, 2002, 04:35 PM: Message edited by: kingspaz ]

kingspaz-I can't find the post by NBK you are refering to? Which method are you thinking of?

The one near the top... :rolleyes:
andreas September 6th, 2002, 11:25 AM

Has someone tested this nitric extraction method before. As I'll be getting 2 liter of dmc and some destillation equipment.I
have a corbondioxide fire extinguisher, could this produce enough dryice to cool 2 liters of prechiled(-30 centigrade)
DMC+nitric to -55 or beter -60. And after that what best to use a, sintred glass funel or a saporatory funell?
[ September 06, 2002, 10:26 AM: Message edited by: andreas ]

Don't waste the extinguisher making dry ice. Save it for putting out the inevitable lab fire.
Dry Ice is cheap...only a dollar or less per pound (US$), get plenty of it so you don't run out. 20 pounds or so should do
nicely.
But don't start out with 2 liters of DCM, use a couple hundred milliliters to start. Then work your way up.
Use the sintered glass to seperate out the crystals. Be sure to precool the filter in the chilled DCM mix, otherwise it'll either
shatter, or the crystals will melt and liquify, <img border="0" title="" alt="[Eek!]" src="eek.gif" /> thus defeating the whole
point of filtering.
You should also try distilling off the DCM, leaving behind the higher boiling point Nitric in anhydrous condition. All glass or
teflon, of course, otherwise (using rubber) you're setup will disintegrate/catch fire.
Mr Cool September 6th, 2002, 02:32 PM

Kingspaz: I don't think hydrolysis will be a problem; the chlorines are very bulky so there isn't much room for a water molecule
to get in and attack the C. I'm sure it happens, but only VERY slowly.
ALENGOSVIG1 September 7th, 2002, 08:41 PM

Alot of aerosol graffiti removers contain Methylene chloride.
Could be a possible source.
[ September 07, 2002, 07:44 PM: Message edited by: ALENGOSVIG1 ]
Trinitrotoluene September 7th, 2002, 09:52 PM

Thanks for the completely uninformative information. :rolleyes:
I hope (for your sake) that your postings rapidly improve...otherwise I don't see much of a future for you here.
[ September 07, 2002, 09:28 PM: Message edited by: nbk2000 ]

It's taking a while to clean this bastard stuff!! I have extracted about 150ml so far and it's still a bit cloudy. I'm sure that all
the methanol is gone now but there is some of that white shit which can't be removed by filtering (that's why it's cloudy). I had
it in a jar with a layer of water on top and it was left standing for about 24 hours. After this, the DCM layer was crystal clear and
the white shit formed a layer between the DCM and water. I tried filtering it (thinking that the white shit was clumping together)
but it still came through!
I now have it in a separatory funnel that is stood upright. I will leave it standing for a day or two for the white shit layer to form
again and then I will let the bottom layer (DCM) feed out of the drain tip.
TNT- That was a bit pointless.It's already been said! :)
edit-sp mistake
[ September 07, 2002, 09:41 PM: Message edited by: mongo blongo ]
Mr Cool September 8th, 2002, 07:17 AM

The cloudiness could be water droplets (like you can get when making NG), which would slowly float up to the water layer and
form bubbles of CH2Cl2 around the water droplets at the boundary. If this is the case, you could shake up the CH2Cl2 with a
saturated salt solution and leave it to settle, then seperate the two layers. This should clear it up.
mongo blongo September 8th, 2002, 08:34 AM

Yes I thought of that but I am sure it is due to the white shit in this case because of the other layer forming is a solid white
substance. It does however it does turn very cloudy when it is shaken but the water separates very quickly. I will make sure
there is no water present by washing it with a dehydrating agent.
andreas September 8th, 2002, 10:44 AM

I was planning to extract the nitric with severall postions of DMC but I think I'll distill it of anyways becouse the method of
freezing it out is quite difficult. This becouse you have to keep the mix cooled even when filtering. As NBK said 98% aint
nothing to spit at. It may not be anhydrous but this concentration is good for nearly every nitration you could probably desire.
With the exeption of maybe HMX and the like. Furthermore considering the low boiling point of DMC it doesn't take a lot of
energy to distill the DMC off and with a bit of ice packing of the condenser and the seceiving flask you get a lot of DMC back.
And you can reuse the sulphuric from the first step to boot.
---------------
its DCM standing for dichloromethane NOT DMC - kingspaz
[ September 08, 2002, 05:24 PM: Message edited by: kingspaz ]

I don't think you'd have to even filter it.
Simply cool it to freeze out the nitric crystals, let settle, then decant off the excess solvent, all while cold (of course).
When it warms back up, there'll be an excess of nitric...too much for the DCM to dissolve, so a layer of anhydrous nitric will
form at the bottom, with the lighter DCM floating on top being sucked off with a turkey baster.
:D
Use the decanted DCM for the next extraction.

Boiling point experiment was a success (it boiled at exactly 40 deg C). Next comes the HNO3 extraction from NaNO3/H2SO4
(when I receive my new scales). Anyone done this before?
I am looking for amounts of DCM to use. Does anyone know the max amount of HNO3 that can be absorbed by DCM and will
temp make a big difference? I know that I should use several small DCM extractions to get the best yield.
I have not yet decided how I will separate the HNO3 from the DCM but it looks like I may be freezing it out.
I was going to try and calculate amounts to use from the patent in respect to the moles of HNO3 that should be produced and
the moles used of DCM. I can't work out how to convert percentages into moles. Can someone help me out on this or has
anyone got any preset amounts?
Boob Raider September 10th, 2002, 12:59 PM

This is really getting pathetic :( . I can get KNO3 or Ca(NO3)2 and one shot drain opener but I can't even find trace anounts of
DCM. Home Depot, wal-mart, revy, local hardware stores ..... no one has Cl HC solvents. This is really shitty :mad: .
Can NaHSO4 be used instead of H2SO4 if trying to dehydrate an acid soln. I can buy shit loads of it from liquidation world dirt
cheap .... its some sort of concrete etchant. I am not so interested in making acrolein anyways.
So any other suggestions about DCM fishing ? And also reguarding NaHSO4 to dehydrate HNO3. Oh BTW I saw HNO3 and also
H3PO4 in a hydroponics store as a pH down soln. Does anyone have any idea on the concentrations as it doesn't say in the
can. I am expecting a shitty concentration.

If it's being used with plants, it's likely to be less than 20%. Might be worth it though if it's cheap enough.

Boob Raider-
<a href="http://ntp-server.niehs.nih.gov/htdocs/Chem_H&S/NTP_Chem7/Radian75-09-2.html" target="_blank">http://ntp-
server.niehs.nih.gov/htdocs/Chem_H&S/NTP_Chem7/Radian75-09-2.html</a>
It has a "uses" part which may help you on your quest. <img border="0" title="" alt="[Wink]" src="wink.gif" />
It also says DCM is liable to explode when mixed with HNO3! Could this be very dangerous? <img border="0" title=""
alt="[Eek!]" src="eek.gif" />
I was also reading this page from Rhodium-
<a href="http://www.rhodium.ws/chemistry/aromatic.nitration.html" target="_blank">http://www.rhodium.ws/chemistry/
aromatic.nitration.html</a>
It is using the units "mmol". What is this? Is it something to do with moles? Is it possible to convert it to grams? how? <img
border="0" title="" alt="[Frown]" src="frown.gif" />
vulture September 13th, 2002, 04:36 PM

mmol is millimole IIRC, so 1/1000th of a mole. Convert to moles, multiply with molecular weight and reaction coefficient and
you have the needed amounts in grams.

Thanks vulture! I know what to do with it once I have it in moles. :)
I haven't got time right now but when I do, I will calculate the amounts and post them here for reference.
mongo blongo September 16th, 2002, 11:17 AM

Right I have worked it out. The amounts used in the "aromatic nitration" link I posted didn't look right(not enough acid)!
I have scaled up and changed a few things so this is what I think looks right.
NaNO3-85g or KNO3-101g
H2SO4-100g (2g excess)
DCM-500ml
Yield-63g HNO3 (theory 100% yield)
That is a shit load of DCM! I am not sure if that is right! 500ml to absorb only 63g?
what do you think?
kingspaz September 21st, 2002, 09:04 AM

not sure if this has been mentioned yet but HNO3 and DCM supposedly form an explosive mixture.
<a href="http://www.biochem.okstate.edu/Safety/SafetyMSDSNitricAcid.html" target="_blank">http://

www.biochem.okstate.edu/Safety/SafetyMSDSNitricAcid.html</a>
maybe a new liquid explosive :)
mongo blongo September 21st, 2002, 09:39 AM

Yes I'm a bit concerned about that! Anyone got any ideas about the sensitivity of the solution?
nbk2000 September 21st, 2002, 10:28 AM

Don't worry about it. Nitric acid forms explosive compounds with practically everything. That's why us pyros love it so much. :D
As long as you don't stick a blasting cap in it, you should be fine.
Korfaction September 21st, 2002, 04:59 PM

Hello everyone, i recently tried to make conc. nitric acid with that method:
I mixed 64 mL of 58% HNO3 and 47 mL of H2SO4 (about those amounts, not very precise), in total number of moles it is
equal to those advised on the us patent. I shaked it with 100 mL DCM for several minutes, cooling the flask because the
temperature rised, then i let it sit for one quarte. There was a lower orange layer and a upper clean layer. I seperated them
and let it cool not exposed to sun for one week (i'm only here on weekends). From the upper layer which smelt DCM before
evaporating, there was only a few mL of clean mix, acid but not too much, with a density of about 1.1 so i'm wondering what
happened.
I got a few ideas of what could have been done wrong (cooling..) and stay in the beaker, but anyone exactly knows why that
easy manipulation failed ?
Thanks all.
mongo blongo September 21st, 2002, 10:15 PM

You could try to devide your DCM into several amounts and extract them in several amounts and combine all the extracts. You
will get better yields from several extractions than doing it all in one go.
How are you measuring the density?
Maybe you should use a bit more H2SO4?
Another reason could be something like I posted above (about HNO3 evaporating off when letting the DCM evaporate off).
Korfaction September 22nd, 2002, 05:30 AM

I mesure density with that archaic method of taking a few mL then weight it. You divide and you get density. The fact is that is
not very precise depending on the way you take the liquid but to measure a density of 1.1 instead of 1.5...
Another fact i don't understand is that there was about 5-6 mL of that liquid left, i assume that it was mostly water. But i
should have got 20 mL of 98+ % HNO3 so how could all this water came ? condensation ? that would mean it's not so easy to
make, precautions, dry air, are needed.
I used 95+ sulfuric acid, and the total molar quantity is the one told in the us patent. And to prevent questions, i used lab
grade 99.9% DCM, the other 0.1% is ethanol to stabilize it.
About the several extractions, allowing the patent, one would use about 700 mL DCM to extract 80% of the nitric acid, in the
best case. But then one would try to reuse the DCM.
[ September 22, 2002, 04:39 AM: Message edited by: Korfaction ]
mongo blongo September 22nd, 2002, 11:32 AM

mmmm... I don't know why it's going wrong.
Where did the H2SO4 you were using come from? I would use more H2SO4 if there is still water in your product.
I would also try a different method of removing the DCM from the HNO3. Try freezing the HNO3 out with dry ice if you can.
Also when you measure the density, use more than a few ml. The more the better because it will be more accurate. Even
better to use a hydrometer (very cheap).
Korfaction October 20th, 2002, 06:42 AM

Hello, I was wondering today about the water solubility of DCM. It appears to be about 13-20g.
So will the solubility of water in pure DCM be the same ?
Therefore, it theorically wouldn't be possible of getting more than 98-98.5% HNO3. I know it's enough for most explosives, but
i wanted to point it out. (And know if I'm right ?)
nbk2000 December 11th, 2002, 07:55 PM

OK, just gone done trying a little experiment. :)
Firstly, some observations on handling dry ice (frozen CO2) and cold baths.
DON'T use rubbing alcohol. It froze into a slushy muck that I couldn't get below -34F, and took forever to do so. It also
"smokes" badly, making it difficult to see what you're doing.
DO use acetone. It got below -52F (the lower limit of my thermometer) within seconds, and with virtually NO "smoke".
Wear rubber gloves over cloth gloves. If you get any of the cold liquid on your hands, without the cloth for insulation, and the
rubber to keep it dry, you'll get instant frostbite.
Do this in a room with an open window or outside. You may not be able to see it, but the CO2 will build up if you've got
enough of it, and smother you. Plus the acetone fumes aren't healthy either.
Now, on to the experiment.
Using a quart sized thermos soda mug, I cooled down a DCM extract made from 3 extractions of an AN/H2SO4 mix, in a test
tube immersed in the acetone/dry ice bath.
After a minute or so, needle-like crystals formed. However, the crystals melted within moments after I removed the test tube
from the bath, making seperation impossible. :(
I tried taking pictures of the crystals, but they didn't show, so I won't bother posting them.
I think what I'll have to do in the future is use a fritted glass disk attached to a rod, and have that at the bottom of the tube.
When the crystals have formed, I can lift out the crystals and immediately dump them into another flask for collection.
Better yet, have two flasks hooked together with a frit in between. Immerse the raffinate mix in the cooling bath, let crystals
form, then invert. All the crystals are filtered out, with the spent extractant being collected in the other flask. The two would
then be immediately seperated and the crytals allowed to melt for collection of the anhydrous acid.
When disposing of the cold bath solution DON'T pour it, even in little drips, into the toilet or sink. It instantly boils over and
sprays all over the place.
Just set it outside somewhere where it can naturally warm up. Somewhere where people won't see white fumes and think
"DOPE LAB!" and call the cops on you. <img border="0" title="" alt="[Wink]" src="wink.gif" />
Cost me a few dollars, and I didn't get any nitric out of it, but I think the failure was just as informative as a success. Next
time I'll be prepared and likely to be successful in collecting anhydrous via freezing.

NBK- How long were the HNO3 crystals? I ask this because I have a very fine sieve made out of what I believe to be
polypropylene (Al would be another choice) which could be used for very fast filtration of the crystals.
I was thinking of keeping all of the apparatus used in one of those ice boxes so that the surrounding environment and
apparatus will be as cold as possible.
Maybe if you make a larger batch it would take longer for the crystals to warm up, giving you some more time to separate the
crystals.
I was also thinking of using Ethylene Glycol for the dry ice bath.
I am having trouble finding dry ice at the moment so it may be a while until I can post some of my results.
Sounds good though, nice work. :)

1/8"-1/4" and very slender.
A fine metal mesh would probably be good since the metal would retain the cold longer, allowing the crystals to be moved
before melting.
Also, a larger quantity would last longer, true. I'll have to try a larger batch next time. Now that I know the process works, I'll
aquire more source material to make a decent sized batch of at least a few ounces worth of nitric.
I'd go with glycol next time. You'd want something for a bath that isn't going to be giving off any fumes or flammable vapors.
I'm off to try freezing out H2O2 now, before all my dry ice disappears.
zeocrash February 24th, 2004, 01:46 PM

the other week i Purified DCM from nitromors paint stripper.
the process was as follows:
250ml of nitromors was added to a 1L flask. 750 ml of water was then added to this.
The mixture seperated out into 3 layers, the top aqueous phase, the middle white crap phase, and the bottom oily phase
(DCM).
The DCM was removed from the beaker using a turkey baster and placed in a 500ml beaker. Concentrated sulphuric acid was
added until all the water was removed from the DCM (untill the mixture stopped boiling and bubbling). the DCM, this time
forming the top layer was again removed using a turkey baster and bottled.
mongo blongo February 27th, 2004, 10:56 PM

It still won't be pure mate. :) Try putting it in the freezer and you will see what I mean. I have found that if you freeze and
filter a few times then distill and then mix it with conc H2SO4 (carbonizes the more hard to remove petrolium distillates) and
filter ,then freeze and filter again, you will then quite pure DCM. Well that's the best method I could come up with and it's a lot
of work. I would wlcome any quicker methods. ;)
senjoronie March 6th, 2004, 07:18 PM

I purify DCM from paint remover by fractional distillation. It's still a somewhat involved process, but it's easier and safer than
the ones mentioned above, since it doesn't have anything to add or any water or acid mess to deal with. It's helpful if you
have a glassware set capable of it, but if not then build yourself a distiller (search for that info).
I use Zar brand paint and varnish remover, which is 91% DCM by weight. The first step is to distill quickly through a Vigreux or
other simple column (a hollow, unpacked tube is fine) to remove all the thickener junk and most of the toluene. There will be
a lot of bumping as the thickener deposits on the bottom of the boiling pot and traps superheated DCM gas pockets, so don't
use too much heat. The column really only serves to prevent the thickener from being blown past the still head and getting
into the distillate. Your setup should allow access to the boiler so that you can dislodge the buildup periodically. Collect the
crude distillate, but don't process it until you've distilled all the paint remover you were planning on, since the later distillations
require an equipment change. Monitor the vapor temperature throughout the distillation; when it reaches 45C you're finished.
The second and any subsequent steps should be done through a packed fractionating column or a Snyder column, and run
fairly slowly. Allow about 6 hours to distill 500mL. Collect the distillate and evaporate a small sample of it; if there is any
residual odor of toluene then you need to distill again. This will result in very pure DCM.
mongo blongo March 6th, 2004, 09:56 PM

It's quicker to leave out the first distillation, if you mix it with water, that will separate the DCM from the thickener and remove
the methanol. Fractional distillation would be a good way to go after that but most people don't have the equipment or time to
run it for that long. I see there are a few different formulas for DCM paint stripper, one I have experimented with did not
contain toluene.
vulture March 9th, 2004, 12:50 PM

BTW, use as less grease on your glass joints as possible, because DCM leaches the grease straight of the joint and vaseline
seems to be volatile when mixed with DCM... :(
To make a long story short: I had a nice layer of vaselin floating on top of my DCM. :mad:
nbk2000 March 10th, 2004, 01:47 AM

When dealing with solvents that can dissolve joint grease, don't use it.
Instead, take a small strip of teflon tape and place it in the joint (leaving a little bit overhanging), assemble your pieces, then
wrap the shit out of the joint with more teflon tape. The joints are able to bee seperated, no nasty fumes escape, and nothing
contaminates your honey. ;)
Learned this trick the hard way. :(
vulture March 10th, 2004, 04:14 PM

Trouble is, I bought a pot of something that's supposed to be Teflon grease, turns out it's already attacked by dilute HNO3!
:mad:
I was expecting it to happen, therefore I only used a tiny little bit, but to no avail.
I can't seem to find a decent source for pure Teflon tape in Belgium. Either way it's Teflon with 50% other crap or it's bloody
expensive.
zeocrash March 10th, 2004, 06:27 PM

doent plumbing shops sell teflon/PTFE tape. i know the DIY stor i work in does.
FrankRizzo March 10th, 2004, 08:41 PM

I've found a solution that's not really OTC, but not incredibly hard to procure either. Google a source for "Glindemann Sealing
Rings." They're a thin, little PTFE ring that slides onto the male portion of your ground-glass joint and seals it VERY well.
They're much cheaper than those Teflon sleeves, and seem to work just as good or even better. I got mine from UGT; 50
rings for about $40-shipped.
EDIT: They also let you use keck clamps, whereas the telfon sleeves make the joint too big.
nbk2000 March 11th, 2004, 02:14 AM

You can find pure PTFE plumbing tape in hardware stores. Used to seal pipe joints. If it's not snow shite, it's not pure PTFE.
Zeo...the I/i capitalization rule applies to you too. ;) You might want to start capitalizing the beginning of your sentences too,
while you're at it.
"Teflon" grease is just teflon powder suspended in a petroleum-based carrier. Not at all immune to chemical attack. :(
jimmyboy March 31st, 2004, 09:39 PM

I have looked at the patent and it looks like a reasonable extraction - has anyone gotten a good yield out of this method yet?
Dave Angel May 26th, 2004, 12:08 AM

I have finally gotten sick of NOx from standard distillations of nitric acid, so I decided to look into the DCM method.
I can get hold of some lab supply DCM but I'd rather get it OTC if possible, so I bought some Nitromors, the yellow one to be
exact. I chose this as it was cheaper than the green one and sounded and felt much less viscous when shaken.
It turned out to be colourless and of low viscosity. I mixed 100mL of it with 300mL of water in a separatory funnel and shook
them. The result was a suspension of small fluffy white blobs (dia. 1 - 2mm) which would not separate into 2 or 3 layers as
some have reported. Some kind of wax had precipitated and was containing the DCM. Adding water first is obviously not an
option with this type of Nitromors.
Instead, I gently distilled some straight paint stripper into a flask equipped with a reflux condenser as the only opening to the
atmosphere. The residue, left to cool, congeals into a soft waxy goo (for want of a more scientific term). The distillate was
washed in portions with two lots of double its volume in water, and the DCM layer was run off into a flask and stored in the
freezer at -20C. No volumes or percentage contents of DCM as yet, this was just a qualitative experiment.
I've just checked the flask and noticed that something has precipitated out of the DCM, possibly some light fractions similar to
the wax left in the heating flask. Mr. Cool reported something like this I see, though what I'm concerned about is that some
may still remain in solution. I shall check the density after filtration tomorrow and if it indicates other than fairly pure DCM then
a final fractional distillation before drying with MgSO4 may remove it.
Any other suggestions as to how to remove this final impurity if any of it remains?
[Edit] It doesn't look like the impurity is going to be a problem. After filtration at -20C the precipitate was removed. It's
important to remove the filter paper and scrape off the precipitate before running more crude DCM through though, as it melts
very quickly and can get carried through.
A calculated density of 300mL gave 1.31(4)g/cm3 with the literature value being 1.316g/cm3. This was however whilst the DCM
was still cold. A weighing of an amount in a volumetric flask at 298K would give a more accurate idea of the density as I have
no hydrometer in the correct range.
It seems pure enough for me though. I'm going to extract the rest of the DCM from the paintstripper and dry it with anhydrous
MgSO4, at which point it should be good enough to make some of the elusive white anhydrous nitric acid.
nbk2000 May 26th, 2004, 05:54 PM

OT:
Zip-strip, a DCM based paint remover, will apparently remove the dye used in dye-bombs by banks, from the money that's
been contaminated with it. :) :D
Dave Angel May 26th, 2004, 10:27 PM

That being the case, I wonder if DCM can be used to remove the dyes used in those foam/dye defense sprays. Washing my
face with DCM doesn't sound too appealing so perhaps a solution of DCM in alcohol would be less aggressive towards the skin
and still remove the dye. Still, if it was a choice between being identified by the dye and subsequently locked up, or walking
around with a bit of a sore, red face for a while I think I'd choose the latter.
nbk2000 May 28th, 2004, 05:31 PM

Makeup hides many sins. ;) seriously, you'd NOT want to put DCM in any concentration on your face. It'll pull all the oils and
fats out of your skin, making it crack and blister something fierce.
Besides, if you're not out trying to "catch" a date ;) on saturday night, you'll not have green dye on your face, right? :D
Reminds me of a joke:
Q: Why do niggers cry after sex?
A: Because of the mace! :p

Tell me about it... I've managed to get a splash on my hands now and again and it chaps them like acetone but worse. I
hope I won't be getting any of that foam on my skin anytime soon, if I was going out to "catch" a date I think I'd profit from a
trip to The Hive first. :D
Anyway, I finished the processing of my Nitromors and got 3300mL of DCM (out of 5L). This indicates a 66% v/v content, but
as some of it was lost in attempting earlier processing (though some of that was recovered) it's more likely to be closer to
70%. This is like Mr Cool's Nitromors, so it's likely that it's a standard 70% DCM with other ingredients to give it different
properties for different jobs.
I had something like 800mL of a 50/50 by volume mix of nitric and sulphuric acid that I gave up on distilling normally. I
shook this in 8 equal portions with 100 - 150mL of DCM each time in a separating funnel (frequent venting was needed!), and
recovered the left over sulphuric acid which, according to the patent, should have plenty of nitric acid left in it.
The DCM/nitric acid is sat in my still now, with a water bath at 50C providing the heat. For the first hour or so there was plenty
of NOx around in solution which worried me slightly, but it's now cleared up and the DCM is just a bit yellow. It should take a
while to remove all the DCM but the results (I hope) will be worth it.
As a side note, I have quite a lot of soft wax left over from processing all that paint stripper which should be usable in ANWax.
Mumble May 30th, 2004, 06:43 PM

I've been experimenting with this method too. I can definatly vouch for the burning from DCM on the skin. Made the mistake
of using shitty gloves, and they didn't hold up well.
The MSDS (http://www.starbronze.com/pdfs/720.pdf) I got from my paint remover, Zip-strip coincidentally, claimed 80% DCM.
From 1 pint(453mL) I got 150mL after purification, a little more that 225mL before purification. I found a purification
proceedure in a chemistry book I have. Wash with concentrated Sulfuric Acid, wash with concentrated (bi)carbonate solution,
and dry over CaCl2. The acid removed all traces of waxy solid. I think the waxy solid may be the mineral spirits. As with most
things, I expect the yield to increase if I used more product. From 1 gallon, I would hope to get 2.5L. Having a separatory
funnel would increase the yield too.
I have a slightly yellow DCM solution right now, after attempting to extract .5 mol of nitric acid from Sulfuric and KNO3. I added
urea to attempt to destroy the NOx, but instead ended up with Urea Nitrate and the same yellow. Once it stops raining I will
distill the DCM off. During a test, I noticed that as the DCM was boiled off, two layers formed. I took a small sample and
placed it in a test tube in warm water. I'm going to see about finding the solublility of nitric acid in DCM, so a more accurate
amount of DCM can be used.

It doesn't even matter if you have nitriles, DCM seems to eat through them in pretty short order, good for splash protection
only really. It doesn't help matters when you have nitric acid in the DCM at times either.
Even at 50C, in my limited experience with it so far, you start to get a definite reddening of the DCM/HNO3 as you have
almost removed all of the DCM. Perhaps lowering the temperature even further could prevent this as the last of the DCM is
distilled off, but then you might just end up with the remaining DCM refluxing in the heating flask. Gentle heating of this in an
open pan would be the solution to this, with the disadvantage of lost DCM.
I've decided to go half and half on this, if you like. I'm collecting all of the DCM/HNO3 I have reduced down and once I have
enough to make it economical I plan to buy dry ice and extract the nitric acid that way. I've no idea how long it'll store in an
insulated box or how much it costs as yet.
Mumble, I've made a couple of useful observations whilst doing this which may help you.
Firstly the DCM will easily distill over without boiling (ie. no bubbling in the flask) which should limit decompostion and nitric
acid carried over. I use a hotplate to heat my water bath and it holds quite well at around 48-50C w/o thermostatic control via
a probe (which I do not have).
Secondly, with the first distillation I did, I noticed a second small layer at the bottom of the heated flask quite early on. I'm
pretty sure this is sulphuric acid (it's quite viscous) which did not separate properly (ie. I didnt leave it long enough). Now, once
I have all my extracted HNO3 in DCM I put the whole lot back into the separating funnel (certainly a useful piece of kit) and
give it a good 15-20 mins so that the remaining H2SO4 can separate out. Was your sample of the other layer miscible with
the warm water though?
Good luck with your experiments.
Bugger August 20th, 2004, 08:51 PM

Dichloromethane, like other volatile chloro- and bromocarbons, is a dangerous liver toxin in large doses. "Glue-sniffers" who
inhale it (or paint-stripper) and similar substances are also in danger of brain damage through its getting into the
bloodstream through the lungs.
It is also very corrosive to practically all plastics.
John W.
Dimroth August 25th, 2004, 06:28 PM

Doesn't glue usually contain methylacetate as a solvent? According to my references you'd need serious exposure to suffer
from any effects.
Mendeleev October 3rd, 2004, 09:56 PM

In the USA, Jasco's paint and epoxy remover is around 82% methylene chloride, and can be bought at either Lowes or ACE.
http://www.jasco-help.com/products/prod_rem.htm
They have msds's for all their products, and the graffiti remover has ammonium hydroxide, so it's likely that other brands like
the aircraft remove that nbk got use it as well. Do not buy any strippers by Crown, they are orange. I attempted to wash the
crown shit straight out of the can, and it separated into the three legendary layers, but the bottom layer was still orange. I
suppose you have to distill first, then wash to get rid of the methanol, then dry with CaCl2, filter, and redistill to get a
relatively pure product. Also, the crown stuff conatians toluene and acetone in addition to methanol.
bobo October 4th, 2004, 07:57 AM

Twice I made con. HNO3 this way. The first time, I used distillation until slightly red color appeared to get rid of the DCM.
Apparently, the boiling temperature rises quite a bit even at moderate DCM concentrations, as the product contained a
respectable bit of DCM.
The screwthread stopper I used, by the way, was no inhibitation at all for the DCM to happily evaporate from the bottle, in a
few months of disuse.
Similarly, using no distillation at all, at 20 degrees, it takes about a week for the DCM to leave the mixture if there is no
stopper present. Although the red gases appear of their own in concentrated solution, so I do not suggest storing this mixture
for long. Vacuum distillation would be best, though a cold trap (liquid nitrogen is safe) is required if you want to use a
membrane pump.
Using nitrogen cooling, I made the nitric acid freeze out and was slightly disappointed at the resulting crystals. The density of
this acid was about the same as the acid obtained through low temperature distillation.
However, in all cases, the acid did not heat to the touch when adding an equal amount of concd sulfuric acid (indicating near
anhydrous acid), although a double layer may appear if there is a lot of DCM still left. This is no problem at all for me, since
DCM does not harm most nitrations one bit, and in fact is a good addition for the more sensitive nitrations.
One thing about paint stripper: there is now a green type of paint stripper as well, containing NO DCM, in the european
hardware stores. This may or may not always be written on the can, but if it is an environmentally friendly paint stripper, you
probably won't find any DCM.
The_Rsert December 23rd, 2004, 02:00 PM

My local paint store sells anything I need from it.
Waterfree isopropyl alcohol, acetone, 24% hydrochlroric acid, 25% liquid ammonia ethanol and ether, styrene and methanol if
you will ask for it but no DCM.
When I asked a clerk of the store for DCM, she told me that chlorinated hydrocarbons are principle forbidden to sell in
Germany.
Is that true?
Does it give some law-vacancies/law-openings or any legal reasons to get the DCM?
FUTI December 23rd, 2004, 03:33 PM

About CH2Cl2 toxicity discussed here I can add only that it is considered cancerogenic in such extent that it is removed from
decaffeine coffee production where it was used for caffeine extraction. Only chlorinated compound that can be found OTC is
trichloroethylene AFAIK.
Mumble December 23rd, 2004, 07:12 PM

No, you can get a handful of chlorinated solvents OTC. I can't speak for Germany specifically, but often times it is not in a
pure state. In the US DCM can be retrieved from "Zip Strip". It supposedly contains something like 80% DCM, but I don't
believe it. Extraction of the DCM is fairly easy. A simple distillation and wash with water will remove everything leaving you with
nearly pure DCM(I dry it of course). I've heard of Tetrachloromethane being available in starting fluids. It's also in some
hobby glues(very low percentage though). There is chlorobenzene in a certain type of herbicide(Monsanto Lasso Herbicide).
Basically it's just a matter of looking, and willingness to extract. Where there is a will to get it, there is a way.
Centimeter January 24th, 2005, 12:15 AM

I mixed 150ml 70% HNO3 and 150ml H2SO4 then added about 300ml MC in 3 portions. I obtained about 50ml of acid. Near
the end of the distillation the HNO3 decomposed A LOT. I kept the distillation between 40 and 43*C. Why did it decompose at
such low temps? There was some sort of solid that formed in the HNO3. I put it in a separatory funnel and got out all of the
solid. Upon titrating the acid, I found the concentration to be ~71%. What the fuck is up with that? Granted the MC was
contaminated with something. Or perhaps there was an impurity in the H2SO4 drain cleaner, that was nitrated? BUt 71% from
70%. Any thoughts on what's going on?
zambozan February 20th, 2005, 01:10 PM

Hallo to all,
I've found a solvent in a home-market which is composed 50% of trichloroethylene and 50% methylene chloride.
It costs 2 for 2 L. This seem to me n ot that e x p e n s ive.
How about using this as a OTC source for methylene chloride?
Can be distillation for separe methylene chloride from trichloroethylene?
Hope that I've helped.
nbk2000 February 22nd, 2005, 02:58 PM

What's it called? :rolleyes:
Pb1 February 22nd, 2005, 07:32 PM

I don t think the trichloroethylene wo uld be a major problem, as it would just boil off with the meth ylen e chloride after
extraction.
FUTI February 23rd, 2005, 11:08 AM

It will be a problem with trichloroethylene...but I'm not sure of its size. NOx if(or better said almost allways) present can make
number of side reactions if that CH2Cl2 is contaminated...I didn't read the papers attached to better then chlorpicrin thread
but this can lead to something similar if my guess is right. Conditions of extraction or reaction (if that is what you want) are
still blurred to me, but I will try to find something to report.
Elucifer March 1st, 2005, 02:31 PM
me, i go down to "-------- Plastics" and ask for a 4 litre container which is used for sealing/fusing lexan, they hand it to me, i
hand them $20 and i go back to work! it is remarkably pure, it is used where ever plastic retail displays are made.
E-Lucifer
Sworn November 24th, 2006, 03:21 PM

I think the solvents are slight volatile and difficult to separate when distilled only one time. A useful separation will work on the
melting points.
trichloroethylene, melting point around -86 C

methylenen chloride, melting point around -95 C
Might that work, trichloroehylene decompose at around 110 C and methylene chloride at around 120 C.
First distill the solvent above the boiling points to clean them from residues and decompose the trichloroehylene. Reflux the
destillate between 110 and 120 C for an hour and distill again. The distillate should be useful.
It`s a pity for the trichloroehylene.
Any thoughts ?
++++++++++++++++
Yeah...in the future, use more paragraph breaks in your posts. NBK
rayman November 27th, 2006, 08:44 PM

Nbk How did your experiments with this go ?
Sworn November 30th, 2006, 01:41 PM

In my opinion, methylene chloride is difficult to make. Maight a decomposition of a small quantity of nitromethane combined
with a chlorination gives various results of a solution of methylene chloride and chloroform.
Such a technique is used to produce ammonium nitrite.
However, anyone may find something more to cool the distillate below -63 C to separate the chloroform.

After reading the above about ease of concentration of Nitric acid, I decided to get myself some paint stripper. Mixed with
water and seperated out the DCM. I bought the cheapest stuff available and didnt get that much DCM. Next time will try a
brand name. Anyway does anyone have any more progress on calculating how much Nitric will dissolve in this? Need to find
some dry ice...!
plutobound May 25th, 2007, 10:18 AM

Has anyone actually been successful at extracting useful quantities of Nitric acid from Dichloromethane (DCM) using the
freezing method?
I mixed 527g of 70% HNO3 with 821g of 96% H2SO4 (I need a significant amount of anhydrous HNO3). Thoroughly agitated
the mixture with 4 liters of DCM (in one liter portions), separated the raffinate from the hydrated acid using a separatory
funnel.
I then cooled the mixture to -70C.
There were a few small crystals in the flask, but even without loss from transferring, the yield was so low as to be useless.
I titrated the raffinate with KOH to verify that there was a significant quantity of HNO3 present (there was).
So now I am distilling the DCM/HNO3 mixture and recovering the DCM for reuse, but the freezing method sure would be
simpler.
PapaMuffin October 6th, 2008, 05:35 PM

Long-time browser of the forum and roguesci.org, first time poster. I know that as a n00blet, I shouldn't be starting my own
thread, but I happened upon this the other day and thought that it would look quite nice in this particular forum.
http://www.freepatentsonline.com/3981975.html
In effect, the guy posits that you can get a yield of around 50-60% anhydrous HNO3 by making a 47:53 solution of 95-98%
H2SO4 and 70% HNO3, respectively, then performing either a series of 100mL extractions using methylene chloride, or one
big extraction (which will, as is generally the case in liquid extractions, produce a lower yield). Anyway, it seems like a less
cumbersome method than distilling it to ~90%, then bubbling air and urea through it. You just have to be willing to shell out
the cash for the additional reagent (methylene chloride), which seems comparably inexpensive.
Has anyone tried this, or has the equipment and time to try it?
+++++++++++++++++++
We don't encourage noobs to start new threads because they usually shit the bed... They rarely have the common dog fuck to
search the forum properly for existing threads...
Merged...
stupid939 October 23rd, 2008, 04:59 AM

OK, there has been a discussion on the subject of concentrating nitric acid using DCM for quite some time now, and there have
been successful results. What I want to know is if anyone here has actually used the anhydrous nitric acid in DCM solution to
nitrate any substance, particularly hexamine. I would assume you would cool the solution, add hexamine (and possibly
ammonium nitrate for better yields), heat the solution (possibly driving some of the DCM off, and then cooling and collecting
the RDX (if it is not soluble in DCM).
I know some have discussed this, but from my searches (for hours) I have not found any claims. I believe nbk mentioned it
awhile ago, and from what I gather, the DCM will not affect the nitration of a substance.
Maybe I will have to be the guinea pig on this one when I find the time.
Alexires October 23rd, 2008, 06:16 AM

stupid939 - Do you know what the reaction method is? If it involves the nitronium ion, you might not be able to do it without
an acid in there to form the nitronium ion. I don't have a copy of urbanski here, so I can't look for you, but just have a look
and see how the reaction method looks.
stupid939 October 24th, 2008, 04:02 AM

My original question came from this:
I think i remember reading a while ago in the patent for this that the nitric acid with the methylene chloride still present in the
acid, can be used for the nitrations without the methylene chloride interfering. Would this work for the prodcution of RDX? All
you would need to do is mix the nitric and sulphuric acid, add the methylene chloride, suck off the sulphuric/water layer, and
PRESTO! Acid for RDX manufacture!
I have also read this in some of the nitric acid extraction technique patents. Anyways, to re-state my idea:
The AN could be left out, and the synthesis proceed as if only using nitric acid and hexamine. So, you would have a solution of
nitric acid and DCM. Hexamine would be added to the solution, keeping it at a low temperature. This would then follow the
basic procedure and the temperature would be held at 55C for several minutes (and the solution would likely boil). Then it
could cool, and the RDX would precipitate. It could then be filtered, and the DCM possibly re-used.
This is all of course if RDX in insoluble in DCM (which I could not find any data on).
Alexires October 25th, 2008, 08:52 PM

Solubility: One gram in 25 ml acetone; slightly soluble in acetonitrile, methanol, ether, ethyl acetate, glacial acetic acid;
practically insoluble in water: carbon tetrachloride, carbon disul-
fide
If this is correct, I would assume that the solubility of RDX is maximum around a dielectric constant of k=20.7 (that of
acetone). Hence, something like dichloromethane (aka dyke) which has a k=9.1 would be less than 1g/25ml, but more than
slightly soluble, I would say.
This is due to dichloromethane having a k lower than acetone, but above things like ethyl acetate (k=6), carbon tetrachloride
(2.2) and carbon disulfide (2.2). The other side of the spectrum are things like water, methanol and acetonitrile which have a
k value significantly above that of acetone. I would expect glacial acetic acid to have a solubility similar to that of acetone, but
that isn't give in the above and has been considered "slightly soluble".
Hence, I would say that using DCM would decrease yield slightly. Then again, if that is all you have, then that is all you have.
I'm sure that by lowering the temperature of the DCM when you are done, you would be able to get the extra RDX out. If you
are planning to reuse the DCM (I don't see why not) then your second batch should have an expected yield.
fluoroantimonic October 25th, 2008, 11:44 PM

A problem that I can with this scheme is that hexamine may precipitate as insoluble hexamine nitrate as soon as it contacts
the DCM-HNO3 solution. This may inhibit further nitration, I don't know. You'd just have to try it and find out.
It sure would take a lot of DCM, about 4 liters of it to dissolve the 500g HNO3 needed to nitrate 50g hexamine at a high yield
(according to COPAE). That is unless having the DCM present would reduce the needed amount of excess HNO3. Again, just
have to try it and find out.. With 4 liters of DCM you might end up dissolving a pretty good portion of the RDX.
"For RDX, though, extraction of a 400-mL sample (of RDX dissolved in water) with 20-mL of methylene chloride resulted in
only a 60% recovery of RDX (Leggett et al., 1990). Using salting out extraction with acetonitrile, however, recovery was 96%..."
This tells me the solubility of of RDX in DCM is probably low. Hard to say how low, but I would bet lower than 1g/100ml. To
decrease it much further you could add something low boiling like erthylene glycol to precipitate it from the DCM, then distill
off the DCM.
stupid939 October 26th, 2008, 05:58 PM

Thank you for that information Alexires. Like fluoroantimonic said, the only way we will really know is if someone tries it, but
the information you both provided gives me a little hope that it may work. When I have the time, I will test this procedure and
report my findings. This would make for a much simpler way of making RDX in my opinion.
FUTI October 27th, 2008, 09:26 AM

If 20 ml DCM extracts 60% RDX out of 400 ml water solution then I would say DCM is good solvent for RDX. Also watch out how
do you perform acetonitrile version of that experiment...AFAIR acetonitrile is prone to acid induced explosive polymerization .
SWIM (no not me) was doing some nitration experiment which involved acetonitrile as solvent and that went wrong... yellow T-
shirt kind of wrong stuff ;-). Reference he was doing experiment was reliable, other components I eliminated as the one I
can't imagine to do something funny under those conditions, I'm certain that experimenter is more reliable then myself and
didn't made some error so only thing that was left was that he used acetonitrile that made problem. I'm kind of surprised that
reference didn't noted that problem...I bet it doesn't occur often only when acetonitrile is contaminated with other stuff like
acrylonitrile etc., so if you don't purify your solvent you play Russian roulette ... which batch did I get today?
fluoroantimonic October 28th, 2008, 02:28 AM

Heh... well considering there might have been a whole 5 or 10 milligrams of RDX in that water, I don't believe DCM would be
that great of a solvent. Hell acetonitrile only dissolves about 1g per 20ml IIRC.
And nobody is recommending acetonitrile as a nitration solvent, I doubt it would be near stable enough, and besides you
wouldn't want it to be a good solvent for your product anyway.

Improvised Manufacture of Nitric Acid > Nitric Acid by Kno3
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View Full Version : Nitric Acid by Kno3
endotherm June 5th, 2002, 06:25 PM

Can someone post a good procedure for synthesizing Nitric Acid using Potassium Nitrate as the nitrate source?
[ June 05, 2002, 05:26 PM: Message edited by: endotherm ]
photonic June 6th, 2002, 02:49 AM

PYRO500 wrote a very good, detailed pdf on this procedure.
It basically just says to mix 32G H2SO4(98% or >) and 68G of KNO3 then vacuum distill at about 90C. If your HNO3 isn't pure
enough, just add some H2SO4 and distill again. THe pdf is/was available on the ftp( which I no longer have access to :( ) but
it has been down for a while. If you want it, i'll put up a server and let you d/l it.
mongo blongo June 6th, 2002, 09:00 AM

I don't think those weights are right. From the equation for this reaction you should end up with 101g of KNO3 and 98g
H2SO4.So for the amount of KNO3 above (68g) you need 65g of H2SO4.Remember that the H2SO4 molecule only gives one H
atom to the HNO3 molecule.
If you vacuum distill it you should heat it at a much lower temp than 90C. The whole point of using a vacuum is that it will boil
at a lower temp so that there is less formation of NOx. I can't remember the right temp but it's something like 60C.
Nitro June 6th, 2002, 04:00 PM

Best Temperature is between 83- 85 C.With this Temp. there is not so much NOx in your nitric acid.Here is an very good
german side with Destilling apparatures/methodes.
<a href="http://www.chemikalienlexikon.de/cheminfo/1248-lex.htm" target="_blank">http://www.chemikalienlexikon.de/
cheminfo/1248-lex.htm</a>
"Was der Affe fr den Menschen ist der Mensch fr den bermenschen"
Celtick June 6th, 2002, 05:27 PM

I uploaded a <a href="http://us.f1.yahoofs.com/users/241add87/bc/E%26W/Synthese+Rood+Rokend+Salpeterzuur.pdf?
bcLb9_8ALEL9 KFsz" target="_blank">PDF</a> with the Fuming Nitric Acid synthesis converted from <a href="http://
www.pyrolabs.cjb.net/" target="_blank">Pyrolabs</a> witch appears to be offline for a while now.
(Its a Dutch article)

I had a wonderful source with pictures, equations, and whatnot, but I will be damned if I can find it. There isn't much to it
really, but it does help to have exact information to be specific. I do however have some related safety information that I
think is relevant to this. Here is a reprint of a discussion about distilling with sulfuric acid and a nitrate:
A retort is not strictly necessary. The best thing to use is a pyrex

distillation rig with ground glass joints. The main thing is that you
cannot use rubber, as the hot nitric acid vapor will eat it.
I have made nitric acid using a pyrex boiling flask with a teflon stopper as the reaction vessel, and a 6' piece of .25" i.d. teflon
tubing run into a separate flask sitting in an ice water bath as the condensor. I made the stopper by turning a piece of teflon
rod down on a lathe. It might be possible to use rubber by wrapping it thoroughly in teflon plumbing tape to protect it, but I
have not tried this. You will have to heat the mixture. You MUST use an oil bath for this. The oil bath eliminates hot spots,
and reduces the tendency to "bump". Vegetable oil is ok, and it's cheap. Mineral oil is better. Don't try motor oil, it stinks like
hell when you heat it. I tried this once using an electric hot plate without an oil bath, and had a liter of boiling hot sulfuric acid/
sodium nitrate slurry shoot out of the flask in a single solid stream, right in front of my face, spray all over the ceiling, and
drip down on my head. I was lucky not to be blinded or killed. You must also be able to control the heat precisely. I use a
variac. If you don't have acess to a fume hood, you can do this in front of a window with a fan. The vapors are intensly
poisonous, and some of the oxides of nitrogen which are formed will not be stopped by the condensor.
When I did this reaction using concentrated sulfuric acid obtained by

boiling down battery acid and sodium nitrate from the local feed and
seed, I did not observe any undue heating when the components were
initially mixed. It might behave differently with KNO3, though I
would tend to doubt it. The nitrate was in form of "prills", little
balls slightly smaller than BB's. The prills did not begin to dissolve
until after the mixture had been boiling for a good five minutes. A
more finely divided nitrate might behave differently. It took a fair
amount of time after the boiling started for the acid to start coming
over, which tells me that you have to drive the reaction pretty hard
in order to get the nitric acid form in the first place. The first thing you get is a bunch of dark brown vapor, but it turns clear
once the acid starts distilling over. For the benefit of those who may have missed the beginning of this thread, I want to stress
again the importance of using an oil bath to heat the distilling flask. This stuff tends to bump violently, to the extent that it
can shatter the flask or spray the the boiling acid/nitrate slurry all over the room. The temperature needs to be brought up
slowly, over the period of an hour, because there is a substantial lag between the the temperature that the oil reaches and the
temperature in the flask. You don't want to overheat it, and it's a good idea not to fill the distilling flask more than one third
full as the goo tends to foam up a lot. This really is a dangerous procedure, but with good equipment and a great deal of
caution it can be performed sucessfully. I would also recommend only doing small batches, especially at first.
photonic June 8th, 2002, 03:50 AM
Hey, I would like to set up a distillation apparatus for making HNO3 from KNO3/H2S04. I don't want to pay for glassware so I
was searching for teflon tubing. I couldn't find a local supplier of it but I did find one that will sell me 50ft of some flexible
plastic tubing called "Nalgene." They say it is very chemically resitant and will handle temperatures up to 550F. Do you think
this would be suitable for distilling nitric acid?
EDIT: Further searching revealed that Nalgene is PTFE which is the chemical name for Teflon. So, I'm assuming this ought to
work?
[ June 08, 2002, 02:56 AM: Message edited by: photonic ]

Nalgene would handle the Nitric acid without any problems. The only substances that PTFE are not chemically resisant to are
very hot flourine and very hot sodium.
Glassware is expensive, and where I live (Australia) if you by anything other than beaker and/or test tubes, the pigs will think
you are setting up a drug lab.
Has anyone tried my method of making nitric acid by decomposing xNO3 and then bubbling the NO2 gas though water?

I once tried making a little bit of HNO3 with H2SO4 and NH4NO3 in a testtube. Although it was not finely divided, I had to
abandon my lab because of the insane formation of HNO3 vapor. The sulfuric was >90%.
Demolition June 10th, 2002, 11:13 PM

Flake2m - Have you found a source of Nalgene (Teflon) tubing in Australia?I've looked around and so far cant find anything.
:(
Also is Aluminum tubing HNO3 resistant?IIRC there was a topic a little while back on making HNO3 and I *think* a member
stated that Aluminum tubing was HNO3 resistant however im not to sure.
Demolition June 10th, 2002, 11:30 PM

I found it,my search button wasnt working before. :o
Originally posted by Microtek.

Helvetica">Did you know that aluminium is compatible with nitric acid ?
My destillation setup is made with Al tubing and foil and the only effect on the Al is that it forms a thin oxide layer ( and on
most tubing this has already occurred).<hr /></blockquote>Originally
posted by 10fingers.
Helvetica">Aluminum is impervious to nitric acid at lower temperatures. I once tried to make a distillation condenser out of
aluminum but the warm nitric acid vapors started to react with it.<hr /></blockquote>Both quotes came from the topic 'HNO3 by desiccation' September 18 2001.
I guess my memory isnt as bad as what I thought it was. :)
Mick June 11th, 2002, 01:29 AM

what aboout nylon and HNO3?
like nylon fuel hose?
maybe its a dumb question, but its easy to get...so it might pay off..
or PVC pipe (or ABS pipe)
i honestly don't have a clue about HNO3, cause i've never made it before(no KN03 :( )

I'm pretty sure that the nitric would eat 'both' of those. Also, i guess it's possible that it would react with the pvc and give
unwanted effects, but I have no chemistry background.

only plastics surviving contact with 68+ % HNO3 is teflone types.
there is something called PVDF (polyvinyledifluoride, similar to PVC, polyvinylechloride) that is partially resistant, but only
shortterm,
Nylon, PVC e t c are all goners.
Stainless steel (316) is resistant to HNO3 at up to ~90% , Al is resistant to 100 %, but it has to be pure Al, not Dural or alloys
with copper, zinc e t c since these metalls causes electrochemical corrosion.
The high oxidation potential of HNO3 increases the passivation process where the surface gets covered with a thin layer of
Al2O3 or Cr2O3(stainless)
But neither cant be used in the reaction vessel , where H2SO4 is present. This causes the metal to corrode very fast.
/rickard
When vacuum distilling, does the material of the hose which concects the vacuum outlet with the vacuum aspirator have to be
HNO3 resistant or do only NOx escape that way?
And can I use the water stream which comes out of the condenser to run the vacuum aspirator or will the pressure be too low
using a Liebich cooler?
mongo blongo June 12th, 2002, 02:31 PM

I have found that Polypropylene resists HNO3 very well. I use polypropylene bottles to store my HNO3.

Seems like PTFE is the only plastic that is 100% nitric acid resistant :( Shame because it's rather expensive for tubing.
Even PP degrades after some time in contact with 100% HNO3.
VX June 19th, 2002, 04:02 PM

Glass tubing is OK though, and can be found at some hobby shops. It's usually soda glass too so it can be softened with heat
and bent into the desired shape. :)

I find the pressure drop (of the vacuum) to be unnaceptable when I use my aspirator for both vacuum and coolent water for a
condenser. Once the water backflowed into my flask :mad: Since I have mine set up for a garden hose connection, you can
get a Y adapter for the hose. You can then get a plastic or metal hose thread to tubing bung adapter for the condenser.
Alternately you can get various pipe thread fittings to do this, the same adapters can be found for the standard faucet (kitchen
type) thread if you wish to use that. Then there are all the connection adapters to go from garden, to pipe, to faucet threads. I
usually spend an hour at a time looking at all the goodies at Home Depot.
[ June 19, 2002, 09:28 PM: Message edited by: megalomania ]
PYRO500 June 20th, 2002, 12:36 AM

I managed to build a water aspirator recirculating station out of a spa turbing pump some pvc and a water aspirator I got from
sigma-aldrich it works fairly well I use PE tubing (for water transport to refridgerators and other low flow jobs it seems at least
NO2 and heat resistant not like vinyl tubing witch I used to use to connect the small tubing to my vacuum adapter and soon
turned to yellow stickey goo. I get around 20 torr with my setup until the water temp rises witch I can prevent by adding a hose
into the tank (10 gallons) and letting the cleanout plug loose to let a little water bleed out but it'sdifficult to get a good
balance of water addition so I normally just let it run at room temp.

Okay, I distilled some nitric today, but the stuff has a funky green color and smokes like hell, even at 10C! <img border="0"
title="" alt="[Eek!]" src="eek.gif" /> What has happened here? It was made by drain opener H2SO4 >95% and NH4NO3.
I managed to connect the vacuum aspirator to the condenser flow and it still pulled a reasonable vacuum, when I accidently
ripped out the tubing I heard a very loud fwwwooooossh and the boiling flask shot off the setup.

think the green colour is caused by HNO2 contamination.

Hmm, could be. Is that a sign it's highly concentrated or the contrary?
Oh, btw, I just found out that my 1l of 70% HNO3 from Fisher scientific is stored in a brown HDPE (High Density
PolyEthylene)bottle.
I recommend everyone who plans on vacuum distilling to buy an aspirator with anti-kickback valve. Then you can simply turn
down the water pressure when you have got the desired vac and no water gets into your setup.
[ July 05, 2002, 05:46 PM: Message edited by: vulture ]
kingspaz July 6th, 2002, 10:39 AM

HNO2 is an impurity and a sign of decomposition.
PYRO500 July 7th, 2002, 05:31 AM

I had green HNO3 once it was one of my first vacuum distilations. it could be that beacuse my vac. was not high enough I had
a small amout of NOx gasses in the flask, it also could have been I heated the acid too strongly. As far as Water aspirators
go keep a long length of tubing between the aspirator and your setup. that will avoid most of the water siphoning problems
that occur when the water pressure is reduced. I happen to have a PE water aspirator that has a kickback valve but when it
wasw hoooked to my water supply the thing would allow water to be sucked into my flask when the water was on regardless of
the fact that it was supposed to stop that. I found that it works ok to stop an abrupt change in pressure but for small changes
such as your well running low on pressure the valve may not firmly seat and will leak waer into your system. I now use a 15
foot length of PE tubing run along the roof of my lab to not only extend the distance from the pump but also it works wonders
at making reverse flow evident ad stoppable before it does damage. I'd recomend a pfte stopcock easily accessable near the
end of the vacuum line to avoid accidents just remember that if you shut of the path of exiting gasses and you are heating a
liquid and creating a much less dense gas that you are going to have the presssure increase untill catastrophe when the
ground glass joints force each other apart possibly damaging your glassware.
Flake2m July 7th, 2002, 10:08 AM

the green colour is an impurity from the distillation process. I think it is N2O3. If you HNO3 starts turning yellow add a small
amount of urea, it will remove the HNO2 from the acid.
vulture July 8th, 2002, 05:40 AM

Well, after a day in cold water (10C) the green color changed to very faint yellow.
shrek August 3rd, 2002, 08:52 PM

Well my synth went a little better... but only to an extent. I made a page explaining what I did at:
<a href="http://www.ogreswamp.net/explosives/nitric1.html" target="_blank">http://www.ogreswamp.net/explosives/

nitric1.html</a>
DBSP August 3rd, 2002, 09:43 PM

Sounds like the anarchist cookboook or some other crap. And I really hate meassuring things that recuire weighting by
volume.
nbk2000 August 4th, 2002, 04:09 AM

Well I'm certainly impressed.
Someone actually tried the BB method and took pictures of it. And it does work, if you're careful (and the gods are smiling on
you :D ) so the bottles don't crack.
Next time, try using teflon tape instead of cloth. Al;so, poke a small hole throgh the tape with a large sewing needle so there's
a pressure relief so the gases don't blow out the tape.
Next, have a continuous flow of cold water running over the collection bottle, rather than occasionally cooling it. The (probable)
reason your bottle cracked was because it got hot from the gases, and when you poured cold water over, it stressed the glass
and broke it.
Finally, you may want to have the acid/nitrate bottle sitting in a slightly largere soup can filled with DRY sand. I can just see
the hot nitric paste splattering on you when the bottle shatters.
kingspaz August 4th, 2002, 10:59 AM

i'm quite surprised it worked! its good when people actually write up their stuff and have pictures and things.
another point to note though, when heating the H2SO4 bottle try and do it very slowly to minimise the risk of a fracture.
trust me i've spilt concentrated 120*C H2SO4 on a burning stove before. made an instant cloud of H2SO4!
shrek August 4th, 2002, 01:06 PM

Thanks for the tips for next time. For teflon the pipe tape should work right? It is not very wide, but I'll just wrap it around a lot
of times. I'll give it another go, hopefully later this week but first I got to go buy some more of that Pina colada concentrate
for the bottles, have a little more time setting up, and wait till the parents aren't home. (They don't mind low explosives and
stuff like ANNM or ANFO, they just hate me synthesizing things.)
shrek
nbk2000 August 4th, 2002, 03:52 PM

Teflon is teflon. As long as it's wrapped tightly and thickly, it'll work fine. I used it for holding together flask and condenser for
refluxing when the clips holding the equipment together litterally dissolved!

when concentrating the nitric, how much sulphuric should one add? also, what temperature for concentrating, and whats the
concentration of the H2SO4 in car battery acid?
[ October 13, 2002, 01:35 AM: Message edited by: Richy ]
vulture October 13th, 2002, 07:05 AM

The amount of sulfuric depends on the amount of water in your HNO3. Calculate the MASS of water that's in it by
measuring density, concentration or pH (quite unreliable unless you got an electronical pH meter). Then calculate how many
moles of water that are.
If you know that 98% H2SO4 binds water like this:
H2SO4.H2O
then you should be able to calculate the stoichiometric amount of H2SO4 needed.
That is, if your H2SO4 is 98%.
The distilling temperature shouldn't exceed 60C. That means vacuum, because nitric boils at 80C at 1 atm.
Car battery acid usually is 37%. It takes quite some time to boil that down. Get drain opener acid.
[ October 13, 2002, 06:07 AM: Message edited by: vulture ]

in addition to vultures post:
the water-binding properties of the sulfuric acid decreases rapidly below 75-80 % so the calculation for how much sulfuric acid
is needed has to take this in account , otherwise some water will also distill off with the nitric acid and dilute it.
/rickard

The nitric acid is bound to sulphuric in a very similar way to water, which is why you need a higher temperature to liberate it.
You can use both acidic hydrogens on sulphuric acid, but this requires a higher temperature. Industrially, when this was done
industrially, it was prefered to leave quite a high percentage of bisulphate as product rather than go all the way to sulphate
becuase the molten bisulphate/sulphate mixture could be poured out of the still.
A tip from somewhere, and I forget where, is to only heat the glass in contact with the liquid, which results in less
decomposition. As an interesting (In my opinion) and apropriate (also in my opinion) sidenote, during the war when germany
only had a weak nitric acid process, in the time before they built a concentrating plant, they reacted the weak nitric acid with
sodium carbonate and evaporated, and then distilled this with conc sulphuric to generate the acid to make explosives.
PhRaZMAkInEtIcS October 26th, 2002, 07:41 AM

Actually my chem books say that the boiling point is 86 C.And i also remember reading in some chemistry book that
Fe(ferrum sp?) also forms an oxyde layer(passivates -don't know if that's the word in english ,sorry)when exposed to
concentrated nitric acid ,but it dissolves in unconcentrated HNO3.
Isn't aluminium supposed to be totaly nitrique acid resistant even at high temperatures(it should form a oxyde layer to protect
it.)
I think some metals are deliberately processed with concentrated HNO3 to increase there corosion resistance.
May someone answer the folowing question becouse i am not so good in chemistry:
I have this equation about producing HNO2:

NO2 +H20=HNO2+HNO3
And this one about producing HNO3
NO2+H2O ->HNO3+NO
........<-
when bubling NO2 throught water which of the above equations would take place?
knowledgehungry October 26th, 2002, 10:40 AM

Correct me if i'm wrong. Pure aluminum is resistant to HNO3 but aluminum often already has a layer of
aluminum oxide on it which reacts with the nitric.
[ October 26, 2002, 09:41 AM: Message edited by: knowledgehungry ]
CyclonitePyro October 27th, 2002, 01:53 AM

I think you got it backwards. My understanding it that the nitric acid will oxidize the aluminum into aluminum oxide, so if the
aluminum already has been oxidized by air, then the nitric acid can't do any further damage.
[ October 27, 2002, 01:54 AM: Message edited by: CyclonitePyro ]
PhRaZMAkInEtIcS October 27th, 2002, 04:48 AM

Boiling metals in HCl,treatating them with atomic hydrogen or when used as a catode.These are some of the metods used for
removing the oxyde layer.Also i think you can scrape it off.But really where are going to get pure aluminium tubing.I think
glass is the cheapest
vulture October 27th, 2002, 01:46 PM

The aluminium needs to be atleast 99.8% pure to resist nitric acid, because other impurities will cause an electrochemical
minicell to form and the corrosion process will continue by itself then.

and also to be resistent the nitric has to be above 90% (guesstimate) concentration. at lower concentration the acid is much
more ionised and will react with the Al.
NoltaiR November 1st, 2002, 01:55 PM

I have tried the IM style on more than one occasion back in the day. I have found that the cracking of glass is not necessarily
because of the instaneous change of temp from the water, but rather it depends on the type of glass used. Try to get a glass
that is fairly heat resistant and not too large. The IM handbook suggests coke bottles which work rather well. Of coarse you
can't make more than 25-50mL at a time because the depression is not much. If you are using larger bottles keep an eye on
the thickness of the bottle, thicker glass will shatter from heat easier (that is why lab glassware is thin). Also do not keep a
continuous flame, you need to regulate it. An easy way to do this is to get one of those thin 'thermometers' made for
aquariums. You can stick it on the inside of the neck of the bottle to be heated. Also I only used a 'pan of fire' (also
suggested by the IMH) in a few labs before abandoning the idea; I decided it was easier to take a oxygen/acetylene torch (for
welding) and turned it on a gentle steady flame--basically I just cut of the oxygen although that meant I had to put up with all
the smoke that un-oxidized acetylene puts off.
I never used cloth (although that is the suggested idea), but rather I made an improvised tape made by taking a lentgth of
duct tape an placing a metal strip (cut from a sheet of aluminum foil) down the center, so that only about 1/4" of duct tape is
in the open on either side of the aluminum strip.
You seem to have yours balanced well enough (from what I can see) but I know that a big problem that I always faced was
that if the lips of each bottle was not perfectly flush, then once the pressure built up the gas always blew (and then the lab is
pretty much ruined unless you fill like trying to retape the bottles while the HNO3 gas is fuming out. Another idea (though I
have never tried this) would be to put wieghts against the foot of each bottle so that there is less chance of the bottles
separating.
As far as puncturing to release the gas, I have never done this but it may make your labs have a much higher chance of being
successful. But I would not suggest just leaving a punctured hole open, rather just cover it up with another small peice of tape
that you can occasionally remove and replace (for maybe a couple seconds) throughout the lab.
And lastly the cooling is a very important part (obviously) especially since the heated chamber is so close to the cooling
chamber. If you are planning on using running water, make sure you have a place for the water to run-off. This may sound
stupid but I can't tell you how many times the water would run collect into a puddle and makes the hole lab quite messy (which
is especially true to the 'real' improvised chemist who is working outside on the ground). But the best way I have found to cool
off the second bottle is to build a wooden (or similar) box that has a hole cut in the side of it just wide enough for the cooling
bottle to set in. The box is partially filled with ice, then the bottle inserted, and then filled the rest of the way with ice. Once
your HNO3 is fuming well inside the bottles, gently pour water into the box to make it cool even quicker.
When the lab is done, separate and close off the bottles as fast as possible (this is just basic lab safety so you don't have any
unnecessary HNO3 fumes floating around). And as far as storage goes, I just like to keep it in the freezer.. that way it didn't
fume when I opened the bottle.
The product always had some impurities (you can see specks floating around near the top and settling on the bottom of the
HNO3). I tried to redistill it in a couple labs but decided it was far to time consuming for my uses (I have only used my
improvised HNO3 for making nitrocellulose in the past, and it worked well enough).
NoltaiR November 4th, 2002, 07:38 PM

You will have to cut and paste the pics on this page.. and sorry about the bad quality, this whole lab was done in a bit of a
hurry.
Well it has been about 5 months since I have done this lab so I decided I would have a go at it today.
Materials (that I used):

*80mL KNO3 (finely powdered)
*40mL 94% drain cleaner H2SO4
*2 Snapple bottles
*2 cloths
*duct tape
*gallon bucket
*vice
*2 100mL graduated cylinders (I know this is supposed to be an improvised lab, but using good measurements is always a
key)
*oxygen/acetylene torch (oxygen turned off)
*ice
*water
Here are my materials

<a href="http://www.geocities.com/noltair/start.jpg" target="_blank">www.geocities.com/noltair/start.jpg</a>
Procedure:
A hole is cut into the gallon bucket for one of the Snapple bottles to fit into. The bottle is inserted and ice is poured around it.
The reason I chose to use Snapple bottles was because of the thinness of the glass (makes it much less likely to crack from
temp change.. the problem is that when using a bottle as large in diameter as this, water and ice isn't really cold enough to do
the job.. this is my first mistake).
The KNO3 and H2SO4 is poured into the other bottle.. fuming will start almost immediately. Mix the two well with a stirring rod
or similar (this is my second mistake.. in my haste to complete this lab before my mom got home I forgot to mix the two..
this doesn't necessarily ruin the lab, but it makes the time required to distill much longer). The second bottle is placed in the
vice.. I would have used a ringstand but my last one was taken from me about 3 months ago during my parents last lab raid.
The two bottles are lined up as close as possible and a cloth is wrapped around the lips of the bottles. Duct tape to follow. The
cloth is best used because extra pressure created in the bottles will be allowed to slowly slip through the cloth, but not enough
to have much of a loss.
Here is the setup:

<a href="http://www.geocities.com/noltair/setup.jpg" target="_blank">www.geocities.com/noltair/setup.jpg</a>
Here is the Snapple bottle in the bucket of ice.

<a href="http://www.geocities.com/noltair/cool.jpg" target="_blank">www.geocities.com/noltair/cool.jpg</a>
The torch is lit and the burning begins.

<a href="http://www.geocities.com/noltair/burn.jpg" target="_blank">www.geocities.com/noltair/burn.jpg</a>
Soon the heating bottle is filled with gas.

<a href="http://www.geocities.com/noltair/gas.jpg" target="_blank">www.geocities.com/noltair/gas.jpg</a>
This went on for about 20 minutes when my mom called and said that she was almost home. I had made only about a few mL
(5mL at most) because I just couldn't keep the cooling bottle cold enough to condense the gas. The bottles were separated
and disposed of. If I would have had more HNO3 I would have saved it, but because 5mL just isn't enough to save I decided
to see if it was possible to pour the HNO3 into another bottle (this is an obvious 'no no' because the liquid was just barely cold
enough to keep from being a gas as it was). As soon as the bottle was turned upside down, the liquid turned into a fumes as
soon as it contacted air, and that was the end of that.
Reasons for error:

*A busen burner or other form of continuous flame should have been used (I used to have bunsen burner that I simply
plugged the hose to the end of the acetylene torch for fuel)... the actylene torch just didn't cut it because I could not hold it
there long enough... especially while the smoke was blowing all around me.
*A smaller bottle (with the same thickness of glass) should have been used and/or a colder form of coolent should have been
used (such as dry ice).
*The two chemicals should have been stirred before heating.
[ November 04, 2002, 06:46 PM: Message edited by: NoltaiR ]
knowledgehungry November 5th, 2002, 07:29 PM

Ammonia nitrate(in water) will work nicely to cool the bottle down.
Speaking of Ammonia nitrate yesterday i decided to be curious and heated a mixture of AN and sulfuric. I heated it in a test
tube with a rubber stopper. Dark orange fumes came out and attacked the rubber was that nitric acid? Thanks.
Anthony November 5th, 2002, 08:24 PM

It was NO2 - Nitrogen Dioxide
kingspaz November 6th, 2002, 07:12 PM

chemistry lesson:
H2SO4 + NH4NO3 ---> HNO3 + NH4HSO4
4HNO3 ---> 4NO2 + 2H2O + O2
NO2 is toxic shit so don't breathe it!
[ November 06, 2002, 06:25 PM: Message edited by: kingspaz ]

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > KNO3 +
HCl
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View Full Version : KNO3 + HCl
Anarchist December 20th, 2002, 08:27 PM

This is a very simple method of synthesizing nitric acid, you should mix them in equal parts, and heat gently. It will start to bubble, this is chlorine gas being released( hold your
breath...). The hard part of this is to seperate the remaining HCl from the HNO3. This I think can be done by boiling off the nitric acid into another container then letting it
recondense(I haven't tried the seperation part yet, I will probably try it sometime today or tomorrow then I'll let you know how it worked).
knowledgehungry December 20th, 2002, 08:58 PM

God Damn you are an idiot. First off new topic as first post!!!! Read the FUCKING rules :mad: . Secondly mixing HCl and KNO3 will not give you HNO3 ( i am pretty sure) xCl
+ HNO3-> xNO3+ HCl so obviously if your reaction works you get HNO3 + KClwhich in turn reacts to give you what you started with. The equilibrium favors the HCl not the
Nitric. Learn how to read the rules and if your lucky they wont block your IP just your nickname.
DUMBASS!!!

...you're wrong..., it does work, i have done it myself. I know that it will start to react back, but it will reach an equillibrium which i think will be about 50/50(though i'm not
sure) which is why you would need to get rid of the excess HCl and KCl and KNO3 to have the pure stuff. If I am in fact wrong then I am very sorry and I will try not to let it
happen again, but from my limited knowledge and experimentation this formula has worked. If you want to see a longer topic where this is discussed look here <a
href="http://www.sciencemadness.org/talk/viewthread.php?tid=308" target="_blank">http://www.sciencemadness.org/talk/viewthread.php?tid=308</a>
btw: the rule about first posts is that you can't ask a question, it does not say that you can't post a new topic.
[ December 20, 2002, 08:14 PM: Message edited by: Anarchist ]
MrSamosa December 20th, 2002, 10:01 PM

Anarchist... you should read the rules more carefully. There are already posts that deal with the synthesis of Nitric Acid, in fact Pyro500 (It was him, right?) has a wonderful PDF
file all about synthesizing Nitric Acid from -NO3 salts. From what I have read, the reaction works much better using Sulfuric Acid instead of Hydrochloric Acid.
Oh well; for me, it is the thought that counts. But that is not the case with angry Nazi forum admins <img border="0" title="" alt="[Wink]" src="wink.gif" /> . I don't expect
for you to see much sympathy when an admin stumbles upon this, if for your name only (Anarchists are not well-liked here).
[ December 20, 2002, 09:03 PM: Message edited by: MrSamosa ]

I know the one with H2SO4 is much easier and better, but for me sulfuric acid is next to impossible to obtain, while HCl is very very easy and cheap. So I thought for anyone
else who had the same problem as I it might be nice to know how to make it an alternate way. I am also sorry if this formula was in pyro500's pdf, I haven't read it yet, but i
will probably read it soon.
btw: about my name, I am not the k3\/\/| kind of anarchist, I don't think we should all go blow up government buildings, I am a real anarchist not some stupid punk
cookbook kiddie. I don't want to blow up any buildings or assasinate any government leaders( though it is fun to plan out how to do the perfect assasination).
Sam December 21st, 2002, 12:06 AM

The only thing that might save you is that your not the average run of the mill kewl. You seem to know a bit. That 'No first posts as new topics' thing seems to be an
'unwritten rule' (I haven't seen it anywhere, but everyone seems to know it). But who knows, the lord...err...mods work in mysterious ways. <img border="0" title=""
alt="[Wink]" src="wink.gif" />
Anarchist December 21st, 2002, 12:22 AM

I'm sorry for uh.. anything and everything i guess. I thought it was only that you couldn't ask questions as the first post. Had I known, I wouldn't have done it.
megalomania December 21st, 2002, 12:29 AM

Well, it's not really against the rules when you provide info. That's why your getting yelled at by members and not the staff :)
nbk2000 December 21st, 2002, 12:34 AM

Using the name "Anarchist" here is tantamont to waving a red flag in front of a pissed off bull. :)
So, given your first post being a new topic, plus the name, it's back to square one for you.
However, since you didn't get all bitchy about it, and you're spelling wasn't retarded, you're not banned. Sign up with a new (less "k3Wl") name, and you can have a second
chance.
And post in existing topics for a while first, eh? :)
End topic.
Angry Nazi Admin...new title? <img border="0" title="" alt="[Wink]" src="wink.gif" />
[ December 20, 2002, 11:35 PM: Message edited by: nbk2000 ]

Improvised Manufacture of Nitric Acid > HNO3 purification via decanting with acetone, and the runaway nitration which ensued
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View Full Version : HNO3 purification via decanting with acetone, and the runaway nitration which
ensued
knowledgehungry Decem ber 22nd, 2002, 04:34 PM

W ell I had the "brilliant" Idea to follow Nbks idea of decanting the m ixture of HNO3 and DC M then allowing the DCM to
evaporate. Except I h a d n o D C M , s o b e i n g t h e d u m bass that I a m i d e c i d e d t o u s e a c e t o n e , i m e a n sulfates are insoluble in
acetone and it evaporates fast. BAD idea, at first i used very small amou nts and the whole thing went off with out a hitch. Then
i decided to try about 150 mls of the stuff. At first the acetone wasn't mixing it was separated by a layer of sulfate so i
d e c a n t e d t h e a c e t o n e a n d a d d e d s o m e more. I stiirred the mixture to try to let the sulfate settle. As i let the mixture sit the
liquid started to bubb le, i figured that it was only Acetone boiling since th e m ixture was relatively warm . It started to b u b b l e
faster and fa ster and i got runaway nitration of acetone i think. Lots of NO2 and foam , I quicly dum p e d m y m i x t u r e d o w n m y
sink with lots of water :rolleyes: . So m y questions are... Can you nitrate acetone And W hy did the first one work and the
second one not.
nbk2000 Decem ber 22nd, 2002, 05:09 PM

Very sm all am ounts don't retain heat. They get hot (and cold) very fast. Whereas, larger am ounts take tim e to hea t up, and
retain that heat longer.
So, when you had the large am ount of acetone, it was getting warm. W hen you stirred it up, it reacted even faster, getting
warmer still. Finally, once it reached a certain point, the heating becam e self sustaining, and then you get a runaway because
the speed of a reaction doubles for every 10C increase in tem perature.
Of course acetone can be nitrated. You can nitrate benzene, toluene, xylene, and other solvents, right? Don't know if it'd be
called nitroacetone (never heard of it), but it m ight be useful som ehow.
Did you have success in the extraction using small amounts of acetone? As far as I know, it has to be a chlorinated solvent to
work.
But hey, m ore power to you for trying. You learn from your failures as well as your successes. :)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > FKT:
HONO2 The inconcievable
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James June 5th, 2002, 09:57 PM

A43tg37 posted on May 13, 2002 at 06:40 PM
<blockquote>quote:<hr /><center>NITRIC ACID
PRODUCTION</center>
U.S. Patents
4,141,715-Method and apparatus for producing nitric acid via an electric arc
4,010,897-Method and apparatus for home production and application of nitrogen fertilizer
4,873,061-Fixation of nitrogen by solar energy
The first two patents are designs (essentially based on the Birkeland-Eyde process) for cheap home or farm based devices that can produce nitric acid via nitrogen oxides, using
only air, water, and 110V electric power as raw materials. The second is of little concern as far as fixation by solar energy, but is more interesting for its mention and description
of the "pebble bed process" which makes use of tungstic oxide catalysts instead of precious metal ones and actually burns air over a superheated medium to create nitric
acid.<hr /></blockquote>If all else fails I suppose Ostwald could be used, but I think it's impractical for less the
90tons/day. Links and stuff will come later.
Ollie Snowie October 23rd, 2003, 10:53 AM

Hmmmm...
Lightbulb filaments are tungsten... They get quite hot...
You guessed it! You'd carefully smash the glass aroung two lightbulbs, and wire them in series to stop the filament getting too hot and corroding all the way through. Then
you'd mount them so the filaments are as close together as they can get without touching, and suck air past them. I'm gonna try this.
PS - Funny that I used the lightbulb icon, considering what the post is about :D
[EDIT -
I have just tried this, and (not surprisingly) it proved very difficult to regulate the current so as not to burn the filament.
Still, a tungsten mesh could also be heated to a high temperature by a very high current flowing from a rod in the center to a ring round the outside. This way a very high
temperature would be created at the center or the disk, while the edges of the disk would be at a much lower temperature. Air could be pumped in from the sides of the
apparatus and sucked out through an array of small water cooled pipes at the center. The air would be heated gradually to a very high temperature and then suddenly cooled,
forming nitrogen oxides.]

Thats a good idea, its a shame it cant work. Regulating the temperature of the filiments isnt the problem, the problem is that at the temperatures you need to make nitric
oxide, tungston burns in air. Unfortunatly theres no way round this as you cant avoid having oxygen in the gas mix. Coating (plating) the filiment with platinum might possibly
help but I doubt it would work well enough to be useful.
Ollie Snowie October 26th, 2003, 03:38 PM

Platinum wire is used as resistance wire in high temperature furnaces (apparently) so that's another thing to look out for at the scrap yard :) .
Another thing I found strange while studying the patent was the mention of ammonia production when water vapour, nitrogen, and a suitable calalyst come together at a high
temperature in the presence of light.
Another thing I'm wondering is how the filaments in halogen bulbs can stand the hot halogen and not corrode. Just from a quick glance the filaments in halogen bulbs look
thicker than those in mains light bulbs. I suppose another explaination for this is that they take a lower voltage so they need to be thicker/shorter to allow enough current
through.
I never thought that platinum was a suitable catalyst for the burning of nitrogen in oxygen, but I know that is is very good at oxidising ammonia. Will someone please clarify
this.
In the patent is says that titanium dioxide will calalyse the reaction of water with nitrogen at a high temperature to make ammonia and, I suppose, oxygen. This mixture could
be passed over a heated platinum catalyst so some of the ammonia would be oxidised (eventually and finally) to nitric acid, and this would neutralise the left over ammonia. I
have the feeling that the excess ammonia would just be decomposed into nitrogen and hydrogen by the high temperature. Will someone please clarify this as well.
Ammonia is also needed for some preps as well as nitric acid, but you can make a great deal more variety of explosives with nitric acid than ammonia, and this was a thread
about nitric acid, after all.
[EDIT - I'm also thinking along the lines of:

(arc welder=power supply)+(tungsten welding rod hammered flat=resistance wire+catalyst)-->setup for making nitric acid.
As well as:
Tungsten screen is placed in front of magnetron from microwave oven for intense heating.
And:
This is getting too similar to another thread involving microwave heated catalysts and air.]
Tuatara October 27th, 2003, 04:58 PM

Not strictly on topic but ...
The halide in tungsten halide lamps is iodine. The filament is usually run hotter than in a standard lamp, so the evapouration rate of the W is higher. The W combines with the
iodine to form tungsten iodide. Tungsten iodide will decompose when heated, into W metal and iodine again. So the iodine acts to sweep up any W vapour, then redeposits the
W back on the filament, mostly at the hottest point (the thinnest point), thus extending the life of the filament. Neat trick, eh?
Chemical_burn October 27th, 2003, 08:43 PM

Very intresting indeed. I believe the toungesten filaments in florsent(sp?) lights it very tought as I have broken these lights before and removed the filiment to use in electric
ignitors and they are very thick and heavy for a filiment. There are two filiments in one light one on each end in the contacts of the bult.
just though I would see if it helped any.

Improvised Manufacture of Nitric Acid > Syntheses of 100% Nitric Acid HNO3
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Here is a gift for your search engine, from a discussion at another bullitin board I love to frequent. I present to you the
greatest gift anyone can give: information. :p
I'm simply going to copy the thread here for the full discussion, as m ore inform ation cam e out in later posts than was
originally pre sented in the first post by the author.
Author:
Preparation of 100% nitric acid

J. Org. Chem . 25, 469-470 (1960)
(a) Nitric acid (6.79 g.; 0.108 m ole as 52.72 g. of a 12.88% solution) was carefully neutralized, with cooling, by addition of
4.32 g. (0.108 m o l e ) o f s o d i u m hydroxide dissolved in the minim u m a m ount of water. The water was remo ved by d istillation
and the dry salt was treated with conce ntrated sulfuric acid (18 m l, 0.32 mole).
Distillation at atmospheric pressure in the abse nce of sunlight gave 5.6g (0.089 mole) of 100% nitric acid, bp 80-83C (82%
recovery).
( b ) P o t a s s i u m nitrate (14.2 g.; 0.07 m o l e ) a n d 31.1 m l. (0.56 m ole) of concentrated sulfuric acid gave, upon distillation, 7.1
g. of 100% bp 78-82C (81% recovery).
User A:
I've tried both KNO3/H2SO 4 and HNO3 /H2SO 4 distillations at ordinary pressure and never got 100 % HNO3. The density was
between 1,49 and 1,505. This indicates about 95% (dissolved NO2 not included in this calculation). I know of one literature
reference where they claim ed that distillation under reduced pressure below 0 degree centigrade is necessary to obtain almost
pure acid.
Of course, 95% is better than com m ercially available 65-70% ...
Author:
Strange, in this article they are even working with nitric acid with a isotopically m a r k e d n i t r o g e n a t o m , so on e would think tha t
they were extra careful when doing it. Perhaps it has som ething to do with the sm all batch size?
User A:
I've done the preparation on a liter-scale with much longer heating than on a sm all scale. My distillate was always yellow
colored due to NO 2 form ation.
Moderator A:
The regularly available azeotropic HNO 3 can be concentrated by distilling it from the same volum e of H2SO4, preferably under
a slight vacuum . I've done this big sca le with 6L RB flasks and it worked great.
User B:
In m y y o u n g e r d a y e s ( e x p l o s i v e s y e a h h ) I d i d l i k e o s m ium but two tim es (mix salpeter acid with sulfuric and destilate, then
m ix the prod uct with sulfuric and destilate againAdding a nitric salt (KNO 3, NaNO3) to salpeter resu lt in a big chunc off
nonsoluble sodium or potasium sulphate.
User C:
" T o 2 5 m l of (cooled) concentrated sulfuric acid in a distillation flask add 30 g of previously dried potassium nitrate and a little
bit of silver nitrate (swirling). Close with stopper and let sit for 1 hour (to com plete conversion). Then distil carefully (I guess it
m eans "slowly" here). The brown-yellow forerun is discarded, only the fraction in the distilling range from 83 to 85 C is
collected. The distillation is finished when red fum es begin to form in the condenser."
T h e y a l s o r e c o m m e n d v a c u u m distillation for the production of larger am ounts of nitric acid in combination with full glass
apparatus with ground glass joints. The joints are lubricated with sulfuric or phosphoric acid.
Boiling point of 100 % nitric acid: 83 C (atm ospheric pressure), 36-38 C (26 m bar)
[Translated from :
"Jan der-Blasius: Lehrbuch der analytischen und praeparativen anorganischen C hemie", 12. ed., 1985, S. Hirzel Verlag,
Stuttgart]
User D:
The joints are lubricated with concentrated sulfuric acid? I understand why... but dam n, I n ever realized how nasty and
dangerous that acid would be to distill.
End Thread.
It is still debatable whether the claims in the article are truthful, but regardless, it good to have m ore evide n c e o f N O T n e e d i n g
N2O5 to produce anhydrous 100% HNO3. I hate oxyacid anhydrides.
Prim oPyro
BleedingLips August 6th, 2002, 06:12 AM

C o m e back Primo! :) You can't be at two places at once.. can you?
[edit: m eaning clarified]
<sm all>[ August 06, 2002, 06:47 AM: Message edited by: BleedingLips ]

???
I'm sorry, I'm not trying to be dense o r anything, but I have to adm it I don't understand your reply. W hat do you m e a n ?
xoo1246 August 6th, 2002, 06:56 AM

Let m e try to translate, I assu me he likes you and wants you to stay at this forum . I have seen yo ur recent posts and you
s e e m to be a bright fellow with experience and com p e t e n c e .
DBSP August 6th, 2002, 07:03 AM

The first reaction is simply a distilllations from NaNO 3.
HNO 3 + NaOH--> NaNO3 + H2O, remove water and you have anhydrus NaNO 3.
Add H2SO4 and you get the HNO3.
So it is "really" not something new but still.

No, it was never m eant to be new at all. Every other thread in this room has HNO 3 in the title. Wha t is good about this is tha t it
is ra w data for the search engine. It is better than ANO THER que stion, is it not? I would lik e t o a s s u m e s o .
W hat struck m e as interesting is the lack of nitrogen ox ides formed, as is usual by dehydration m ethods with H2SO4. I
t h o u g h t t h a t p e r h a p s t h i s n e e d e d m entioning is all. Pure HNO3 devoid of nitrogen oxides (adding untasteful color a n d
precipitates to the liquid) is a highly prized item , and rightly so.
Prim oPyro

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Little
problem during distillation
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I don't know if someone got this problem before but I guess 'cause it bugs myself each time I distill my HNO3 !
So, whatever the method I choose (nitrate+sulfuric or low concentrated HNO3+sulfuric), before the end of the distillation, there are always lot of red fumes in my boiling flask
and no more HNO3 comes into the receiver flask ! In other words, I maybe loose 100 or 200 more mL of HNO3 !!! and I cannot accept that !
I think a vacuum pump could solve the "problem" but it's a bit expensive and I have another project...
what could I do ? heat the flask harder ? it's a bad idea...
see ya !
[ December 24, 2002, 11:47 AM: Message edited by: stanfield ]

Less heat, more patience.
vulture December 24th, 2002, 03:04 PM

Vacuum aspirator, just uses alot of water but works well.
Very cheap also.

"Less heat, more patience", hehehehe... The other problem is I have a 5L boiling flask ! so, at the end of the reaction, I already heated 6 or 7 hours the boiling flask, I'm not
gonna wait for another 5 hours to complete !
yeah, the only solution is a vacuum. As you said, vacuum aspirator uses lot of water and "electric" pump is expensive... that's not easy !
But I'm lucky, I wanna bought the 10L boiling flask ! imagine : 10 or 12 hours for a complete distillation !
thanx !
ALENGOSVIG1 December 24th, 2002, 06:20 PM

If youre distilling a small amount (1/3 full flask) in a 5 or 10L flask, then theres gonna be lots of refluxing on the walls of the flask. Unless your using a nice heating mantle or
you fully immerse the flask ofcourse. Mabe this is why your distillations are taking so long. Perhaps you should use some insulation around the flask etc if thats the problem.
Oh, and why dont you just use a refrigerator compressor for vacuum? You could get one for free most likely.

refrigerator compressor for vacuum ?
this is for "freezer", right ? if no, what's it ?

where could it be found ? because I think this is going to be hard to find this one...
thanx !
EDIT : but, you're right, most of the time, I don't fill the boiling flask until the bottom (correct english?), so, there is a "reflux" effect...
[ December 24, 2002, 06:27 PM: Message edited by: stanfield ]

stanfield, just go down to the dump and rip one off the back of a refrigerator with a crow bar or somthing. or even if there is some waste land people use to dump stuff on
there will be one lying round there to exploit.
photonic December 24th, 2002, 11:28 PM

I recently tried to use a refrigerator pump to pump water and it shorted. Is there anyway to prevent this from happening? Also, how do you keep the fumes out of the pump? I
remember something about dropping the line into water but this seems like it would suck water into my vacuum pump and short it again.
Thanks.
nbk2000 December 25th, 2002, 12:43 AM

You're not going to be using a fridge compressor for pumping water.
A refrigerator COMPRESSOR isn't intended to pump fluids like water. It's purpose is to take freon GAS, and COMPRESS it till it liquifies. Freon is non-conductive, unlike water.
[ December 24, 2002, 11:44 PM: Message edited by: nbk2000 ]
megalomania December 25th, 2002, 04:27 AM

I think there is probably plenty of information about using a fridge compresser over at The Hive if I am not mistaken. Perhaps Rhodium's site as well.
rikkitikkitavi December 25th, 2002, 05:45 AM

if you use a frige/freezer compressor as a vacuum pump it will pump HNO3 vapour and it is definiately not made for such a corrosive media.
Problem is that any HNO3 will condense at the pressure side and the compression heats the gas being compressed , giving a very warm high-conc HNO3.
Before the pump you need a cold trap (LN2 filled) to fully condense any HNO3 or a stack of free compressors to replace the ones that gets corroded away.
but since they most likely are free from the junkyard it can be worth a try..easiy to replace and a lot safer handling than LN2. experience will show how long they last.
I have a slight memory of this being covered in old topics?

/rickard
[ December 25, 2002, 04:54 AM: Message edited by: rikkitikkitavi ]
BrAiNFeVeR December 25th, 2002, 07:09 AM
Not only is it made to pump a non-corrosive gas, it also relies on the cold gas to cool the copper windings in it's engine !!
So it won't last long anyway if you'd just pump normal air with it.
How can you maximise the useful life of this compressor:

-filter out the corrosive gasses (bubble it up through water)
-cool the air it sucks up in some way (use ice water in the above step ?)
-make sure there is no water coming into the pump (lead the vapor over some dessicant)
Basicly the only things that can enter ANY compressor is oil vapor (final oil bath ?) and dry cool air.
lucifer December 25th, 2002, 08:24 AM

I also did use a freezer compressor but after it sucked up some water from the wash bottle it got shorted.
A freezer compressor also isn't designed to continue to run for hours and it did get very hot.
Now I use a vacuum aspirator connected to a pump and a big can of water, where the water is recycled.
This way I don't use any water (except for filling the can once) and water is quite expensive.
The drawback is, I can only create vacuum to 200mBar (or look for a pump with a higher pressure). But it works fine enough for me.
[ December 25, 2002, 09:08 AM: Message edited by: nbk2000 ]
nbk2000 December 25th, 2002, 10:12 AM

Since the compressor is being used to create a vacuum, you need to keep the nitric vapor from getting in it.
The easiest way to do this would be a scrubber tower. First the nitric fumes (after passing through the condenser into the receiving flask) are bubbled through water to get it
wet.
These wet fumes are then passed over hydroxide pellets. This absorbs the water, and reacts with the nitric to form a solution of nitrate in water. This remains in the tower. As
the gases continue up the tower, they are dried by the unreacted hydroxide, till finally the (now) dry and non-corrosive air gets exhausted.
rikkitikkitavi December 25th, 2002, 07:51 PM

stanfield, have you tried to insulate the flask? I had similar troubles, but I couldnt get any HNO3 at all until I heated so hard that I had severe decomposition. Insulation took
down heat loss and more came over at lower temperature.
the major problem with a compressor is that pressure can get very low, so low that the condensation point of HNO3 gets below what you can cool, which of course depends on
your water temperature.
the lower the temperature difference between boiling point-cooling water the slower you must perform your distillation so that the condenser has enough capacity to fully
condense all HNO3.
Thus you need some sort of pressure reglutation( a small bleeder for air into the system) . I m not sure , but I would guess that the boiling point of HNO3 is so low at 0,2 atm
that it can be distilled witout much decomposition.
If you have a scrubber system, it will not wash out much HNO3 at low pressures, since the efficency of these suffers greatly from reduced pressure. It will probably have to be
very tall too, increasing contacting surface to compensate for less molecules in the gas phase at low pressures.
Using a chemical absorbent like sodium hydroxide is much more efficient under this conditions.
Remember that water also has a vapour pressure, it will slowly evaporate too!
At proffesional labs cold traps filled with LN2 (for components < boiling point 100C ) or dry ice is the only option to protect the very expensive vacuum pumps. I have never
seen any other method used in vacuum distillation.

don't worry, when I will buy and use my vacuum, I will put an "erlenmeyer trap" with saturated solution of sodium carbonate to avoid injuries in the pump...
They are "all teflon" type vacuum... but a bit expensive :)
ALENGOSVIG1 December 27th, 2002, 04:01 PM

I wouldnt use an erlenmeyer flask. Most cant take high vacuum. Some can, but most wont. Be sure to house the flask in a wooden box or something for protection incase it
implodes.

they are special erlenmeyer flask designed especially for vacuum ! :)
I will buy one when ready...

Vacuum distilling with a aspirator and a jetpump/reservoir setup works very well for me, but keep in mind that the water needs to be cold to get the highest vacuum. Also the
vacuum hose should be as short as can be. I always throw a bag with icecubes into the reservoir to keep it very cold.
In order to prevent the breakdown of the nitric acid I collect the nitric acid into a flask wich is supercooled with a mixture of dry-ice and rubbing alcohol. The nitic acid will freeze
into the collecting flask. Nitric acid contracts on freezing, there is no danger of breaking the flask. Store the nitric acid in the freezer and in the dark.(still wondering if the light in
the freezer goes off when I close the door. :D <img border="0" title="" alt="[Wink]" src="wink.gif" /> )
stanfield January 13th, 2003, 03:13 PM

ok thanx for the tips !
Furthermore, I have won 500 in some hazard games, wonderful, no ? so, shortly, I will buy a vacuum... I just need to choose one because it's not an easy task (lot of
models!)
bye!

Ooh, I just threw away my latest issue of American Laboratory which had an article about picking a vacuum pump for the lab.
nbk2000 January 14th, 2003, 01:36 AM

I saw at least three vacuum pumps small enough to to fit in a small duffel bag while I was visiting a friend (non-pyro related) at the hospital today. Not bolted down or
anything, just sitting there.
The one I hefted weighed about 15-20 pounds and had a gauge and everything. :) Didn't snag any, but it'd have been easy if that's what I wanted to do.
Eliteforum January 14th, 2003, 06:26 AM

What's this nbk? You? Friends? I smell a RTPB violation here!
nbk2000 January 14th, 2003, 07:04 AM

Stuff it up your ass 'cause I'm not interested in hearing your shit.
Flake2m January 15th, 2003, 01:55 AM

@ Eliteforum:
Their is no RTBP that says you can't have friends. I also know that when you are hospital and you feel like shit because of the drugs they put you on. That their is nothing
more comforting (other then being told you can leave :) ) then friends/family coming around to visit you. So Eliteforum go to HED hell if you you are going to piss of the velox
Mortifer.
I think their might be a way to create a vacuum without needing a vacuum pump. I dont know if this would work though:
You will need 2 flasks and a heat source aswell as some tubing a valve.
In flask 1 you have your nitrate/H2SO4 or HNO3 + H2SO4 mix.

Flask 2 contains some water for the gases to disolve into.
Flask 1 is conected to flask 2 with tubing. Flask 2 also contains a valve that is connected to the tubing, flask 2 and the outside air.
You heat up flask 2 with valve open to the outside air. The idea is that you are trying to create a lower pressure in the flask. Once you have lowered the pressure enough, the
valve is closed and flask to is cooled. Flask 1 now has the gasses in it. You then open the valve to flask 1 and because of the difference in air pressure, the gasses should go
into flask 2.
BASF January 15th, 2003, 02:27 PM

Stanfield
"So, whatever the method I choose (nitrate+sulfuric or low concentrated HNO3+sulfuric), before the end of the distillation, there are always lot of red fumes in my boiling flask
and no more HNO3 comes into the receiver flask !"
Preparative chemistry books describing absolute HNO3-distillation call this "vorlauf"/"nachlauf"(german; dont know the damn word..).
It means, the batch generally tends to develop nitrous oxides both at the beginning and towards the end of distillation, the procedures recommend to drop these
fractions(nitrous oxides will often cause your nitrations to yield sensitive by-products).
nbk2000 January 15th, 2003, 04:27 PM

It's just good lab technique to discard the forerun and to NOT finish the distillation to completion.
Also, there is no RTPB against friends...just one saying you can't trust them. <img border="0" title="" alt="[Wink]" src="wink.gif" /> Hence none of them know about my
time in the clink, or my "hobbies". :)

Question: In order to distill my own nitric acid, I was planning to use sulphric acid(>98%) and NaNO3(fertilizer grade a.k.a chilisalpeter) of which I happend to have a 50kg
bag. De reading on the bag is as follows CHILISALPETER N total 16%
Na2O total 35%
and then some kind of additive Boruim (B) 0.2%
Iam wondering, does this additive have any effect on the distillation or the purity of the nitric acid.
I think the Borium is ment to prevent sucking up moisture from the air, the stuf does come in little prills.Or is it better to use KNO3 anyway. phew!!!! 50 kg, thats a lot of
distilling and a shipload of nitric acid!!!!!
thanks
stanfield January 27th, 2003, 10:06 AM

no, I don't think it'll fuck up your distillation
Like you my NaNO3 isn't pure and it works damn well dor distillation.
mongo blongo January 27th, 2003, 11:00 AM

Well if it's only 0.2% then you have good NaNO3 and should not have anything to worry about. 50 kg!.. you lucky bastard!! :)

Catalyst
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10fingers November 11th, 2000, 01:48 AM

*
[This message has been edited by 10fingers (edited July 19, 2001).]
Bitter November 11th, 2000, 06:36 AM

It's an equilibrium reaction, so you will have to control the temperature very carefully of you won't get any product. Look in chemistry books.
------------------
'Guns will make us greedy. Butter will only make us fat.'
Anthony November 11th, 2000, 09:16 AM

Don't you also need high pressures? I think this is the same process as one I learned about in school, can't remeber the name, but it was German.
Jhonbus November 11th, 2000, 10:30 AM

that'll be the haber process for making ammonia.
------------------
A physicist can make a bigger explosion than a chemist ever did
http://ww w.geocities.com/jhon_bus/

We have gone over this before..but since we don't have the archives up yet, I shall elaborate since I was just thinking about this yesterday. I will be performing this very
experiment (again) in the near future. I moved recently and "misplaced" all my notes http://theforum.virtualave.net/ubb/frown.gif
First of all I found out you can use copper as a catalyst, no need to go all the trouble of getting platinum. Copper sponge and wire is readily available. Second, in my
experiments I didn't use concentrated ammonium hydroxide, I just used the grocery store stuff, so it didn't w ork. I have the information to make concentrated ammonia on my
website. All you need to do is heat a spiral of copper wire to red heat in a blowtorch flame (about 5 seconds of heating) and immerse it in the neck of a flask of boiling
ammonium hydroxide. Heating the hydroxide will cause ammonia gas to vaporize, react with the wire, and the heat of the reaction keeps it red hot. The product immediatly
reacts with air to for nitrogen dioxide, which w hen bubbled into water makes nitric acid. Now, there are some technicial concerns here, like how to keep a constant air flow with
enough oxygen, but I need my notes for that.
Everything needed is available in the stores, no exotic temps or pressures, and it works w hen done right. The cost of your acid is directly related to the cost of your ammonia.
------------------
For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Explosives and Stuff at http://surf.to/megalomania
10fingers November 11th, 2000, 05:02 PM

*
PYRO500 November 11th, 2000, 05:23 PM

the way it is is that the copper is a catalist, and only needs to get hot for a short time, so just get a 12 volt car battery, and run the current through the wire til it gets hot (not
very long) the copper wont for copper oxide beacuse the whole point of it is just a catalist, not anything else, meaning: it influences a chemical reaction on a substance without
canging its own substance
10fingers November 11th, 2000, 10:12 PM

*
PYRO500 November 11th, 2000, 10:35 PM

yes, but you see that the gas in the flask in not oxyagen, it is ammonia coming from the ammonium hydroxide
10fingers November 12th, 2000, 12:11 AM

*
Jhonbus November 12th, 2000, 11:32 AM

We did this in school once for a laugh (pretty yellow flames!) Instead of boiling the ammonia, w e bubbled pure oxygen into it, both supplying the oxygen and spraying the
vapour up. We used a platinum w ire also, we didn't know copper would w ork!
------------------
A physicist can make a bigger explosion than a chemist ever did
http://ww w.geocities.com/jhon_bus/
nbk2000 November 12th, 2000, 12:47 PM

It's fairly easy to make anhydrous ammonia. Just boil ammonia solution, pass the vapors through a condenser cooled with ice to remove most of the w ater, and pass the
remaining fumes through (I believe) calcium chloride to remove all the remaining water vapor.
You can then liquify the pure ammonia gas by passing it into a flask cooled with a dry ice/acetone slush. The ammonia boils at (I believe) -40F.
Once you have your pure gas you could pass it through a steel pipe, the inlet tube for the ammonia gas extending into the pipe past air inlet holes drilled in the steel pipe. The
copper catalyst is heated and tossed into the pipe immediately before connecting the tube that leads into the water.
The error most people make is trying to pump the gas into the water. BBZZZZ! Wrong. Rather, you SUCK it through the water by using a vacuum source (like a draining jug).
This draws the ammonia past the catalyst while draw ing in plenty of air and pulling it into the water to form the nitric acid.
Mega, any idea the maximum concentration you can obtain using this process? Or will this form a dilute solution that will have to be distilled to concentrate?
------------------
Go here (http://members.nbci.com/angelo_444/here.html) to download the NBK2000 website PDF.
megalomania December 30th, 2000, 01:12 PM

This process can easily yield up to about 120% nitric acid! The nitrogen dioxide reacts directly with water forming nitric acid. When all of the water is used up (100% acid) you
get free nitrogen dioxide dissolved in the nitric acid, which can go up to 20%, or 120% acid. This is fuming nitric acid, it can be used for many explosive nitrations, or diluted
down to the required strength. No further distillations needed.
------------------
Cricket December 30th, 2000, 02:06 PM

COOL! Now it seems more interesting, much more. Who w ould of thought?
Nitro December 31st, 2000, 07:09 AM

NBK the best ammonia source is NH4CL and CaO
this will form anhydrous NH3 gas.
Alternatively for CaO can used NaOH powder.
SofaKing December 31st, 2000, 02:41 PM

You can make Ammonium Chloride from ammonia hyroxide and HCl right ?

Before I stick this in the archive...
I have consulted the modern tomes of chemical engineering to devise a more perfect method of nitric acid creation. I have devised a new system and w ill hopefully soon build
and experimental setup.
I have opted to start by directly boiling store bought ammonia, returning water by cooling in a refluxer, and then drying in calcium oxide (lime). You cannot use calcium chloride,
I checked. This method is cheaper, as it does not require hydrochloric acid and sodium hydroxide ($). Furthermore, large quantities of ammonia (generated from ammonium
chloride) may be too much for the machine, any excess unreacted ammonia will neutralize the nitric acid, thus lowering yield.
The dry ammonia gas is then passed through a copper pipe stuffed w ith copper sponge. The pipe is cut into several foot long sections and connected such as to make a "U" type
of pattern. There will be no single long pipe this w ay, it will be easier to heat in this collapsed pattern. The pipe is then set into a bed of hot coals, like a little hibache grill, to get
it nice and hot. The exit gas then goes into w ater.
There is more to this, and it is easier to see than describe. Then there are the problems, hence the need for experiment. First of all, I do not know w hat temperature this needs
to be, or if the coals are going to be too much/little. My info says industry uses 750°C temps and the gas contacts the platinum sponge for 1x10 -4 sec. That
temp w ill melt oridinary solder connections on the pipe, so I may not be able to use more than a foot or 2 of pipe (no U shape). Perhaps the extra length of pipe w ill make up
for lower temps, perhaps it will heat up from the rxn, perhaps it w ill be too much and cause unw anted side reactions... Second, are the problems of oxidation and moisture. If
this does not get dry enough, you will create nitric acid inside your pipe! The copper w ill not last long that way. I have every reason to believe that a little copper oxide may
actually be a better catalyst than pure copper, but I do not know how much.
So, then, anybody have some thoughts on the topic? As an aside, this same system can be used to make formaldehyde from methyl alcohol (formaldehyde--
>hexamethylenetetramine-->RDX or HMTD). There may even be more chems that this can make, I am checking.
------------------
10fingers March 10th, 2001, 10:11 PM

deleting post.
[This message has been edited by 10fingers (edited March 19, 2001).]
[This message has been edited by 10fingers (edited March 19, 2001).]
c0deblue March 11th, 2001, 01:43 AM

The idea of a "universal" catalyzing reactor is exciting indeed!
Is there any reason the pipe itself must be made of copper? Annealed 316 stainless tubing in the desired diameter would be pretty much impervious and could easily be formed
to a U shape using an ordinary conduit bender. This could be packed with the copper sponge, which could be replenished at any time as necessary. Custom SS inlet fittings could
be tig welded in for a really professional apparatus.
Initial heating of the copper could probably be accomplished in-situ using a hydrogen/oxygen flame (in a separate chamber) with the U-tube connected as a "remote" flue. This
would prevent premature contamination of the catalyst w hile a balanced gas mixture would minimize oxide formation. A tandem valve would simultaneously shut off the gas
supply and admit the ammonia solution, after which the reaction would be self-sustaining.
A good source of ammonia might be the "developer" used in diazo (otherwise known as Ozalid or blueline) copiers. This is nasty stuff - 24-28 Baume is typical - but only
requires low heat to produce a steady release of pure ammonia gas (the system used in high speed blueline machines). Price today should be $8-$10 per gallon, maybe less.
Automotive catalytic converters for model years prior to 1982 were single-stage and used only the platinum/rhodium honeycomb. One of these (if obtainable) might be usable
as-is, since the convertor shell itself is stainless steel - only the protective shield is carbon steel. Bears investigation.
Do keep us posted on your progress Mega. Proceed with due scientific diligence, but hurry up for cripes sake! http://theforum.virtualave.net/ubb/smilies/smile.gif
HMTD Factory March 11th, 2001, 03:25 AM

Some input here...I just went through the Ostwald process in an chemical industry book,
the process seem to require a lot of control...It might not be as simple as some of you w ant it to be. Probably w ill need more sophisticated plan to realize.
For example, temperature :
Oxidation of NH3 is exothermic but to make the environment favor the production of NO
will need low temperature as possible. Temperature being too low will not activate the catalyst; temperature being too high will destroy NO just produced.
There's also an optimum mixture of air and ammonia ( 10~20 : 1 ). Flow rate of gas must be controlled too.
I can type the whole section regarding industrial Ostwald process if you want to read it but it has to be on monday, I am occupied on sunday.
c0deblue March 11th, 2001, 02:57 PM

Found this, but it seems to only be the contents section of a comprehensive treatment of the Ostwald process. If anyone can suss out the URL for the rest of this paper . . .
http://ww w.chemsystems.com/search/docs/toc/97s12toc.pdf
[edit]
Oops . . . this paper may in fact have some decent information (if it can be found), but I was rushing out when I came across it and it sure isn't what I thought it w as. Sorry
http://theforum.virtualave.net/ubb/smilies/frown.gif
Lesson: "Always make sure brain is engaged before posting."
[This message has been edited by c0deblue (edited March 11, 2001).]

There is no reason the pipe has to be copper, it just seemed the logical choice, it being a catalyst too. A threaded steel pipe might be better still, it may not need to be welded
at all. This isn't a pressure reaction or anything, nor is there a hazard of flammible gas getting out, so just thread may be enough. The reason I suggest using small lengths is
ease of adding and removing the catalyst. Also the U is not actually a U but accordian shaped, like on the back of you refrigerator. The total distance of pipe may be 5 feet or
more, all w rapped in a small space. I suppose with the threaded steel I could add and remove sections as needed. Wrapped like this it w ould be nearly impossible to add or
remove the catalyst unless it is able to be dissassembled.
If temperature control becaomes a problem, there should be ways around that. The only reason I suggest using coals is ease for me right now. I hope to use gas in time, it is
cheaper than charcoal. The use of a gas burner for me is a larger initial investment for what I have in mind. A type of burner used in gas grills spreads the flame out over a wide
area, perfect for a bent length of pipe. The pipe can be raised and low ered to get a good temp. Also a copper pipe could be wound around a steel tube. A torch could fire inside
the tube causing heating of the copper. I can get a pyrometer to check either way. If my experiments w ork, I may be able to provide the results in a manner wheras you w ill
not require thermometer devices. Air flow can easily be controlled with an aspirator (I hope so).
I think I have a catalytic converter somew here. Of course I design my experiments to use materials available to the least common denominator (meaning what I can buy in the
store everyone can).
Oh, that pdf article is a big tease. That company wants $35,000 to be able to access it http://theforum.virtualave.net/ubb/smilies/frown.gif Unless a username could be hacked.
------------------
10fingers March 12th, 2001, 01:42 AM

*
nbk2000 March 12th, 2001, 11:49 AM

An all copper tube might work, but the reaction produces enough heat to melt copper so you may even have to cool it to keep it from melting. Steel tubing with copper mesh
(chore boy pads) inside w ould probably work just fine. The copper w ould have to be heated first to get the reaction started though so a propane torch heats the copper and
then the ammonia flow started.
If excess ammonia gets into the acid, ammonium nitrate is formed so it w ouldn't be a total loss.
Anhydrous ammonia is available in rural areas as a soil fertilzer for pennies a pound (in ton quantities http://theforum.virtualave.net/ubb/smilies/smile.gif) Wonder how much
copper that would need? http://theforum.virtualave.net/ubb/smilies/wink.gif
What if a U of steel pipe was made, and enough copper added that, when melted, w ould completely fill the bottom of the U so that the ammonia gas w ould have to pass
through molten copper to get to the other side of the U. Wouldn't the brief moment of passage be enough to catalyze the change with the reaction keeping the copper molten?
The lack of strong nitric is what's preventing a lot of peoples progress from weak explosives like AP to REAL explosives like RDX, NG, NC, and the rest of the high explosives.
With nitric, it's almost as easy as flushing the toilet to make high explosives. Without it, you're forced to improvise w eak substitutes like HTH+naptha+Al dust.
------------------
Go here (http://members.nbci.com/angelo_444/dload.html) to download the NBK2000 website PDF.

I just found a useful bit of data that may or may not be a bad thing, depending on how you look at it.
Hot copper oxide actually reduces ammonia to nitrogen gas, but it doing so it returns the oxide back to copper metal.
2NH3 + 3CuO --> N 2 + 3Cu + 3H2O
Any copper oxide that forms during the making of NO will be converted back to the metal. I doubt that the loss of ammonia to nitrogen will be that great unless you start w ith
oxidized copper. The presence of moisture, and thus copper nitrate formation, may be a way to judge the extensiveness of this rxn. This assumes you start with anhydrous
ammonia going in.
------------------

I have some bad new s now. I just happened to be browsing one of my chemistry books when I happened onto a section on reaction rates and catalysts. They had a picture of
an experiment using a coil of copper wire to burn ammonia in air. It said the principal products of using a copper catalyst will be nitrogen and hydrogen gas, very little NO w ill be
produced, and that's w hy they use platinum, which does not break down ammonia. Well that is not the kind of news I w anted to hear. I am now inclined to believe using copper
will waste so much ammonia that it could be a very expensive to make nitric acid in the end.
Now where did I put my catalytic converter...
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10fingers October 8th, 2001, 06:26 PM

*
[This message has been edited by 10fingers (edited October 26, 2001).]

an alternative method for ammonia generation kills two birds with one stone. mix NaOH with AN and add a little water (few drops). this produces ammonia gas which is fairly
dry due to only a drop of w ater being needed to make the reactants aquarious so they w ill react. also no heating is required making it even easier to make.
megalomania October 9th, 2001, 01:37 AM

My car did break down last week, the worthless piece of crap. Time to rip off the cat converter before I sell it to the scrap yard or some sucker stupid enough to pay cash.
To assist everyone (well, me mostly) in performing acid synthesis experiments, I am creating a new section just for all the threads about nitric acid and sulfuric acid. We can all
pool our knowledge in a central database until success is achieved. Sound good?
------------------
For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Controversial Chem Lab at http://surf.to/megalomania
10fingers October 9th, 2001, 02:19 AM

*
CodeMason October 9th, 2001, 02:44 AM

To make anhydrous ammonia gas, to a glass coke bottle, equal parts finely pow dered ammonium sulfate fertilizer and caustic soda is added and well shaken. When w ater is
added, it reacts like this:
(NH 4)2SO 4 + 2NaOH -> 2NH3 + Na2SO 4 + 2H2 O
Ammonia gas will pour out of the top.
rikkitikkitavi October 9th, 2001, 08:14 AM

1)
(NH4)2SO4 => NH3 + NH4HSO4 at about 100-200 C
2)
NH4HSO4(aq)+ Ca(NO3)2(aq) = > CaSO4 * 2H20(s) + HNO3 (aq) + NH4NO3(aq) (by solubility product of CaSO4)
3)
NH4HSO4 + NaCl => NaNH4SO4 + HCl
4)
NaNH4SO4 = > NaHSO4 + NH3 (200-400 C)
5)
2 NaHSO4 => Na2S2O7 + H20 (400-500 C)
6)
Na2S2O7 => Na2SO4 + SO3 (500C+ )
7)
SO3+ H2O => H2SO4 (in 98 % H2SO4)
SO3 cant be absorbed in water only!
all the reactions come from Gmelin Handbook of inorganic chemistry, a very very useful
encyclopedia found in most university librarys
conclusion
From easily orbtained fertilizers (NH4)2SO4 , Ca(NO3)2 and NaCL it should be possible to
produce all the three important acids
HNO3 , H2SO4 and HCl! I have so far only made nitric acid by reaction 2) and tested reaction 3) (it is cheaper and far easier to buy HCl!)
/rickard
CodeMason October 9th, 2001, 10:22 AM

But then, how would one go about removing the ammonium nitrate from the nitric? I'm thinking H 2SO4 + 2NH4NO3 -
> 2HNO 3 + (NH 4)2SO 4 (s). Thus creating more nitric acid and leaving you with ammonium sulfate to start the
process all over again.

distillation of course...It is a drag to filter since the CaSO4 forms very tiny crystals.
that is what I used, to get aezotropic HNO3.
I calculated that the reaction with Ca(NO3)2 and NH4HSO4 cant produce more than 50-55 % acid , if you start with saturated solutions at 20 C. Higher temperature can give
higher acid concentration due to higher solubility but NH4HSO4 solubility doesnt increase as much as Ca(NO3)2. Not to mention the problem of having to very thick solutions to
mix.
But it could be possible to make, I just distilled the acid out of solution to be sure that I had a clean product.
When you are mixing H2SO4 and NH4NO3 you need to distill the mixture to remove HNO3.
/rickard

Improvised Manufacture of Nitric Acid > HNO3 from air, using an electric arc.
Log in
View Full Version : HNO3 from air, using an electric arc.

This is about the only method for production which has not been discussed so far, so I thought I'd start a thread for it.
There are patents describing this method, but they are for producing low conc HNO3 for fertilisers. Those methods basically
involve having air blown through an arc, and bubbled through water.
But we want high conc obviously, for nitrations etc. Therefore, the continuous method is unsuitable, because it produces a low
conc of NO2 in the air, and since the NO2 will be in equilibrium between the air and water, this can only produce a low conc of
HNO3.
I am thinking about having an arc in a sealed container of air at a few atmospheres, at a low temperature of -15*C to -20*C,
with ice at the bottom. This would hopefully liquefy the NO2 (N2O4 under these conditions) as it was formed, and the still
sealed container could be allowed to warm up, and the N2O4/NO2 would dissolve in the water as the ice melted. It would then
be exposed to the air, or have air blown through it (if necessary, since there is a lot of air in the container) to convert the
HNO2 that is also formed.
What do you think? I intend to start experimenting with this method this summer.
Alchemist August 6th, 2002, 03:45 PM

Hello all,
Mr. Cool, I have also been experimenting with the same thing after reading all the discussion and info Mega posted on HNO3
production! I have so far tried a old Model "T" spark coil in a boiling flask through a two hole cork! This was only atmospheric
pressure though. After about an hour the there was a VERY slight amount of NO2! This was with air though. I then tried pure
Oxgen
via H2O2/MnO2. After only about 7 minutes the entire flask was brown/red with NO2. These where just some tests though
and I really do think a good vacuum and better arc (maybe a computer or TV flyback tranformer) would work much better.
I stopped as I do NOT have a vacuum pump, no flyback (YET), and ran out of time. I keep juming from one experiment to
the
next. I do think your on the right track, so keep it up.
Bye for now then.......
Mr Cool August 6th, 2002, 05:09 PM

Pure oxygen?? You need nitrogen!
Also, HIGH pressure is what you need, not a vaccuum, in order to shift to the right side of the equilibrium of N2 + 2O2 = 2 NO2
= N2O4
Interesting to note that NO is colourless, and IIRC gaseous N2O4 is a light brown (lighter than NO2, anyway).
My first tests will be done with a car ignition coil, 15V 5A power supply and 555 oscillator, because that's what I have at the
moment. At first I'll use a glass flask and maybe only a slight pressure increase if any, so that I can see how much NO2/N2O4
is made.
Alchemist August 6th, 2002, 07:30 PM

whoops!!!
MR.Cool is correct!
My big mistake! It is pressure and NOT a vacuum. The pure oxgen was used to in rich the air only!
*** It's been one of those days. I must think before I write! ***
[ August 06, 2002, 06:34 PM: Message edited by: Alchemist ]

I have come accross this method during my research and from what I can gather it has always just been a scientific curosity,
not a means of production. However, considering that this is late 19th century science their supply of electricity would be a
serious issue. Even so it seems to me to be a highly wasteful practice unless you can let this go for a long time (the very
reason I only get all utilities paid apartments). They had plenty of nitrates back then and by the time they really figured this
out they had Haber and Ostwald.
I read recently that this can be done to completly exhaust the supply of oxygen from the air in a closed system, so I am not
sure you have to worry about this forming an equilibrium. This was a 150 year old reference, so it may be a bit suspect for
accuracy.
Even so you are likely to at least get a small percentage of unreacted oxygen and nitrogen. By adding extra oxygen you could
increase your yield on a batch reaction, but I am not sure it is worth the effirt. Assuming you don't have to foot the electric bill,
just let it run for hours and hours, purge the container with air, flush the exhaust into water to catch the NO2 fumes, and start
again.
If I really wanted to improve the process I would set up a series of spark gaps down a long tube, say a 4 foot incadesant light
bulb, and I would run a very slight pressure through the system so that air would flow continuously. The process may be
improved by adding a pressure release valve that opens at say 1.5-2 atm and then closes. I don't imagine such a valve would
be that expensive, but I have not exactly seen one.
You could let this run all the time (continuous process) largely unattended. The air flows through, gets zapped, and the exit
gas is bubbled into water which slowly becomes nitric acid.
I am not sure how you have rigged up your sparking apparatus, nor am I familiar with the technology available, so I hope my
characterization of small sparking devices is not impracticle. I am thinking sparkplug tip size here. If an incandesant bulb
proves to be too fragile (they can be tricky to work with) you could use several short lengths of plastic plumbing. I have a
bunch of these taking up space from the cast off of various plumbing projects. These come threaded with a male and female
end. With these you could drill holes into the top to install the sparker and screw them together.
You could attach any number of these together. You can even add them as you buy them if you wanted to improve your yield
at a later time. They don't even have to be straight, you could spiral them or accordian them so the apparatus dosn't take up
too much space as well as keep all externial wiring closer together. Using plastic would preclude using massive amounts of
electricity (this is not an electric furnace), but you just need a little spark.
[ August 07, 2002, 12:54 AM: Message edited by: megalomania ]

You will get much better results if you do as suggested and spike the air with excess oxygen. "Air" is only 21% available
oxygen, the majority of the rest is nitrogen with some 1-2% trace gasses that will affect nothing.
Your reaction will be slow do to the slowed collision rate between N radicals and O radicals. Most of your N radicals will just be
wasted by pairing up with much more available N radicals to regenerate N2 again. This is in turn going to detriment your
process in two ways.
1. It's wasteful of the energy provided by the spark, and this translates to wasted time.
2.Heat will become a bigger problem than with the higher oxygen content. The energy transformed into heat will be much
greater from 2N: --> N2 than from N + 2O --> NO2.
In the reaction N + 2O --> NO2 much of the energy is needed to form the bonds, and only a fraction of the input energy is
transformed into excess heat, whereas the reaction 2N --> N2 takes the entire 100% of the energy placed into the molecule
to make radicals and changes it all into heat.
I'd add one volume of air and one equal volume of oxygen to compensate. Again, just my $0.02
PrimoPyro

Yes, more oxygen could be added easily, so I'll try that.
If I was having a continuous process, the first thing I'd try would be to blow the air through a thin copper pipe, the end of which
would be close to a copper plate, and the arc would be struck between pipe and plate. With a bit of adjustment of current,
voltage and seperation I think it would be possible to have the arc form all around the openning of the pipe, so all the air
would have to pass through the arc.

Um, sorry if this ends up being k3wl or something, but how well would a Van de Graaf generator work? You know, those purple
lightning ball things? They're based on mechanically induced static generation and discharge. Beyond that I really don't know.
I know the amperage is very low because they are not harmful. But what of the voltage in these things? Not the input of
course, but the spark voltage that jumpts the gap from the center to the glass orb outer shell.
Fuck, I really dont know what the hell Im asking. Umm, well look at its shape. If it had inlet valves at the top for gas, the
sphere represents the best shape for maximum spark coverage and even generation.
If you had a bowl or something in the bottom, and kept it in the freezer at -10C or so, any formed NO2 would condense to
N2O4. And you could watch it happening too, and take pictures. :D
I wouldnt recommend using a store bought one, but rather build a device lightly based on the same principle and dimensions.
What do you guys think? Good idea, or k3wl dud?
PrimoPyro

I don't think electrostatic devices have a high enough average power.
Oh, hang on a minute, that's not a VDG you're talking about! You mean the glass things you touch and get swirly purple
plasma being attracted to your fingers? "Plasma Ball" or "Lighning Sphere", they're normally called something like that. A VDG
is an electrostatic generator that looks like an Al sphere on a big cylinder and sparks jump off the sphere, the thing you're
referring to has an induction coil as the power source.
Well, one of the patents I read had a sphere (one elctrode) with the other electrode at the centre, and air was blown in at an
angle so the arc swirled round inside (don't know why it couldn't just be allowed to stay still), similar to a metal "Plasma Ball"
or whatever they're called.
Don't know how well it'd work, a normal spark gap would certainly be easier though.
rikkitikkitavi August 9th, 2002, 05:27 PM

A van de Graaf generator could work but it would take aaaages because of it low power output. In the Birkeland-Oestlund
process they used up to 4 MW electrical arcs
By inducing a magnetic field the arc was spread out to form a disk, aka electrical sun and air was blow perpendicular into the
disk so the residence time was as short as possible.
Still the gas leaving the reaction chamber contained about 3-4 % NO , mainly due to the fact that NO quickly decomposes at
the high temperatures in the arc.
I think the better way to do it is to do like in a similar way of the

Birkeland--process , the only one comercially feasible (until Haber-Bosch kicked their asses with cheap NH3)
You can get up to 68 % acid by reacting NO2 with water.
/rickard
vir sapit qui pauca loquitur September 21st, 2002, 05:54 AM

as mega has pointed out, i should have posted a few points in THIS thread. whoops. :(
with my intended apparatus, (so that i get it clear) i have 3

chambers(formed from seamelss stainless steel) each one is larger then the last (for examples sake A=6" B=12" C=18") A
and B are linked to C (at the ends of all pipes are turn valves, so i can shut off/open the flow)
i feed pure 02 into B, pure N2 into A (after flushing all tubes/pipes with helium to provide inert aptmoshpere)this pressurises A
and B to about 2000 PSI. After that i open the valves to C, this pressurises C with N2 and 02. Valves are then closed.
In tube C i would have installed a small bank of car-spark plugs (due to the high pressures used i was limited in what to use)
about
4.these are located at the TOP of the chamber (i was hoping that with NO2 being heavier, i would increase the yeild if i located
the spark units where the substrate is lost likely to be located)
i would power the spark plugs from a car spark-gap generator, and i would power it rom the mains. power is not an issue as i
also get utilities included in rent.
My aim was for the ability to set up this, and walk away for a few hours/days and to come back and to _slowly_ bleed the
gases formed into water. Providing Hno3, i would know if cylinder C has been effected, as i will include a pressure guage to
inform me if the pressure has gone done (a sign of formation of something) as there would be a lower number of moles of
gas, hence pressure is lower
(PV=NRT, if the V=volume remains constant, and the P=pressure
lowers,and the T=temperature remains near constant
(R is the gas constant, 8.32 j/mol) then we must have a reduction of N=number of moles)
but are we talking about hours or days or even weeks ?? thats my new question, as unfortunatly i have limited knowledge of a
reaction involving spark-plugs :p i'm willing to leave it for two weeks to keep on going, but i dont want to start bleeding it and
lose the 99% of the gaseous aptmosphere that hasn't reacted.
i did have the idea flitter across my troglodytian brain that i shoul include an amount of water in C so that the NO2 can
disslove into solution. after i coat the stainless with ptfe! and then i could drain this water from the vessel, this means that i
lose virtually nothing from the reaction vessel in the way of unreacted gasses.
what do you think ?
megalomania September 23rd, 2002, 06:10 AM

Perhaps there is an even simplier way of doing this. I found this blurb from a published reference:

Helvetica"> When strong electric sparks are passed through a confined portion of air, standing over a solution of potassium
hydroxide, the volueme gradually lessens and potassium nitrate may be detected in the liquid. So when ozone acts upon the
nitrogen of the air, upon ammonia, or upon the lower oxides of nitrogen, water being present, nitric acid is produced. <hr /></blockquote>I assume the presence of potassium hydroxide is
intended to increase the solubility of the gas such that it reacts before it can be broken down again. You could still use a
pressurized system with pure O2 and N2, but I don't see a reason to use pure gas, or necessarily high pressure. I would go
with pressure if I could just because it will increase yields. I would settle for a few atm's if I did it. I would definitely modify
your procedure to include the alkaline solution (I am sure sodium hydroxide would work just as good).
vir sapit qui pauca loquitur September 23rd, 2002, 02:52 PM

thanks for that, i have just got the reaction chamber back from the company that coats my equipment with PTFE (ironically i
said i was dealing with a high conc KOH solution :rolleyes: )
so in a short while i should be up and running, but i need for the money to roll in. As i bought some rather expensive
investments, and being a student does not help things much.
interesting.... verrryy interesting.

Would you mind elaborating on your sparking equipment. I think I may try this myself, but I don't know much about
electronics. Any references would also be good.
I found this pdf document about building a sparking device:

<a href="http://www.imagineeringezine.com/PDF-FILES/spark4.pdf" target="_blank">http://www.imagineeringezine.com/PDF-
FILES/spark4.pdf</a>
Nitro September 24th, 2002, 04:57 PM

Very intresting high Voltage source is an industrial Powder painter(Dont know how you call this but it used in car industrie to
make an black colerd powder over some Axes parts).They use an ionisation sparc(80 000V and an curent over 50mA
Deadly).If you can get one of this transformer your lucky.P.s you need an cooling defice for the Transformer i had forgett this
and it was destroyed after 2 minutes(sparc range was over 15cm and 1cm thick . :)
rikkitikkitavi September 26th, 2002, 02:25 PM

Just one notion about making NO2 from N2 and O2 from air and an electrical arc.
For the reaction

N2 + O2 => 2 NO
Heat of reaction is + 90,8 kJ / mole of NO
Since not even the best of the industrial methods utilizing an electrical arc would come over 10 % efficency
(energy bound in NO / total energy input)
this means that more than about 1000 kJ of energy is needed for one mole NO.
1 kWh then gives about 3,6 moles of NO.
so by running an electrical arc consuming 1 kW (which is quite a lot) for one hour you would at best get 3,6 moles of NO.
Then by reacting this with air to NO2 and then absorbing this into water
(3 NO2 + H2O => 2 HNO3 + NO net reaction)
you would at maximum efficency produce
2/3 * 3,6 = 2,4 moles of HNO3 = 151 grams / h .
Most likely efficency will be a lot less, lets say 50 % of above.
But still 75 grms is produced /.
I dont know the price of electricity in f e x USA, but in Sweden we pay about 0,05 for o ne kWh, which m eans the price for one
liter 68 % would be
1 4 1 0 *0,68 / 75 * 1 * 0,05 = 6,5 /litre
/rickard
megalomania September 27th, 2002, 02:56 AM

Actually all of the NO produced would react to form NO2 in this system that would then be reacted with a hydroxide to make a
nitrate. From nitrate distillation, assuming you can get a 90% yield (not exactly unreasonable) your yield would be a bit
higher, about 102 g of nitric acid for the amount of NO produced.
One thing I did notice is that the reaction is not the direct combination of nitrogen with oxygen. It goes to ozone first and that
reacts with nitrogen. That means we have to deal with 143 kJ of energy needed to make 1 mole of ozone. Assuming 10% of
that does react we are looking at 1430 kJ of energy to make one mole or about 2.517 moles per kWh. Now we are looking at
about 158.6 g of nitric acid being produced assuming a 10% conversion of nitrogen. I dont have an electric bill handy so I
cant calc that.
After a quick Internet search I came up with a rather good report of Average US electricity prices <a href="http://
www.eia.doe.gov/emeu/mer/pdf/pages/sec9_14.pdf" target="_blank">here</a> which shows currently we pay about 8 cents a
kWh. Last week the Euro and the dollar were almost equal. My 8 cents will get me 56.1 mL of 70% nitric acid, or about $1.43
per liter. Oh, that is at 5% efficiency by the way. To put that into perspective a bulk purchase of technical grade 70% nitric acid
from Fisher (18 L) would run you $8.83 a liter. That does not even include shipping and handling.
rikkitikkitavi, shouldn't you be paying less?

75g HNO3 per kWh and 1.410 g/ml at 68% conc
75g HNO3 / 1.410g/mL = 53.19 mL 68% HNO3 per kWh
1000mL / 53.19mL = 18.8 or 18.8 kWh per L
18.8 x E0.05 ($0.05) = E0.94 ($0.94)
That comes to about 94 cents per liter, not E6.50 ($6.50).
[ September 27, 2002, 02:00 AM: Message edited by: megalomania ]
rikkitikkitavi September 27th, 2002, 07:29 AM

your absolutely right about the price, mega. I missed by a decade :)
somehow I transformed it into swedish crowns (about 9-10 SEK for a )
So it improves the situation very much, making nitric this way is so much more cheaper than purchasing.
For simplicity I assumed that any NO formed in the absorbtion-reaction step of NO2-H2O would be lost. In practice this would
probably lead to large amounts of toxic NOx released into the surroundings.
NO2 + NO + 2OH- => NO2- + NO3- + H2O
as long as pH> 8 the NO2- will not decompose into NO3-.

(this is a comercial route to nitrite production)
Tailgases from HNO3 production are scrubbed by lye, minimizing pollution and recovering nitrite, a useful chemical in many
ways:)
Anyway , it doesnt matter if the reaction goes bu intermediates like ozone for the energy consumtion.
For the calculation, only net reaction is neccessary.
/rickard
[ September 27, 2002, 06:34 AM: Message edited by: rikkitikkitavi ]
Marvin September 28th, 2002, 06:59 PM
The idea of making nitric acid out of air and water is a very attractive one. I researched this in detail in the time before NO2
chose to reveal quite how toxic it was. A very good reference for this is Mellor Volume 8, I'm not sure how common this series
is in the US, if there is a problem I will scan and OCR. The book is quite dated so modern interpretations need to be applied.
If a volume of air is enclosed and heated to a high temperature around 3000K you start to get nitric oxide forming. The higher
the temperature, the more is present at equilibrium and the faster equilibrium is reached. If the mix is cooled slowly the
amount of NO decreases with the equilibrium until it neerly vanishes. Whats required to make nitric oxide is to cool the hot
gas much faster than the reaction rate can enable it to reach equilibrium. Fast cooling is the reason both the air and the arc
move in different directions in the furnace designs. Long below the temperature where rate of reaction is an issue, the nitric
oxide starts to oxidise to nitrogen dioxide.
The limiting reaction is thus N2 + O2 => 2NO, and since the volumes are the same on both sides is independnt of pressure.
Reports of maximum yeilds at 50% oxygen are consistant with this. At higher pressure you get more collisions per unit time in
the gas and as a result higher pressure faciliates the destruction of NO during the cooling stage. High pressure also results in
greater difficulty cooling the gas repidly (Surface area to specific heat capacity), and alows only much shorter arc lengths.
According to Mellor the highest yeilds were obtained by Haber (Yes the same Haber) at a pressure of around 100torr. No
industial furnace I know of attempted to use reduced pressure as the total nitric acid will be reduced for a given furnace
design, and its total product rather than pure efficiency that matter.
Yeilds for most furnaces were of the order of 50 grams of nitric acid per kwh. Total power is what matters most in producing
nitric acid, its pointless having a super efficient system if it only outputs a few grams a day. Electrostatic machines, induction
coils etc are unlikley to output enough power for a useful system. To get something up and running try building a jacobs
ladder using 2 coathangers, a bell jar and a neon sign transformer. Neon sign transformers are ideal for this sort of nitric acid
research as they output reasonable power and are current limited magnetically. An arc starts small due to the breakdown of
air, about 30kv/cm for dry air at atmospheric pressure, but the arc can be pulled much much wider when its started, which is
exactly what happens in a jacobs ladder. Jacobs ladders are notorius for the amount of NO2 they produce while running in air,
so it seems like this would be a useful start.
Its hard to produce concentrated acid from dilute nitrogen peroxide, but there are a few cunning inprovements that can be
made. Silica gel will not only catalyse the production of NO2 from NO (which is much slower in dilute amounts) but will absorb
the resulting nitrogen peroxide. The nitrogen peroxide can be expelled from the silica gel by heating it. Some ceramic oxides
are thought to increase the rate of formation of NO in the arc area, tungston oxide I bilieve is one. The information on the net
on this subject is largly rubbish, with people claiming 'vortex' reactors being cheaper at making nitric acid than large haber/
ostwald plants. They may be an improvement over the old designs but reliable data wont be obtained from the designers,
most of whom seem to bilieve they have solved all of the worlds problems if everyone else would just listen to them, or the
increasing number of nutcases that believe science is wrong and therfore shoudlnt be learned.
The fact the internet is free for anyone to publish anything unfortunatly removes the emphasis on reproduceable experiments
and unbiased trials. I suspect none of these methods produce a massive improvement, equal N2 to O2 aparently only makes
a difference of about 18% at atmospheric pressure over ordinary air.
Anyone who is interested in nitric acid might want to think about electrolysis of molten sodium nitrate, which yeilds copious
amounts of nitrogen oxides/oxygen at the anode, and liquid sodium at the cathode. Why the sodium is stable in the presence
of the oxidising salt I wasnt able to find out, maybe the area around the cathode reduces before it forms, maybe it is more
stable becuase of the electric potential. Furthur info from reliable sources needs to be obtained before attempting this. It kind
of defeats the object of making nitric acid from air and water alone, but this will always be much more trouble than simply
buying sulphuric acid and an alkalie nitrate and making the acid directly.
NO2 is toxic in the extreme, take all precautions to avoid breathing it in.
A-BOMB December 20th, 2002, 12:10 PM

Sorry to bring up a old'ish topic but I have just gotten all the componets to build my own version of this type of devise, I'll be
testing several differnt power sources. The first will be a stun-gun,
the second a high voltage devise I ripped out of a "Ionic Breeze" air cleaner, the thired will be a old laser power supply that I
snagger from the carnegie science center, and the last an old induction coil.
I'm setting it up with a small compressor that will mix the two gasses as they are relessed from the tanks. Next the gas
mixure will be pumped into a 3 foot long glass pipe with spark gaps every few inches alone the length ending in a (extemely
thick) filtering flask were the mix will be bubbled through the water the first time befor it is sucked out and somewhat
pressureized before being sent through the system againg.
10fingers December 22nd, 2002, 12:50 AM

Deleted
[ March 02, 2003, 04:03 PM: Message edited by: 10fingers ]
10fingers December 29th, 2002, 05:27 PM

deleted
[ January 01, 2003, 07:34 PM: Message edited by: 10fingers ]
Mr Cool December 29th, 2002, 06:19 PM

"The home experimenter may want to scale this down a bit."
I rather think that a 3500*C, 1.8 metre disc of electric fire sounds rather neat :) . But I think we should scale it up :D .
Anyway, it sounds like you've had good results! Please give as many details as you can on your setup, I never got round to
doing any serious experimenting with this but if you get 250mL of 70% each day, for 0.16, then I think I'll give it more
thought!!

I saw on a laser site how you can use a hacksaw blade, instead of a smooth wire, to provide multiple plasma arcs for a
nitrogen UV laser.
This may improve efficency for your electric NOx producer since it's the arc that does the converting.
Naturally we'll want pictures or diagrams so we can build our own converters.
A-BOMB December 29th, 2002, 10:02 PM

THAT BITCH!!! :mad: :mad: I told her to stay out of my lab, but no she just has to go down there and mess with shit :mad:
Well my stupid dumb asshole that I call a mother just broke a foot off my glass tube that I had. It not totaly destroyed but
still, :mad: that cost me 47$ I think I go kill her now. :mad: Well my unit didn't get that good of effcienty but that me using a
couple stun guns for my spark gaps.
kingspaz December 31st, 2002, 09:25 PM

could the mist be HNO3 vapour?
10fingers January 17th, 2003, 05:40 PM

Deleted

What was the max conc you were able to achieve with the water vapor? I found out that rubber can conduct the electricity too.
It went straight through a rubber covering on a crocodile clip at 8K. I was working with latex gloves thinking it would prevent
any shocks so I'm glad I found out sooner than later. Now I ware latex gloves under cooking gloves. That shock must have
hurt dude!
I probably would use this to make nitrates but all the hydroxides I can get are very expensive.

Deleted
nbk2000 January 18th, 2003, 12:49 AM

Well, if it takes 4 days to make about a cup of 68% nitric, then how much will the electricity that it took to make have cost
you? More, or less, than making it some other way?

Deleted
Marvin January 20th, 2003, 12:38 AM

Just a few comments.
68% is only the az point, it has nothing to do with this experiment, your limitation is mainly the concentration of NO2 in the
gas you produce. Should you wish to increase this, you can use silica gel as Ive mentioned before to store, and then expell by
heat, the next major limit being the partial pressure of oxygen you can supply at equilibrium.
The arc should not be constricted, it should be alowed as wide as it can without breaking for any given supply voltage. This
provides the highest voltage drop over the arc possible for the configureation, and this provides the best power efficiency for
the total circuit. (Not max throughput, which is at 50% power efficiency). A jacobs ladder electrode arangement is very good for
this, but doesnt alow for ideal air contact, which is best done with the magnet setup.
Voltage is just as important as current for power dissupation by the arc. Power = VI. Substitute ohms law and you get the other
two generally useful power equations for resistive loads, Power = I^2R = V^2/R. in this case R will depend on other factors,
including current flowing and arc length. The only thing you can be sure of is VI by actually measureing them, which is the
voltage over the arc and the current through it, in short arcs you cripple V, and most of the power ends up being dissupated by
the transformer, without actually measureing your setup, I would guess this is the major problem.
Alchemist January 20th, 2003, 12:21 PM

Hello,
I'd also try pumping the air through concentrated hydroxide or etc. to remove as much Co2 as possible before the arcing!
Good luck and keep us all updated. P.S., do you have pictures you can post?

Deleted
rikkitikkitavi January 20th, 2003, 03:56 PM
just one note on absorbing NO2 in water.
At atmospheric pressure it is very difficult to drive the conc beyond 53-55 % , due to the kinetics. It is easy to increas conc by
distillation of course.
Over azeotropic HNO3 can be made by reacting NO2,O2 and H2O in autoclaves at high pressures ~50 bar, this is a method
used in some european plants. But it is of course not feasible to perform at home.
/rickard
Genital-Warfare January 24th, 2003, 11:06 PM

Keep in mind that platinum is used as a cat for this reaction; 600*C oxygen enriched air is blow over Pt and then the
procedure continues.
CTR
J February 3rd, 2003, 07:51 PM

Not much to add, but I think the current is going to be a lot more important than the voltage. Part of my work involves
experimenting with machines that ionize gas to form a plasma. Although voltage does have a bearing on the amount of
plasma produced, current is far more important. I'd want to use a current of at least an amp or two, up to around 7 or 8. This
would be extremely hot, and ionization would be far more efficient than at a few mA.
For an expedient power supply, a microwave oven transformer will supply about 500mA at 2000v IIRC. The spark gap would be
a maximum of 2mm at atmospheric pressure, but using a jacobs ladder this could be increased.
Another idea would be to use a trigger transformer to get the arc going, and a lower voltage for the main arc. This method is
used by some welders to trigger the arc, which is only a few tens of volts but many tens of amps. Perhaps a welder could be
adapted for this purpose.
I'd love to build a machine of this type myself. Unfortunately I have no mains power in my garage, or safe means of getting
any there :-( I have a number of very lethal power supplies that I've collected. These include a 10kv 30mA neon sign
transformer, a variable voltage DC power supply that can put out 200v at 6A, and a voltage multiplier that will put out upto
80kV at 100mA when fed from a suitable PSU! This is a lot more power than I could get out of a 13A socket.
If only I had a proper lab. Maybe next year...
10fingers February 3rd, 2003, 09:48 PM

Deleted
Anthony February 3rd, 2003, 11:05 PM

If an arc welder is deemed a suitable power supply, then I would use a rewound microwave oven transformer instead of pulling
apart a welder.
The secondary windings are simply hacked off and replaced with suitably thick insulated wire with the required number of turns
to give the voltage desired.
Should be good for a Kw and many could be used as MOTs can be had for free.
Some people have done this to make their own arc welders BTW.
Marvin February 8th, 2003, 02:46 PM

10fingers, the az point is not limiting in your design becuase below 100% nitric concentration, the vapour will always be a mix
of acid and water. Decomposition equilibrium with the exiting gasees is as youve found. To get high concentration acid you
need to concentrate the NO2 as several people have discussed viable means of, higher than az should be easily possible but
a good design would add one or more low concentration scrubber(s) at the exhaust to reduce wastage.
Putting more power in the arc does mean you have to cool the aperatus much better, but then power into the arc will be
proportional to the amount of nitric you can produce with the resultent gasses.
By your numbers you are a fair amount below the birkland values but considering its a first attempt Id call it a roaring success.
CTR, I havnt heard of this method, Id have thought 600C would be far too low to produce a reasonable concentration of NO,
do you have any more information on this?
J, you are right about current being the limiting factor for producing plasma. This is because plasma = ions + electrons, which
are your only charge carriers and therfore the greater current the more charge carriers must be carrying it, and therfore the
more plasma you have. This is even more true at low pressure, where I suspect you are making your plasmas.
Unfortunatly, we dont want plasma. We dont want ions or electrons, what we are after is vast volumes of very hot air (3000K
ish) being rapidly cooled. This requires having ionised gas present becuase otherwise it wont conduct the electricity that is
doing the heating, but our limiting factor is power into the arc, not current through it. NO can be made without an arc, by
burning fossil fuels, and this is how it ends up in a car exhaust, purely thermal.
MOTs are excellent becuase they provide high power into an arc that can be 6 inches long. The air going through it can be
rapidly cooled, and relativly little power goes into the electrodes that form the arc.
A Jacobs ladder does alow an arc to start small and be pulled very wide, but the starting arc must be wide enough for the rising
air to pull it up. 2mm sounds about right for a MOT but this is not wide enough to start a jacobs ladder rising, Ive tried, it sits
there arcing into 2mm and most of the power is being dissupated by the MOT itself brcuase of the matched load problem.
Generally, I am unsure how far its possible to pull a 25v arc @ 50 Amps in air, but my guess would be not far enough. Arc
welders are designed to put as much power as possible into the metal, not into the air around it, hense high current, low
voltage.
Making the arc 'hotter' is one other obvios way of getting more NO that doesnt actually work, its impossible to cool the gas
quickly enough to take advantage of the higher equilibrium concentration of NO. I just thought Id add this as an afterthought.
I'm convinced stacked MOTs, long moving arcs (magnetic field) and high total power is the way to go for nitric by arc.
10fingers February 9th, 2003, 07:02 PM

Deleted

You are quite correct about the products of the reaction moving up with the arc, and that this is counter productive. It does
stretch the arc considerably though, and due to its higher voltage drop more NO should be produced with less power wasted
into the transformer. Ideally a setup of this type would have 2 main differences, firstly it would have its electrodes trimmed
short enough to prevent the arc breaking, and secondly would have a vertical magnetic field to force the arc to move
horizontally, perpendicular to the current flow. The two reasons I would expect the arc to break, are more obviosly that the
current cant sustain the arc, and less obviosly that the voltage drop over it exceeds air breakdown for the gap at the base.
The comment that rikkitikkitavi made about concentrations over 55% being difficult to make with this process turn out to be
remarkably accurate for equilibrium too. Numbers from a table I thought Id lost (or Id have posted them earlier) on practical
values, just those relavent to arc processes to avoid a table formatting nightmare.
NO2 conversion to nitric acid for 2% NO2 in air by absorption in nitric acid at 10C and atmospheric pressure (higher yeilds at
low temps).
5% Nitric, 65.7% conversion.

I will OCR the full table soon.
Some general features of the whole table Ive noticed, conversion drops a lot for higher temperatures, eg for 25% nitric acid a
60% conversion at 10C drops to 23.6% conversion at 75C. This may entirly be due to evaporation of acid, or bad absorbtion
values it doesnt say, this is overall yeild for a single absorbtion stage. Rather disturbingly for the whole table, it doesnt rise to
100% conversion for a single stage at the limit of pure water, implying 40% of our possible product is lost in any single stage
absorbtion. This isnt a limit due to the low concentration of NO2 in air though, as the following values show for a mere 0.1%
NO2 in air.

The secret to getting the most nitric acid from NO2 seems to be absorbing it in a series of successive wash baths at room
temp, or lower.
Ok, methods of getting stronger nitric with the arc process, apart from the obvios distillation of the product acid. Use of silica
gel. After cooling exit gasses to room temp, silica gel will catalyse the conversion of NO to NO2, and also absorb it. It can be
expelled by heating and presumably this must be a substantial mole fraction of the silica gel used and the same sort of effect
as removing water from air. Being able to produce virtually pure NO2 should alow rather more concentrated nitric acid to be
produced than with 2% in air. Another idea Ive been working on, involves ozone. Ozone isnt required for the formation of NO,
and isnt produced by the arc chamber. If you add it to the produced NO2 however, it oxidises it to nitrogen pentoxide rapidly
and from what I'm reading, quantativly. Freezing out the nitrogen pentoxide and using it to make 99%+ acid in a single step
would be very nice, but oweing to its relativly high (sublimation) vapour pressure the numbers look unfriendly. For 2% by
volume NO2, mixing with an equal quantity of 1% ozone in air, producing 1% nitrogen pentoxide by volume would require a
temp of about -25C to start forming solid and about -30C to produce half of the total N2O5 as solid. Simply running the 1%
N2O5 into water or acid however. should prove a much easier route to neerly pure nitric acid than anything involving NO2
directly.
Ozone is very nasty stuff, but we're dealing with NO2 anyway and have allready discussed those horrors.
Tuatara February 20th, 2003, 04:47 AM

Ozone can be readily produced by a corona discharge. This involves raising a bunch of sharp needles or a fine wire to several
kV dc. The electric field intensity around the wire is sufficient to ionise the oxygen, but drops off fast enough to prevent arcing.
If you were to put this ahead of your main arc you'd get the additonal benefit of reducing the breakdown voltage of the air,
facilitating the use of a larger arc gap.
The ozone generation problem is one reason negative ion generators (supposed to be good for you) only run at about 3kV. A
good DC supply could be built from the horizontal output transformer of a TV - that'll get you at least 25kV. They can be easily
found at electronics surplus stores.
Anthony February 20th, 2003, 12:13 PM
How much ozone would be required?
The domestic generators seem to be rather limited in output:
MorZone 30 30mg/hour ozone generator. $67.50
Red Sea 50 mg/hour ozone generator $160.99


I had envisioned using a series of water filled bottles to react my NO2, but I only knew the yield was lowered
because of production of NO in the reaction. In order to react the NO back into NO2 another bottle seemed
logical. I wonder if this is the same principle behind your figures, Marvin? It is nice to see some data to validating this system.
Industrially they use a water mist that trickels down the side of a tall chimney to react the nitric oxides as they rise up. They
get a max conc. of 65% doing this. This is basicially the same thing, but in one system.
Does anyone think using a strong base (like NaOH) in solution would increase the yields of nitric conversion? The base would
neutralize any acid formed thus keeping the concentration low. Of course the presence of nitrates may effect the equilbrium in
other ways that limit the usefulness of this.
My hopes for the successive bottle system is that the first bottle would become more and more concentrated, eventually
reaching fuming, while successive bottles would accept an increasing share of the nitric oxides. With enough botles in series
the last should be very dilute thus getting a very high yield of acid because almost all nitric oxides are captured. Now I see
that obtaining a fuming acid in the first bottle is not likely to happen. Your data, Marvin, will help me make a more accurate
determiniation of how many bottles to put in the series. More will be needed, or the reaction run less, to convert all the oxides.
10fingers February 21st, 2003, 12:25 AM

Deleted

That is doubly dissapointing. In retrospect its likley the constant rapid changes in voltage degraded the insulation. How hot
was it getting while constantly on? It shouldnt have a problem thermally at least. I cant get neon sign tranformers here easily,
or Id have tried something similar myself.
With regard to ozone, 10g/hour would be borderline useful. Putting it in front of the arc chamber would be counterproductive
though, as the conditions that form NO, would destroy the ozone. Domestic generators are useless, as would be expected,
commercial or industrial water cleaning/pool cleaning equipment seems to be much more viable. Ive found a unit being sold
that produces about 30g of ozone an hour, and though I dont know what it costs (probably much more than I could justify
spending) the stated power consumption values are useful. It produces 30g/hour @ 6% ozone in oxygen, (It uses an oxygen
enricher from air), and consumes just over 600W, not including the enricher itself.
The standard ozone generator uses concentric glass tubes to produce a 'silent' discharge, I bilieve with high frequency AC at
20kv. This rules out use of voltage multipliers of the cockroft walton type, a single TV loptx would be capable of around 9Kv,
so maybe this is possible, but would probably only supply a few 10's of watts at the most. If a fine wire corona discharge will
work at power, then DC operation becomes possible and a voltage ladder with a neon transformer might be feasable. The
problem I forsee with the fine wire, is this might need a very large box to be operating in without heating problems of the wire
itself which would decompose the ozone as its formed.
2 moles of nitric acid require 1 mole of ozone, so the numbers are about 126g nitric, needing 48 grams of ozone. An arc
chamber should be easiliy capable of 50g nitric acid per kilowatthour, so a 1 kilowatt 'furnace' needs an additional 400 watts or
so to produce enough ozone to completely turn the nitrogen peroxide into pentoxide. Ignoring the cost and additional
complexity of the ozone generator, its a small increase in running costs to be able to produce neerly 100% nitric in 1 step.
Multiple stages to produce 65% acid from NO2 with a nitrogen pentoxide 'booster' to turn that into 100% acid would save some
power due to less ozone, but 65% odd nitric is still much more than half water on a molar basis, so the saving is small and it
turns a potential tabletop generator into a small chemical plant.
A closed vessel over caustic soda will absorb oxides of nitrogen almost completely, forming mostly nitrate, with some nitrite.
Argon was discovered this way by Cavandish, who added oxygen to air contained in a glass bulb, and removed nitric oxides
with lye while sparks were passed through the gas. I have to say if I was going to the trouble of fixing atmospheric nitrogen,
Id be very dissapointed with anything other than high concentration nitric acid. In terms of areas that cant get nitrate fertilzers,
manure is much more likley to be of use for making nitrates than mains electricity.
More current than your neon tx was providing would do only fractionally worse than the extra power it provides, but not better.
Very low current sparks, such as static electricity circa 100na do very well for producing nitric acid (in excess of 70g/kilowatthour
IIRC), but as the total power is very small, throughput is miniscule.
Mr Cool February 24th, 2003, 11:54 AM

"Silica gel will catalyse the conversion of NO to NO2, and also absorb it."
I wonder what it's like at removing NO2 from things other than air, for example highly concentrated nitric acid :D
.
It's probably just wishful thinking, but I'll try it anyway. And if it absorbs water in preference to HNO3, then it
could kill two birds with one stone.
The trouble with urea is that it produces moisture (CO(NH2)2 + 2 NO2 -->
CO2 + 2 H2O + 2 N2 + 0.5 O2 I assume, but correct me if I'm wrong),
and when you warm it and buble dry air through you lose some by evapouration and you get nasty fumes. While none of
these problems are very significant, it would still be nicer just to add silica gel and filter it!

Deleted
Mr Cool February 25th, 2003, 07:04 AM

What are the advantages of using silica gel to absorb NO2 rather than MgCO3, for example, if
any?
It strikes me that using a basic magnesium compound slurried in water would be more efficient. Silica gel must form an
equilibrium of NO2 with the atmosphere, and will thus reach saturation quite easily in low partial pressures of
NO2 I would have thought.
MgCO3 in water, however, will keep on absorbing the gas until it has all reacted.
Then you roast it like you would with silica gel (after drying it out) to get back your NO2. Calcium nitrate
decomposes at around 600*C, magnesium nitrate will therefore decompose below that.
To make the NO2 into HNO3, I personally would condense it with a freezing mixture, and pour it
into a container with the appropriate amount of ice, below the bp of N2O4. Then seal it up and
allow it to warm to room temperature. This will create the combination of higher pressures and lower temperatures that you
want.
Microtek February 25th, 2003, 01:45 PM

While working on my HMX procedure, I came across a patent about generating N2O5 in nitric acid by electrolysis. The idea was
to start with essetially anhydrous HNO3 then dissolve N2O4 in it and electrolyse the solution with a carefully controlled voltage.
Now, N2O4 exists in equilibrium with NO2 and low temperatures favour the dimer so maybe you could distil a portion of HNO3
90% at atmospheric pressure so there was a certain amount of NO2 dissolved in it. Then lower the temp to form N2O4 and
convert this into N2O5 via electrolysis. You could then add more NO2 and continue the electrolysis until the nitric had become
too viscous from the N2O5 for proper mixing. Then simply dilute with water to convert the N2O5 to HNO3, add more NO2, cool,
etc. etc.
Tuatara February 26th, 2003, 09:03 PM

I did a lot of searching yesterday and found a very interesting patent FR2549459 on <a href="http://ep.espacenet.com/"
target="_blank">esp@cenet</a>. Its in French, so if theres any French speakers out there please correct me.
Summarised (from Google translator): Use a microwave powered plasma in air at a pressure of 25-75 millibars to generate
NOx. Can be powered by a microwave oven magnetron (refer to <a href="http://www.belljar.net/plasma.htm"
target="_blank">The Bell Jar</a> )
Notes 1/ Suitable catalysts are Tungsten trioxide or Molybdenum trioxide
2/ best energetic efficiency with 65% N2, 35% O2 , but does not alter NOx ratios
3/ with MoO3 catalyst energy use is 28MJ/kg of NO at 6% conc in gas leaving reactor
4/ without catalyst energy use is 43MJ/kg of NO at 4% conc
Saw another site where someone created a plasma is a glass container in a microwave oven at atmospheric pressure. At end
of run the container was full of brown gas!

Do you mean <a href="http://www.kronjaeger.com/hv/hv/exp/no/index.html" target="_blank">this</a> site?
Tuatara February 28th, 2003, 05:02 PM

No, actually I was talking about this <a href="http://jnaudin.free.fr/html/oa_plsm2.htm" target="_blank">web page</a>
I foolishly didn't bookmark it and it took me a while to find it again

Deleted
Tuatara March 2nd, 2003, 02:23 AM

10fingers you will need an impedance in your arc circuit! If you strike an arc directly out of your MOT you will pull a lot more
than 2kW as they are not current limited, so your transformer will die rapidly and spectacularly. Neon sign transformers are
impedance limited - when you short the output (which is basically what an arc does) they become a current source, limited to
30mA or so. Your impedance should be an inductor of about 10 to 20 H for 60Hz mains(thats HUGE), or a capacitor of about
400nF, and it must be capable of handling at least 2kV.
Why not use the microwave to create the plasma? You've got 3 magnetrons, with waveguides and power supplies ...
10fingers March 2nd, 2003, 02:48 AM

Deleted
Tuatara March 2nd, 2003, 04:34 PM

Always happy to help!
Here comes Electronics 101 <img border="0" title="" alt="[Wink]" src="wink.gif" />
Had to think about the primary/secondary question - the answer is yes, you can put the impedance on the primary side but it
needs to be smaller (smaller inductor or bigger capacitor). A resistor can be used but it will dissipate huge amounts of heat ,
2kW. Inductors and capacitors don't do this (well, not much anyway) as they are imaginary impedances - current and voltage
are 90 degrees out of phase (ideally) so when you multiply volts x amps and integrate over the complete sine wave you get ...
zero!
Microwave isn't that hard. The microwave energy is absorbe in the plasma. Heres a couple of good links
<a href="http://www.tpub.com/neets/book11/index.htm" target="_blank">Microwave theory</a>
<a href="http://www.psfc.mit.edu/plasmatech/plasma_technology.html" target="_blank">MIT plasma research</a>
Putting your transformers in series is no problem - if you get it wrong you will get no volts out the end.
Marvin March 2nd, 2003, 06:25 PM

I would think the big advantage to silica gel would be a vastly reduced temperature for driving off virtually all of the NO2. I
would think substantially below 200C. Silica gel decomposes itself so that limits the temperature it must work at.
My understanding of the urea reaction is it is the diazotising of an aliphatic amine, which promply decomposes to nitrogen gas.
I would not expect oxygen to be in the products, and NO2 to be effrctivly exhausted by the equilibrium shift.
MOTs are in another level entirly to neon sign transformers, you need to do your EE homework. <img border="0" title=""
alt="[Wink]" src="wink.gif" />
Taking 80% of the max power of the transformer wont get you even within a factor of 10 of whats really going on if you dont
get the design of the electronics and arc sorted.
A single MOT, with a peak output of about 2kv will need an external starting system. The ones Ive used would stand being
shorted long enough to start the arc, but would get very hot very quickly. When a MOT is shorted it pulls its max power, and
dissupates all the energy entirly within intself. A short arc is indeed much the same as a direct short, but a long arc - close to
the maximum the transformer can produce is usually enough of a load to prevent the transformer overheating (in the case of
MOTs). I am unsure what rating the transformers I had were, so your experience may differ.
My best 2kv MOT developed a stable, curved arc in excess of 6 inches total length. Putting 2 transformers in series should not
be required or advantagous. The semiconductor diode the doublers use wont be happy with your total power, the short current
at arcing, or the high peak transients formation of a sparc produces.
In purely theoretical grounds, using microwaves has quite a lot going for it, dispite the large reduction in overall power, dispite
only half of the energy ending up in the plasma, the electronics is allready expertly designed and working, the transfomer
wont overheat, nothing will be overloaded, and if the arc is at low pressure, its a good way of solving the arcing problem.
You dont have a waveguide to use however, the connection between the magnetron and the oven is short and stubby with the
magnetron grafted on so that the oppasit of a waveguide happens to the oven. The waves bounce around randomly so the
food is evenly irradiated. Leaks are the main worry, not just to simply seal the gas cavity, but also to get the gas in, arced,
cooled and out, and the cooling water youd need to shift potentially 2kw of thermal power out of the system. The first thing
youd know about a minor leak would probably be not being able to read this forum anymore. Not using this method is
probably a very good plan overall.
If you do still decide to wire 2 of the transformers in series, remeber one side of the secondary is grounded to the core, so the
second transformer needs to be connected backwards (and therefore the primary also backwards) to avoid being shorted. Even
if you isolate both cores, putting them both forwards potentially overstresses the insulation even without the voltage doublers
you were thinking of leaving on, remebering these produce DC from AC, if you thought the electronics/math was hard for
neons, you aint seen nothing yet :D . Let us know how long the max arc you can pull is with one transformer. Try using 2
gloves, one for insulation on the inside, one for padding. The padded one cant conduct electricity (obvoisly), but you need the
electrical insulation on the inside in case what your touching is hot.
[ March 02, 2003, 05:33 PM: Message edited by: Marvin ]
Tuatara March 5th, 2003, 03:48 AM

How could you possibly be worried about microwave leakage when your trying to make nitric acid, in order to make chemicals
that will gleefully remove your limbs at the slightest provocation :p ?
Seriously though, do check the MIT plasma link above - they built a kW atmospheric pressure plasma torch using microwave
oven magnetrons, they got 95% coupling into the plasma from the magnetron (with a simple 3 screw tuner). All I need now is
the circulator to avoid magnetron destruction while I tune the waveguide...
BTW microwave don't fly randomly inside the oven - its actually a multimode cavity, and will develop hot spots, or even destroy
the magnetron if not loaded (with food).
All that aside (no circulator remember?) I gather from earlier posts that it is best to cool the reacted air as fast as possible to
favour the NO2 over NO. So how about putting one electrode partialy into a quartz tube ( from a halogen lamp?), insert the
tube endon into the water so the terminal is within arc strike distance of the surface, then make the water the other terminal.
When the arc strikes, the air pump can be turned on, forcing the water out of the quartz tube and lengthening the arc to the
desired operating point. The air from the arc then bubbles directly into the water and should cool very fast. Only problem is
your water is going to get very hot very quickly. Also the ideal terminal material is probably the thoriated tungsten electrodes
used in plasma welding torches - I've no idea what they cost though.
Mr Cool March 5th, 2003, 11:51 AM

1mm diameter TIG electrodes, 150mm long, cost about 20p each, but are sold in packs of ten usually.
photonic March 5th, 2003, 11:44 PM

I think this question can be made to fit in this topic..
Do any of you know of a source that has rules or information describing reactions involving electricity/electrolysis? I have an
experiment in mind, but it's derived solely from curiousity, and I want to find out whether or not its completely assanine before
I try it.
Marvin March 6th, 2003, 02:34 PM

Nitric acid, oxides of nitrogen, and the type and quantity of anything made are the sort of things anyone seriously interested
in chemistry are going to have to learn to control sooner or later, and the sooner the better. Building power microwave devices
requires specific training and safety equipment. If someone was building a microwave device becuase they wanted to build a
microwave device and understand the principles then my attitude would be different than to people that simply want nitric acid
- virtually everyone reading this thread I think.
Sometimes 'multimode cavity' is just a fancy way of saying 'box in which the waves fly randomly around'. In the case of
domestic microwave ovens, this is exactly what it is. Domestic ovens have no active mode switching, they rely on a
combination of the food moving through any hotspots, and the position of the food changing the operating mode, and thus
the position of any hotspots to evenly cook the food. The path of the microwaves is random overall, becuase the food is
random.
Ive read the MIT paper, it was interesting but I'm not exactly impressed. Some of the ideas they seem to want to claim, have
been in use for decades, for example short coupling distances and off the shelf microwave componants in argon plasma
cutters. The artical looks like an undergrad project, and reads like an advert. The 95% coupling they are so proud of for
example, is achieved at the expense of using 2.45GHz systems that only produce slightly more than half the microwave power
they consume, this should have been included and discussed, they clearly know about this problem from the discussion of
moving to lower frequency microwaves. (2.45GHz magnetron alone is typically 70% , add power supply and coupling factor, its
down to 50-60% in a well engineered system). In the specific case of nitric acid production, the output temperature is too high,
reducing this to about 3000C, will almost certainly reduce the coupling factor due to reduced ion concentration. In a low
pressure system microwaves have advantages, and the low power efficiency of the microwave system would be offset by the
higher nitric acid yeilds. One might ask though, if the low tech system and the high tech system are going to produce roughly
the same amounts of nitric acid, why bother with the extra complexity?
Fast cooling isnt about NO2, its about 2NO <-> N2 + O2. Formation of NO is endothermic, so at a high enough
temperature it has a reasonable equilibrium concentration in air (about 4.5% at 3000C). Cooling this rapidly to around 1000C
or below will reduce the rate of reaction, which is negligable at 1000C, before the equilibium has had a chance to change
much. The output gas at this point typically has 2-3% NO in it. When the temperature drops below about 600C the NO starts to
oxidise to NO2, max concentration of NO2 occurs (IIRC around 120C), below which the NO2, which has an unpaired electron,
making it a radical, paramagnetic and strongly coloured, dimerises to colourless N2O4. How much NO/NOx you think you have
in the gas is thus highly dependant on temperature, and this is worth bearing in mind for anyone experimenting.
Tungsten is fantastic stuff for high temperature applications, provided oxygen be excluded as in lightbulbs, inert gas welding
etc. I have no idea if this will be a problem for this application, if well cooled the tungsten might not oxidise at all compaired
to say copper, used in several furnace designs.
I like the idea for the water electrode chamber, but I'm not sure how well it would work if the water, which would be boiling at
the electrode, would interfere with the process. I'm currently trying to understand why the yeilds of existing processes in the
french patent, fail to match the birkeland eyed's values, which seem pretty consistant with most arc methods. The best way for
atmospheric pressure air arc furnaces seems to be widening the arc magnetically, and blowing air directly through it.
photonic, unless you plan to calculate the redox potentials for every possible reaction in the system, its easier just to ask if its
likley to work, I suggest modifying your question to include your exact idea, and if its not directly nitric acid related, you might
get away with it anyway. :)
rikkitikkitavi March 6th, 2003, 03:20 PM

marvin, just a point about the NO2/N2O4 equlibrium.
When it comes to absorbing into water, they are similar.

However the lower the temperature the faster and further the absorbtion goes. The reaction between NO2(aq) and H2O =>
HNO3 is strongly exothermic.
I have some pages from Ullmans encyclopedia describing the kinetics

of NO oxidation to NO2 and absorbtion mechanism.
I will scan them with my companys new printer/scanner/copy machine (3 s scanning time for 600 dpi!!!, and it even sends it as
an email to my work computer!Isnt technology great!!) and upload them to the FTP. Very interesting reading for anyone
seriously interested in designing a HNO3 absorber.
/rickard
Tuatara March 6th, 2003, 04:00 PM

I suggest thoriated tungsten due to the high melt point, and improved electron emission. Every time I play with my neon txfr I
melt the ends of what ever wire is supporting the arc (copper, steel, stainless). Next time I'm near a welding shop I'm going to
get some electrodes.
I wasn't sure what the water vapour would do to the rxn in the water electrode system I decribed - can water react with NO2 in
vapour phase? It might not matter anyway as the air stream blowing down into the water should provide good local stirring,
and carry away any steam.
Sorry about my fixation with microwaves - I'm an electronics engineer and I can't help it :rolleyes: . Your right marvin, most
here would not want to play with that stuff so I'll shutup.
[ March 06, 2003, 03:01 PM: Message edited by: Tuatara ]

Well, I'm afraid some chemistry knowledge I don't possess may make this a stupid question. At that risk, here it goes. I was
wondering if you dissolved/mixed some KNO3 in water and then ran a current through the water if there would be anyway to
obtain HNO3. All the right elements are there but they normally won't react. I was thinking it might be possible to put a basin
full of the H2O/KNO3 solution at the bottom of a column and then pull HNO3 vapor off the column at a certain point. LIke they
do in industrial gas plants. Any ideas or info that would help?
Thanks
mongo blongo March 7th, 2003, 11:16 AM

If you can get KNO3 then it will much simpler to just mix it with an acid.

No, it wont work because you will form OH- and H2 at the cathode, and H+ and O2 at the anode. The gases escapes and the
ions wanders about in the solution, immedieately reacting, forming water. Thus you will just decompose water into H2+O2.
This reaction is much faster than the evaporation of HNO3, giving a extremely low yield.
A few caveats though:

First, NO3- can be reduced cathodically (it has been used to decompose NO3- containing nuclear waste) giving NOx and NO.
Yield is very low though.
Second, more important, if you put the correct ion exchange membrane bewteen the electrodes, creating two separatable
chambers, it will prevent the OH- and H+ ions from reacting, thus you will get
KOH at the cathode, and HNO3 at the anode. These liquids can be sepatated. This kind of methods are patented in numerous
ways , with various components.
Getting hands on the ion exchanger, let me know if you find any!!
/rickard

I got my 3 MOTs out and have almost finished a power supply. I must say I like MOTs. They put out some power! The main
drawback with them, as others have noted is that they are not current limited and they have a tendencey to get hot very fast
with an arc, i.e. smoke in 10 secs.
The one I am using I believe to be 1 kilowatt but am not sure since there is no rating on the oven it came out of, however it is
the biggest of the three and I know one of the smaller ones is 500 watt.
I took this xfmr and put a 8 uF 200 Vac capacitor in parallel with the primary, this keeps it from popping the circuit breaker
when it is initially powered up. I then took one of the smaller xfmrs and used it as a ballast on the secondary. I shorted its
primary and wired the secondary in series with the arc gap. This seems to work pretty well. It can run fairly long without getting
too hot. It does get warm though and I think some cooling is necessary, I may try putting it in a container of oil. What would
be the best type of oil for this? It needs to be readily available and cheap. Will motor oil work? It must not dissolve the
varnish on the wire.
The finished power supply must be able to run for days without overheating.
Initially I wanted to put 2 MOTs in series to double the output voltage but I think this is unnecessary. You were right Marvin.
The way I have it configured right now it will draw a horizontal arc of about 1 inch and a vertical arc of about 3 inches. The
electrodes get pretty hot though, which is another reason I decided not to use two xfmrs in series, I think it would cause a lot
of problems in keeping the electrodes cool. I'm going to try using electrodes that have a lot of copper attached to act as a
heat sink, if that doesn't work I'll try using copper tubing with air blown through it. Also, I have some pieces of tungsten
carbide that I could braze to the tubing to keep the copper from melting.

I think that you will have no problems using motor oil to cool the small transformer, it shouldn't eat the insulation or anything.

Motor oil will be fine. Just make sure there's no bubbles when you pour it. I used motor oil in a salt water bottle cap and it
worked fine until it broke(after about 30 seconds of use). You can use vegetable oil too, but it rots and will start to smell after
a while. Also, if you're going to have it in an airtight container you might want to consider some sort of pressure release valve.
A perfect container for this sort of thing can be had by going to your grocery store and asking them for their old icing buckets.

You might want to use a synthetic motor oil - there should be fewer volatile compounds in it. I've used it successfully to
insulate a high voltage transformer for an electric fence - (had some trouble with micro-discharges inside the secondary
causing EMI problems - oil fixed it beautifully).

I have uploaded a file, scanned from Ullmans describing the reactions and their kinetics (rate expressions, rate konstants)
and the mechanisms involved from NO oxidised to NO2 and furthter reacting NO2 with water .
Very serious reading ( 7 pages) but very useful for anyone seriously interested in designing a maximum yield NO2 reactor and
NO2 absorber.
The file is called "Kinetics of HNO3 formation.pdf"
/rickard

photonic, in fact it does work, provided you have a diaphram of some description, salt bridge, clay pot, specific ion membranes
would be better. Heres the catch though, you need obscene currents to make useful amounts of acid, and the concentration is
deeply dissapointing, think a few percent at the very most. Ive tried this with a few hundred milliamps (a bridge of any sort
rather limits current flow), and it was barely detectable after several hours. I had more luck, though not much more,
electrolysing copper into sodium nitrate with a salt bridge, also of sodium nitrate between partitions, forming sodium nitrate
with sodium hydroxide in it on one side, and sodium nitrate with copper nitrate in it on the other side. The reaction produced
more copper hydroxide than anything else, but the copper nitrate could be fractionally crystalised out of the anolyte, which was
incidently, light blue when dilute/cold, and dark green when concentrated/hot.
I came to the conclusion that these methods wernt at all useful. A good ion specific membrane might change that, but would
probably cripple current flow for a given area, thus in terms of efficiancy its a big improvement, but in terms of throughput,
isnt.
10fingers, MOTs will pull a lot more than the oven was rated for, this is becuase theres no magnetic limiting and becuase low
resistance primaries/secondaries reduce the power wasted in the transformer. A transformer that is capable of 500W would
only be able to power an oven up to 250W, into a matched load, and would waste half of the power put into the equipment
doing it. A tranformer capable of several kilowatts (In terms of peak power, not thermal limitations) would be able to power a
500W microwave while wasting much much less power. The limiting cap should not be in parallel with the primary, this is very
bad, and might hike up your electricity bill somewhat though its interesting it stops your breakers blowing, power breakers are
not friendly to this research compaired with fuse wire. Find a cap small enough to do the job, and put it in series with the
primary, or use the microwave ovens own doubling cap, and put it in series with the secondary. Another transformer secondary
in series with the secondary is good, it will be a big impedence, though a lower power one might saturate. Do not short the
primary of the ballest, or it starts dissupating power becuase you effectivly have a resistor in the circuit magnified by the
transformer turns ratio. Done well, only one or the other should be required, Id put my money on a low enough valued, high
voltage cap in series with the secondary. The one in the doubling circuit might be much too big, but try it anyway. An identical
transformer secondary in series only doubles the impedence of the high voltage side, you may need a factor of 3 or 4 to
reduce the power down to something the transformer can cope with thermally, hense my preference for a series cap, which can
be done much more easily. If your arc goes out when your electrodes are only 1 inch apart horizontally, I think you are
probably crippling the power too much. So long as the power limiting doesnt waste power, resitivly, or by shorting the system
out from mains, as the parallel cap on the primary does (a gross simplification, but it does draw current which you might be
charged for depending on how the meter works, and the power gets dissupated not in the cap, but in the lines of the power
company), so long as the system you make doesnt waste power, you are only left with a rate of production problem, and not a
unit cost problem.
(generally to readers). EE people might be forgiven for thinking what is formed is a tank circuit, but it wont work as one
becuase it isnt decoupled from the mains. I seem to recall saying the EE was hard in MOT systems, so no apologies for how
difficult any of this might sound, or how badly Ive explained it.
I will need liquid insulation myself for another project, but oweing to the high voltages I need, over 100kV, I'll be using a
fluorinated hydrocarbon, like fluorinert. If anyone plans to try stuff over 20kV or so (not for nitric acid), they might like to
consider the same thing.
Tuatara, I think you breed patriotic scottish canaries in cages and look to see if theyre trying to put their wings in their ears.

Ok, thanks a lot for your help Marvin. I'll give your ideas a try.
Right now I just have a test setup to get everything working right and then I have to make an airtight, heat resistant container
to put the arc in. Also, I put the transformer in a container of oil but it still gets too hot after 10 minutes or so. I think I have
to make the arc gap wider so that there is a little less current flowing.
I did a little test by putting a glass jar over the arc and after a few minutes it was intense with NO2 vapor, I had to turn it off
and air out my workshop. It is producing a lot more NO than the neon sign xfmr.

It will be interesting to see which is more efficient - neon tfr or MOT. Somebody do some measurements please?
Thanks for that canary suggestion Marvin - I'm off to save the world a whole lotta pain...
Dammit I need a new signature now!

I'm a little confused here on even the basic idea. Is the premise to bubble NOx through water to form HNO3? If this is so,
could a small/medium tesla coil be employed to generate the NOx? I have a medium(900 watt) tesla coil that will probably
affixiate you after a few minutes in a non-ventilated area. I was thinking(if I even have the basic idea right) that I could
enclose the toroid in a rubbermaid bin or something and bubble that bin's output through water.
Forgive my ignorance.

You have the idea right! Get a good arc off your coil and your bound to produce NO2 - try it and see if your
container fills with brown gas. Is that 900W wall-plug or output? How long can you run your coil for before it melts?
You'd be in a good position to try an atmospheric pressure glow discharge (APGD) with a tesla coil. Here's a link that explains
the concept <a href="http://optics.phys.spbu.ru/~golub/english/barrier.html" target="_blank">Barrier discharge</a>
A quick search with google will provide more info. I don't have the gear to hand, or I'd try it myself.

The 900 watts is the input power(2 30ma 15kv trannies in parallel). I built a pi filter to protect the trannies from the rf current
and after I build a safety gap for the capacitor I should be able to run it for quite some time. Right now I only give it about
30-60 second runs. I'd guess I could run it for about 5-10 minutes. I guess I'll have to get a container big enough that the
sparks won't strike it or else it probably will melt the bin. The sparks are about 36" long.

36" sparks? Excellent fun! Sounds like you need a piece of plastic drain pipe to contain your spark, wont melt if you've got
enough air flow round the outside.
Here's a caveat for all who are contemplating putting an arc inside glass - glass becomes quite conductive if you get it hot
enough. As I remembered tonight, after putting an arc inside a Pyrex ground joint flask - arc too close to side, heated glass,
arc jumps to glass, panic switch off, 'ping' goes the flask with a nice little stress crack where the arc melted the glass :(
Gots lots of lovely NO2 in about 30sec, well the gas was visibly brown anyway!

To get any usable amout of NO2 you need a device that can run for days without trouble.
I would not use plastic, but pyrex glass. Even then you do not want the arc too close to the inside wall of the glass chamber. It
will break as Tuatara said. One time I tried a quart glass chamber which was very small and the arc start flowing along the
inside of it and it broke in less than a minute.
But I would think a tesla coil with that much power would be able to produce NO fairly well. Most Tesla coils have high voltage
but little current so it is questionable that the arc gets hot enough to produce NO. The temp ref I have says you need over
3000*K. The more current through the arc the higher the temperature and the greater the amount of NO produced.

Hmm, I'm glad you told me that. Well, I guess that's a days work down the drain. I didn't realize the NOx would eat away at
the plastic or does it? Currently my setup is two electrodes inside a pvc chamber with a microwave fan feeding it air. I was
going to take the output of that chamber and bubble it through some water in a flask or jar. I'll take pictures of it later today.
I was going to feed it with an NST but that will only provide about 30ma of current. I guess I'll put a couple of MOTs in parralel
and ballast them with a roll of wire. Also, what's the highest concentration anybody's achieved with this personally?

I don't think the NO will affect the plastic, it's the heat that I was thinking about. I don't know exactly how your setup works but
if your dissipating 900 watts into the arc then the plastic might melt.

You'd probably want to pick a plastic with a lower dielectric dissipation factor, PVC isn't terribly good IIRC. Polystyrene or
polyethylene are better, but the melt point is rather low. Teflon would be perfect, but where does one find teflon pipe?

This setup isn't for the tesla coil. This is simply two electrodes in a pvc pipe connected to a fan. The electrodes will be
connected to either an NST or a MOT. I haven't decide yet. Did somebody say a microwave oven capacitor will be a sufficient
ballast for the MOTs? I guess I'll go take pictures of it.
EDIT:
You can see pictures of everything at <a href="http://www.sensorystatic.com/explosives/" target="_blank">http://
www.sensorystatic.com/explosives/</a>
[ March 11, 2003, 09:48 PM: Message edited by: photonic ]

It really is true that a picture is worth a thousand words! Heres a couple of ideas to stop your pipe melting.
1/ deflect your air flow tangentially to the pipe, so the air swirls. This should keep a layer of nice cold air next to the wall, and
hold the plasma in the centre of the pipe.
2/ All that spare thread on your electrodes could be covered with alternating fender washers and nuts, to create a heatsink for
the electrodes. In my experience the electrodes will get damn hot, and brass conducts heat far too well.
BTW a 'fender washer' is a big, thin, washer with a little hole - for those unfamiliar with the term.

Hmm, things just aren't going my way this week. I've hooked two different trannies up to the electrode system and neither of
them will arc. One was 12kv so it definately should have. The other(approx. 1.5 kv) probably should have as well. Especially
when I adjusted the spacing down to about 5 mm. So, I'm not really sure what to do. Has anybody ever seen a MOT that the
core wasn't the second output of the secondary? Would shorting the filament winding on the MOT help at all?

I have three MOTs and they all have one side of the secondary winding connected to the core. The MOT I am trying to use will
only arc about 2mm but then you can move the electrodes apart to maybe 40 or 50mm. Shorting the filament winding will not
be beneficial, just cut it off.
A 12 Kv NST should be able to arc at least 15mm.

Try making your electrodes pointy. The electric field concentration your get around a sharp point aids ionisation, and hence arc
strike.
I think with MOTs being only 2kV or so, some form of ignitor circuit will be required to get the long arc started. I'll have a think
and post anything I come up with
photonic March 13th, 2003, 03:43 AM

What about a voltage doubling circuit? Also, couldn't you create a marx generator hooked to a high current power supply. That
would provide the voltage and current and if you could get a high current PSU then the charge/fire rate wouldn't be too bad.
On a separate note, I have a friend who has done lots of research on using magnets to form electric arcs. It might be possible
to form the arc into a disk with a larger surface area using rare earth magnets or a powerful(about 1 tesla) electromagnet. It
probably isn't worth the effort however. I will try again tommorrow and hopefully we'll have some pictures after that.
BTW, I added a slurpee lid to the top of the pvc pipe and duct taped it. Now it looks like a proper miniature industrial model.

using a magnetic field to extend the surface of the arc was used in the original Birkeland process, hence the name "electrical
sun" since the arc was disc shaped.
A mot can to start to arc over 1-2 mm, since the breakdown voltage is about 2500 V/mm. However when the air is ionized, it is
a completely different matter. Then the arc can be extended further, compare it to a welding machine, where you have an arc
of a few mm @ 20-30V .
/rickard

A Cockroft-Walton multipier would do for starting. 10 stages would give you 20kV strike voltage at least. Caps would not need
to be a large value, just rated at at least 5kV. Could use 1N5408 diodes - series 4 to get 4kV breakdown. These are 1kV 3A
rated. Better still use 6A10 diodes - 1kV 10A.
Once the arc is started the current just runs through the diode chain. This trick is often used for starting HeNe lasers.
photonic March 14th, 2003, 01:02 AM

First trial run is a failure I would say. I ran the "generator" for about 30 seconds and I could smell ozone(or whatever it is, my
tesla coil makes the same smell) but that was about it. It did succeed in melting the slurpee lid I have on it.
I have taken pictures and video of it. If a larger video is needed I can just export another one. I was trying to keep the
filesize small.
Pictures:
<a href="http://www.sensorystatic.com/explosives/NOxGenerator%20001.jpg" target="_blank">http://www.sensorystatic.com/
explosives/NOxGenerator%20001.jpg</a> - Picture of Arc inside Tube

explosives/NOxGenerator%20002.jpg</a> -
Picture with No Arc

explosives/NOxGenerator%20003.jpg</a> -
Entire Setup
Video:
<a href="http://www.sensorystatic.com/explosives/NOxGenerator.mpg" target="_blank">http://www.sensorystatic.com/
explosives/NOxGenerator.mpg</a> -
Setup Running for 35 Seconds. The arc gets kind of wild when the fan is on full power.
I ran the setup for about 30-60 seconds normally. The pictures and video are without the top capped. During tests I put a box
over the lid to try and keep gases in. Any suggestions?

Improvised Manufacture of Nitric Acid > NaNo2!!!!! can I get HNO3?
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THEBOARDER April 14th, 2003, 09:36 AM

HI a ll.......i h ave a few killooo of nano2,,,if any body kn ow how can i get hno3 from it??????????????????????
or if i can convert nano2 to na n o 3 ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? : c o n f u s e d :
rikkitikkitavi April 14th, 2003, 03:03 PM

this is gonna hert, ne wbie....
well, waisting NaNO2 to m a k e H N O 3 i s a l m ost a crim e. Search for what you can do with NaNO2.
NaNO3 or other nitrates are fa irly easily accessible com pared to NaNO 2.
Anyway, heating NaNO2 decom poses it into NaNO3, Na2O , Na2O2 . The latter reacts with water to NaOH, wich can be neutralized
with H2SO4, and voila , you have Na2SO4 and NaNO 3 in solution.
But for f-k sake, dont react H2SO4 with Na2O o r Na2O2 directly, unless you are standing far away. It will all come back into
your face.
If you have an oxidizer perhaps you can oxidize NO2- to NO3-

, but again it will yeild a m ixture of various com p o u n d s a n d i s a w a s t e o f g o o d c h e m icals..
/rick ard

This is a classic, a good informative procedure is to be found here:
http://www.roguesci.org/theforum/misc.php?s=&action=faq
Beware, it m ay increase your HED-dodging skills if you read it carefully.

The world is full of injustice, how can som eone like this be treated to NaNO2?
Maybe you shouldn't play with it till you know what to do with it? That and learning how to FUCKING TYPE PR OPERLY!:m a d :
Marvin April 18th, 2003, 12:45 AM

Hm m, I like weird problem s. Like the m aking sulphuric acid from nitric th read.
How about m ixing with sodium hydrogen sulphate, or a transition metal salt, a little heat should produce NOx and water vapour
very easily, add a little oxygen and condense the nitric acid. NO2 is rather toxic though. If it wernt for the oxygen problem it
c o u l d b e d o n e i n a s e m i s e a l e d c o n t a i n er.
If you m a k e a N a N O 2 solution acid, it should start absorbing oxygen from the air. Not sure how fast though. Seems like rather
a wasted opertunity to convert to nitrate and then do the usual. Must be a m ore devious method for nitrc acid from this salt.
Sulp huric acid probably liberates NO/NO2 in stociometric am ounts on contact, add a little oxygen and you could probably enrich
W NA to conc acid without distillation.
I get the nasty feeling I'm m i s s i n g s o m ething clever that could be done with this.
knowledgehungry April 18th, 2003, 01:48 PM

I h a v e a n e a sy solution to this problem. Here is how you can change you r NaNO2 to NaNO3 which you can then use to m a k e
HNO 3. Send m e your NaNO2 and i will send you an equal am ount of NaNO3 you will get more than 100% th eoritical yeild, cant
go wrong with that.:D

Improvised Manufacture of Nitric Acid > HNO3 the NH3 way
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Trinitrotoluene April 16th, 2003, 08:28 PM

Had anyone tried using this m ethod to produce nitric acid. Oxidization of amm onia. 2 NH3 + O 2= 2 HNO3
++++++++++++++++++++++++++++++++
Gee, I don't think so...oh...wa it...m ega wrote a W HOLE HUGE FUC KIN' THREAD ABO U T I T !
UTFSE!
Or, for you special types U SE THE FUCKING SEAR CH ENGINE!
:mad:

Improvised Manufacture of Nitric Acid > Nitric acid purification
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I have composed a guide for purifying nitric acid and am posting it for all to read and also com ment on the procedure if you
think there is a false statement or incorrect information, so please do share your opinion on my procedure.
Nitric acid purification
PURIFICATION
The nitric acid obtained at the end of my distillation is red to yellow-red. W hat this means is there is NO x present in our acid .
NOx is not wanted so we need to extra ct it using an air pum p , T e f l o n t u b i n g a n d u r e a . T h e a i r u s e d f o r b u b b l i n g n e e d s t o b e
dry, the air around u s h a s too m uch m oisture in it. To dry air is to desiccant air, for those that didn t know that ;) .
PREPARATION
Ob tain a tube that can be used for drying gases eg, U-tube (an im provised tube will do) and fill tube with the drying m edia .
(Silica gel, Activated Clay (Montmorillonite) or others.) (http://www.s-cpp.com /pdf/Desiccant_Perf_Data-1.pdf)
Get your pump and find the inlet hole/valve, (this is where it sucks the air in) put your thumb over the hole to com pletely cut
off intake. Turn the p ump on and see if air is still being pum p e d t h r o u g h . I f s o t h e n t a k e y o u p u m p apart and find where the
a i r i s b e i n g s u c k e d i n , ( s o m e p u m p s h a v e m ore than on e inlet.) To detect the air intake if it is not easily seen, blow smoke on
the pum p area and you should be able to see where the smoke is being sucked in. After these holes are found, block them
l e a v i n g t h e o n e m ain inlet. (using glue, silicon or whatever it calls for.)
Attach the drying tube to this hole/va lve. Do not attach the glass directly! U se tubing, because this is how you will brake
your glass wa r e . M a k e s u r e t h e r e are NO leaks, reinforce your joints with plum b e r s t a p e , this is the white tape t h a t i s o f t e n
around plumbing joints.
H o o k t h e T e f l o n t u b ing up to the tubing from t h e p u m p (using an improvised joiner eg: duck tape.) Again m a k e s u r e t h e r e
are NO l e a k s .
To find leaks if not easily de tected hold your thumb over the outlet (com pletely blocking the hole) and start your pum p. Blow
s m o ke over your joints an if a leak is present than the sm oke will be blown away or sucked in to the tubein g.
P R O DUCER
NO TE that time fram es are a guidelin e. If you notice a n abnormality (using your judgment best a s you can) stop, try again
later and seek advice if it reoccurs continually.
First fill a round bottom flask with your impure nitric acid (not to full to allow for error, 1/2 is sufficient) we do this because
t h i s b e c a u s e w e d o n t want any acid to spill on our skin or cloths, O UCH!
After inserting the Teflon tube into th e acid start bubbling dry air through it, (A constant stream o f dry air, not so much as to
cause the acid to foam up but enough to have lots of nice little stream s of bubbles, youse your judgm ent.) You can slow the
flow of air by slightly clam ping the tube using a p e g o r s o m e t h i n g e l s e .
Ratio for urea addition is 1g urea to 100g acid (1% urea)
For 100g acid add the urea over a tim e of 1 h our (0.1g every 10min) and contin ue bubbling for a nother 2 hours. If you just
d u m p the urea in you will get urea nitrate and this is no t wanted. (If you have twice the amount of acid, double the bubbling
tim e, if three tim es then triple it, ect.)
Swirl the fla sk (for a good minute) while adding the urea and then every now and again for the remainder of the bubbling.
W h e n b u b b ling is finished re move the tubing from the acid and while still inside the flask let any acid drip off.
Ou r acid is now ready for use in other synthesises.
BUBBLER
There are many ways to m ake a bubbler this is just one idea, just rem ember it all needs to be Teflon or resistant to the acid.
Make a bubbler by blocking the end of the Teflon tubing and poking holes in it. Start by cutting two 10mm lengths of tube o ff
the end.
Cut down one side so it folds out and you have a rectangle of Teflon. Flatten th is piece. (In a clamp, und e r s o m e b o o k s
ect ) after it is f lat and will not cu rl, cut a circle out that has a diam e t e r t h e s a m e a s t h e b o r e o f y o u r tube. ( k e e p t h e scraps)
DO THIS TWICE
Pic #1 (http://www.angelfire.com/pro/jarrod/im a g e s . h t m l)
Carefully insert the circles as to perfectly fit and block the tube (DO NOT glue, place it and leave it there)
Pic 2 (http://www.angelfire.com/pro/jarrod/im a g e s . h t m l )
Cut strip of Teflon from the scraps you saved . P o k e a h o l e t h r o u g h t h e very end of the tube, now thread the strip through
the holes. Thus block ing the most of the airflow, there will be air still com ing out. (it should not be to m uch)
Pic #3 (http://www.angelfire.com/pro/jarrod/im a g e s . h t m l)
N o w p o k e h o l e s u p t h e t u b e f o r t h e n e x t 4 0 m m (after the circles finish) and there is your bubbler.
Test your b ubbler in water and tinker until you have lots o f nice little s tream s o f b u b b l e s c o m ing from e a c h o f t h e h o les you
poked.
H o ok it all u p s o y o u r e r e a d y t o p u m p Dry Air.
So what do you think ?

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > nitric acid
from sulfamic acid
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zeocrash May 1st, 2003, 02:51 PM

ok, my mom has just bought some lime lite. being my curious self i decided to look on the bottle to see if it contained hydrochloric acid. to my suprise it did not, it instead
contained sulfamic acid. being a name i did not recognise i decided to look it up on the merck index and found it had the formula H3NO3S.
i was wondering if there was any simple way to convert this to nitric acid.
i was playing around with the idea of catylitic breakdown
H3NO3S ==> H2S + HNO3
but i do not know what would contitions and or catylists would break it down
this is not critical at the moment as i have a winchester (cant remember the capacity of a wincester) full of nitric acid in my lab, but my suply is finite, and will run out
sometime.
if this idea has been mentioned before, i apologise, but i searched for english and US spellings of sulfamic acid, as well as its alternate name (amino something)
Mr Cool May 1st, 2003, 04:40 PM

I'm quite sure it is not possible.
Sulphamic acid is formed by reacting ammonia with sulphur trioxide. H2N-SO2-OH. Breaking it down into nitric acid and hydrogen sulphide would require that you reduce the
sulphur all the way from +6 to -2 (a lot of reduction!), and this process will be very endothermic, ie, if it occured the extreme conditions would totally destroy any nitric
formed, and it would then oxidise your H2S... Plus everything's in the wrong place, the nitrogen's on one side of the molecule and the O's are all the way over on that sulphur,
which they are quite happy to be bonded to.
I don't have any way of proving or showing that it won't work, but it won't :p.
It is a potentially useful chemical though... used for making dinitramides, and RDX (in theory, I have not had luck with this method).
jfk May 2nd, 2003, 07:12 AM

Mr cool, what process did you try (link?) because i tried to synth RDX using sulfamic acid andgot nothing either, but surely someone has done it, the link i had was quite osme
time ago but the guy who wrote it said hed done it.........
annother thing was looking things up in the MERK index, you gotta look at the structure of the compound. like in sulfamic acid the HNO3 that 'is' in there is not really there as
nitricacid - its all over the place, you cant really get it out even if you did manage to reduce it from +6 to -2, which i would say was just short of impossible, and being highly
economically unpheasible
zeocrash May 30th, 2003, 06:44 PM

i was wondering, is sulfamic acid a strong enough acid to catylise the production of AP
Arthis May 31st, 2003, 06:38 AM

with a pKa of 0.99, sulfamic acid should be ok, considering that it works with citric acid, whose pKa are 3.13, 4.76 and 6.40.
zeocrash June 1st, 2003, 06:05 AM

pKA?? i'm afraid i'm unfamiliar with that abrviation
vulture June 1st, 2003, 10:55 AM

pKa = - log Ka
The lower the pKa, the higher the Ka and thus the higher the "strength" of the acid.
Where Ka is the acidity equilibrium constant which indicates how well an acid dissociates.
HA <-> H+ + A-

Ka = { [H+] [A-] } / HA
Where [] stands for molar concentration.
Arthis June 1st, 2003, 11:03 AM

Noob ! go and take a book and get close with chemistry before proceeding with explosives !
Hey that's a joke man ! I cannot really tells you what it is really by definition, pKa=-log(Ka), where Ka is the dissolution constant. The highest it is, like for H2SO4 -> 2 H+ + 2 SO42-, the constant of dissolution is really high, so the pKa is very low. So the comparison is:
the lower the pKa the higher the Ka so if citric acid has a pKa of 3.13, the Ka will be 10^(-3.13). (blabla in fact) -> the citric acid is strong enough to decompose and give
enough H+ ions so the sulfamic acid, which is stronger will give enough H+. So it should work. I guess of course that there will not be any side reaction due to the sulfamic
ions.
[EDIT]: vulture answered while I was typing !!!

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > short
question about hno3 - Archive File
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megalomania May 9th, 2003, 11:53 PM

jam007
A new voice
Posts: 36
From:
--------------------------------------------------------------------------------
ok in the nitration proces of rdx it sais that it needs nitric acid free of nitrogen oxides so how do i eliminate this oxides after making it from ammonia bubbled into water????
PHILOU Zrealone
Frequent Poster
Posts: 479
From: Brussels,Belgium,Europe
--------------------------------------------------------------------------------
Could you be more concise I don't see the point: RDX or HNO3 made from ammonia bubbled trough water?????? Maybe some more readings couldn't hut you!
------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
But if you really mean what I guess:
urea is the key to your problem.
NH2-C=O-NH2 gives urea nitrate what react whit the NxOy leading to HNO3, H2O, CO2 and N2!!!!!
------------------
SafetyLast
Frequent Poster
Posts: 233
From: the cretaceous period
Registered: OCT 2000
--------------------------------------------------------------------------------
hey jam007 don't you mean heating ammonium nitrate and bubbling N2O gas into water?
you should just do a search on nitric acid there are a few topics about it already.
I think red and white HNO3 can be used (concentration must be above 80%) also which process will you be using? I suggest either the K process or the W process.
Mr Cool
Frequent Poster
Posts: 991
From: None of your bloody business!
--------------------------------------------------------------------------------
Philou: you've confused me! In the little formula you wrote, the carbon only makes 3 bonds, and the oxygen also makes 3! What's going on?! I'm not saying you're wrong, I
just can't see how it works. Is it like in the ammonium ion, where the N is bonded to 4 H's?
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Yeah NH2-CO-NH2 is actually H2N-C(O)-NH2 or (H2N)2C=O; it is a formalism of organic chemistry to write things like NH3 HN3 HNO3 CO2 and not like O2C H3N N3H or
O3NH....you just have to live with that!I have written it NH2-C=O-NH2 so that everybody can see it is a cetolike form....
------------------
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Ahh, I see now. That makes a lot more sense!
nbk2000
Moderator
Posts: 1135
From: Guess
--------------------------------------------------------------------------------
OH __// / \ = C H OH = C7H6O \__/ 6 5

Which one is easier to write and still get across the structure?
Pop quiz hot shot, what's AcH and MeOH stand for?
As far as nitric from ammonia through water, I thinks he's referring to the catalyzed breakdown of ammonia into nitric oxides, which are then bubbled through the water to
form nitric acid.
------------------
"The knowledge that they fear is a weapon to be used against them"
Go here to download the NBK2000 website PDF.
[This message has been edited by nbk2000 (edited February 17, 2001).]
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Well, C6H5OH (yes, I know the numbers should be subscript but it doesn't seem to be working on my comp. for some reason) is the easiest to write while still getting the
formula accross because it makes it clear that there's a hydroxyl group, although it could be some kind of unsaturated alcohol I guess, because you can't tell that it contains the
benzene ring from just the formula. C6H6O could be loads of things, and the structural formula is just too time consuming to write.
As for the AcH and MeOH, I have no idea (or were you talking to Philou?). I suppose the MeOH could be methylamine hydroxide or something, and the AcH could be acetyl
hydride. But I've never used those abbreviations before so I don't know.
He would need to react the ammonia with oxygen with a catalyst to form water and nitrogen monoxide, and then dissolve the nitrogen monoxide with oxygen into water to
form nitric acid
4NH3 + 5O2 ->(??iron catalyst??)-> 6H2O + 4NO
4NO + 3O2 + 2H2O -> 4HNO3
PHILOU Zrealone
Frequent Poster
Posts: 479
posted March 14, 2001 11:29 AM
--------------------------------------------------------------------------------
MeOH is methyl-hydroxyde or methyl-ol and thus it is methanol CH3-OH an hybrid form often used in org. chem. between chemical formula and written name.
So does AcH; it is acetic protonated thus acetic acid (or more conveniently ethanoic acid CH3-CO2-H (Ac= CH3-CO2(-)))
Marvin May 12th, 2003, 11:19 PM

Just thought Id clear up since it seems to have gone uncorrected...
Bubbling N2O into water will not produce nitric acid.
chemwarrior May 18th, 2003, 03:14 AM

*kewlish voice on* But Marvin, the ACB says its so it MUST be true! The ACB is NEVER WRONG! *kewlish voice off*:p

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > NA from
Ca(NO3)2 - Archive File
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the_wingman
Frequent Poster
Posts: 49
From:
posted 03-31-2001 03:26 PM
--------------------------------------------------------------------------------
I'm not able to obtain nitric acid so I'll try this soon:
Ca(NO3)2 + H2SO4 => 2 HNO3 + CaSO4
Calcium nitrate is freely available as fertilizer.
Has sb tried this before? Is CaSO4 ( which is gypsum) insoluble in nitric acid or will the reaction give HSO4(-)ions (which will stay in solution) ?
pete
Frequent Poster
Posts: 56
From: u.k
posted 04-02-2001 02:01 PM
--------------------------------------------------------------------------------
without the distillation step the nitric acid that you get will be quite impure, and not that concentrated. However the answer to your question is that no the sulphate will not
cpmplex in the nitric acid, however it will be difficult to remove fully, and there will be the formation of an equalibrum in the reaction, so yeild will also be affected.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-06-2001 05:48 AM
--------------------------------------------------------------------------------
Ca(NO3)2 is very hygroscopic so it means you can dissolve a lot in a little water. Add H2SO4 conc and distil.
------------------
the_wingman
Frequent Poster
Posts: 49
From:
posted 04-06-2001 11:13 AM
--------------------------------------------------------------------------------
I think this is not completely correct. If you mix Ca(NO3)2 with a little water you won't get a solution but a hydrated form of it ( for example Ca(NO3)2.2H20 )
gliper October 11th, 2003, 06:28 PM

Do's anyone know if Ca(N03)2 + heat = NO2 + CaO? If so you would have pure HNO3 bubling NO2 through H2O.
also CaO + cole + heet = CaC2 and CaC2 +H2O = welding gas and CaO
Hang-Man October 11th, 2003, 06:47 PM

CaO + cole + heet = CaC2 and CaC2 +H2O = welding gas and CaO
lets just go over a few equation pointers shall we.
if by cole you mean coal, write 'C' coal is carbon

use '-->' instead of '="
don't write X=Y=Z
Balance your equations
don't use generic terms like 'welding gas' I assume that is CO, but you need to write that in formula.
Explain odd statements like this: 'CaC2 and CaC2 + H20' ? do you mean its hydrated?
Anthony October 11th, 2003, 07:45 PM

CaC2 is calcium carbide. Reacted with water, it releases acetylene, which is often used for flame welding.
YayItGoBoom! October 25th, 2003, 08:07 PM

Ahhhhh, my friend and I have been wanting to know how to make CaC2, never thought I could learn something from someone with poor grammer and even worse chemistry
annotations ;) . Hangman, what gliper is trying to say is:
2Ca0 + 4C --(heat)--> 2CaC2 + O2
then
2CaC2 + 2H20 --> 2Ca + 2C2H2 + O2
Though I find it very interesting that Carbon will replace out Oxygen, it seems like CaO would be more stable than CaC2 but I guess not. Anyways thanks that has been
bothering me for a while.
gliper October 27th, 2003, 10:42 PM

First CaO is more stable.
I still don't know if Ca(NO3)2 + heat = Cao +NO2 or not. so don't get your hopes up
and what I read was that KNO3 + heat = K2O + NO2. This thed was about Ca(NO3)2 and geting
old so I thew that idea in.
Can anyone conferm (X)(NO3)x + heat = (X)xO?

Tuatara October 27th, 2003, 11:39 PM

Well, I know for certain that heating Cu(NO3)2 will release NO2, having found out by accident while trying to crystalise my newly made copper nitrate! At that point I had
molten nitrate, not a solution, without realising. (Stupid)
Guerilla October 28th, 2003, 08:07 AM

Found these two
Ca(NO3)2 => CaO + 2 NO2 + 1/2 O2 + 369 kJ/mol
Ca(NO3)2 => CaO + 2 NO2
The latter is probably more reliable. Anyway, the nitrate should start decompose somewhere at 500C degrees. I think I will try this out soon, first drying the Ca(NO3)2 so that
there wont be no water reacting with NOx as I'm only interested in CaO, and then heating the nitrate in a flask till no more NOx is released.
What sort of temps should be used in the CaO + C process, and would it be better to be done in an oxygen free atmosphere?
gliper October 29th, 2003, 03:48 AM

Thanks everyone! I first read that CaO burnt with coal = CaC2 but later some one said he tried that and it diden't work. Doesen't sound likely because the O2 should just
oxadize it back to CaO so O2 redused seems more resonable.
Three notes 1 this will still release CO and CO2 so you can't just seal it. 2 I remember that a normal fame is hot enough. 3 After CaC2 reacts with water it reverts back to CaO
so the reaction can be rerun with more coal and water.
The only remaning question I can think of is, will the acetylene ignite from the heat of its formation?
gliper November 4th, 2003, 08:37 PM

Update: Having looked aroumd CaC2 + H2O aparently will not ignite.
YayItGoBoom! November 14th, 2003, 08:39 PM

Update: Having looked aroumd CaC2 + H2O aparently will not ignite.
Yes, if you try and light a wet pile of CaC2, it won't do crap. But if you collect the gas from this reaction, this is acetylene gas, and sure as hell is flamable! I know this is going
way off topic but I don't want to start a new topic on this.
If you have a burning pile of CaO and carbon, combustion would prevent all oxygen from bonding with the calcium. To keep it from recombining with oxygen, you would have
to stuff out the rest of the oxygen. I am thinking this would be done in a crucible in a metal foundry set up, and quickly cover the top of the crucible with a lid.
rikkitikkitavi December 6th, 2003, 03:22 PM

US3572991...
During preliminary feasibility test with decomposing CaN (in an open steelpan, outdoors) by heating with a blowtorch , first to anhydrous CaN (about 300 C ) and then further ,
I got only a little of NO2. I probably used to much heat since the
Ca(NO)3 => CaO + 2 NO2 + O2 continues with 2NO2=> 2NO + O2.
The NO will quickly react with O2 forming NO2 again , especially if done in a closed vessel where O2 content is higher than in air. (from the decomposition)
Since I had only a crude method of heating and decomposition starts to catch up first when the salt is molten I assume to much heat decomposed the NO2 and combined with
a low decomposition rate diluted the NO in the surrounding air so much that I couldnt see the NO2 forming . But there was an obvious NO2 smell (careful boy, careful :)
As comparison I tried Cu(NO3)2 *5 H2O . First it melted in its own crystalwater, then at about 200 C heavy NO2 smoke formed (which I didnt tried to smell) in the same pan,
same day e t c.
My conclusions are:
It is possible to produce NOx by decomposing CaN
It will take some time to think up of some sort of steel cruicible that is sealed , preventing gases from escaping. It should be easy to recharge with fresh CaN.
Some sort of thermostatic control of heat is needed.
There should be enough gas volume in the system allowing NO react to NO2 (O2 is on excess anyway)
the gas should be cooled (promotes NO2 forming and further N2O4) and absorbed in H2O to yeild HNO3.
BTW I have tried CaN(dried at 200 C ) with H2SO4. What a fucking mess... easier with KNO3 or NaNO3...
/rickard
Rosco Bodine December 6th, 2003, 04:26 PM

Another way in which Calcium Nitrate or Calcium Nitrate / AN hydrated
double salt ( Norsk Hydro manufacture ) might be used is to mix
a hot fairly concentrated solution of it with a similar solution of
Epsom Salt , to form a solution of Magnesium Nitrate and a precipitate
of Calcium Sulfate which is filtered out . The Mg Nitrate solution
could be boiled down to a concentrate , useful as a dehydrating agent
for breaking the azeotrope of 68 per cent nitric acid mixed with the
Mg Nitrate and distilled . This Mg Nitrate "syrup" could be used the same way
as sulfuric acid is used for the same purpose , and recycled by heating
it further to drive off the water before it is used for a new distillation
of nitric .
Alternately , by treatment with sulfuric acid , and distilling the acid / nitrate mixture in the usual way , nitric acid could be produced
directly from the Mg Nitrate , and the byproduct would be Mg Sulfate ,
which , after being rehydrated , is the same Epsom Salt
as is used in the beginning of the process ,
being regenerated for reuse in such a synthetic scheme .
If the presence of Ammonium Nitrate in the original CN / AN double salt

should complicate the process , then boiling the solution with an excess
of lime until no more ammonia is evolved , should convert any AN to CN
so that the remaining solution is entirely a CN solution . Excess lime
could be filtered out before use and reused in subsequent conversions .
simply RED December 14th, 2003, 01:06 PM

I've made conc HNO3 using the hydrated AN/CN fertilizer + H2SO4. And distilling. It works.
It does not work if you don't crush the prills.
gliper February 10th, 2004, 02:33 AM

If you just want CaO it can also be prepared from CaCo3, easyer to find as chalk, lime and soil sweetener than Ca(NO3)2. Just add heat, bypoduct is CO2.
markgollum February 10th, 2004, 01:23 PM

If all you want is CaO then just buy it, I think that Home depot stocks it as lime.
Lime is used to keep the smell down in outhouses. There really isint a way for a backyard hobbyist to make CaC2 via CaO(L) + 3C(S) --> CaC2(L) + CO(g) as the temp
needed is very high, (the reaction starts to happen at 1600 degC).
gliper February 10th, 2004, 09:03 PM

All the lime I have ever seen is CaCO3 (or that and MgCO3 in Dolomite lime), I have heard of slack lime as Ca(OH)2. I recall store bought charcoal gets 2,000 degs C.
Mumble February 10th, 2004, 11:44 PM

Calcium Oxide and Calcium Hydroxide are kind of interchangeable for the term lime. There is Magnesium impurity in the comercial product. CaCO3 probably too, as its formed
from CO2 from the atmosphere acting on CaO. I think all they do is crush lime stone, filter out the rocks and bag it up. I think the general comercial product is around 90%
Ca(OH)2. If you want CaO specifically try burnt lime or quicklime. Hydrated or slaked lime for Calcium Hydroxide.
Centimeter September 13th, 2004, 12:04 AM

I plan to use calcium nitrate to make iron (III) nitrate by mixing solutions of calcium nitrate and iron sulfate. I beleive this will precipitate out calcium sulfate leaving iron (III)
nitrate in solution. Iron sulfate can be purchased at almost any gardening store including home depot. I then plan on using the iron (III) nitrate to produce 68% HNO3 by
decomposing it and bubbling the NOx through water. Of all the metal nitrates I looked up, iron (III) nitrate had the lowest decomposition temperature; ~100*C. Furthermore,
the byproducts of the reaction can be disposed of w/o problems of contaminating your water. The reason I would go through all this trouble is so that I can distill fumming nitric
acid w/o waisting the H2SO4 as it can then be recycled. Does this sond like it will work?

Update: I made a sample batch of calcium nitrate by adding calcium hydroxide to excess nitric acid then evaporating. I then used this to try and make some metal nitrates. I
first tried making iron (III) nitrate by mixing a solution of iron sulfate (probably in the form of ferrous sulfate) and a solution of Ca(NO3)2. A calcium sulfate precipitate clearly
formed, however when I filtered and evaporated off the water it formed an orange syrup rather than a purple solid. I attempted to decompose anyway. It began to smell very
much like nitric acid fumes however there was no visible NO2. Iron (III) nitrate is a bad choice as its low decomposition point makes it difficult to dry properly and it stains one's
glassware. I next tried making aluminum nitrate by mixing a solution of alum of potash and a solution of calcium carbonate. A calcium sulfate precipitate clearly formed and
was filtered off. After drying in an oven, the substance was heated to decomposition. This reaction once again produced a strong nitric acid smell (including what looked like
HNO3 vapor) however no visible NO2 was produced. At this point, I don't think that decomposition of metal nitrates is a very viable method of producing HNO3. I will however
make some more aluminum nitrate and try to collect the observed vapors in my soon to arive distillation kit. I will titrate it and see just how concentrated the acid vapor is. I
guess I will just have to accept that H2SO4 is going to have to be used in a non-recyclable way. But why am I whinning when I just got a job at the hardware that I buy my
H2SO4 from so now I get a 20% discount. :D
ProdigyChild September 17th, 2004, 04:35 PM

It began to smell very much like nitric acid fumes however there was no visible NO2. Iron (III) nitrate is a bad choice as its low decomposition point makes it difficult to dry
properly and it stains one's glassware.
Centimeter, chemistry sometimes demands a bit of patience!
I've done e very similar experiment (described yesterday in the 'concentrating n

itric by decomposition...' thread). I dissolved a screw in dilute HNO3 (over a d
ay). Then I poured the dirty brown liquid into a flat plastic container and put
it on the heating (50° at most) for over 24h. The Fe(NO3)3 is then completel
y dry with no significant decomposition. I dried indoors although I must have had some HNO3 traces left!
Decomposition of the final product is pure fun! In a test tube obvious brown gas after heating with a candle!

What color was your product; mine was definately not purple like the MSDS says it should be. My main problem with the iron method is that it stained all of my glass. Now I
have to boil all of my glass in HCL. I must say that the aluminum nitrate method is a much easier synthesis and I was able to easily get NOx to evolve. It is also easily cleaned
up. The only problem is finding alum that's not ammonium alum. The only alum I can find in the market is ammonium alum. I was however able to utilize a large bag of
potash alum that I acquired from a crystal growing kit. I do admit that I am a sucker for haste and aluminum nitrate is conducive to this tendency. I guess I will give the iron
(III) nitrate method another shot.
tmp September 18th, 2004, 12:53 PM

Centimeter, let me get this straight. You used HNO3 to make a nitrate so that
you can make HNO3 ? Why not just take your existing HNO3 and vacuum
distill it ? On the question of Ca(NO3)2 - melting point for the anhydrous
version is 561 C according to both the 52nd and 81st editions of the CRC.
Centimeter September 19th, 2004, 06:49 PM

Yup, you got that right. My source of calcium nitrate fertilizer is a long ways away so I have to save up a lot of money before I go there so that I can make the trip worth
while. I have plenty of nitric acid, I just wanted to do some experimenting. After all, it will take me a couple weaks to save up enough money. It all sounds logicle in my head!
:p
lucas October 16th, 2004, 04:58 PM

NOTE: All distillations done under reduced pressure obtained by water-jet vacuum pump. Most were conducted using 500ml round bottom flask.
When distilling potassium nitate with sulphuric acid, I typically use 1:1 mass ratio. 100g Sulphuric acid and 100g potassium nitrate has yielded typically approx 60g nitric acid,
which is a high yield. This is close to 1:1 molar ratio. Using 1:1 mass will result in a thick pasty mixture of potassium nitrate and sulphuric acid. This mixture will distill but
doesn't allow easy movement of heat throughout the mixture. It results in the mixture acting like a solid, "melting" at the source of heat before distilling. It provides a pale-
bright yellow nitric acid, depending on particular conditions. The first vapours are deep red, but this soon clears and quickly fades as nitric acid becomes the main gas flowing.
The late stages of the distillation involes a molten mass of KNO3, H2SO4 KHSO4 which is over well 100 degrees C. Since the HNO3 vaporises as it forms, it has little time to
decompose and the acid distilled at this stage is nearlyas pure as in the earlier stages of distillation. The final waste product, mainly composed of KHSO4, can be poured out
while molten, into a very large amount of cold water, using heat resistant gloves, but beware, it will still be evolveing nitric acid fumes at this stage. Cleaning with water is
effective in removing the waste material. Adding cold water to a very hot glass vessel is not advised as cracking may occur!
Use of excess KNO3 is effective in maximising yield of nitric acid with respect to sulphuric acid used. I have obtained 112% yield in moles HNO3 per mole H2SO4, without any
more trouble than otaining 100% I used approximately 20% excess of nitrate. This is done by distilling excess potassium nitrate and forcing, with heat, a second proton to
move from the hydrogensulphate ion to the nitrate which will then vaporise as nitric acid. This means the mixture used to start with will be a particularly thick paste. Even when
using reduced pressure the temperature of vapour passing into the stillhead will be 90 deg C or more later in the distillation. The colour of the condensate is still pale yellow
with this method.
Use of just below, ie 20%, molar ratio of potassium nitrate to sulphuric acid means starting with a viscous fluid which tends to foam on heating. This yields a slightly better
product than the above mixture, but lower final yield, wrt sulphuric acid consumed. I do not enjoy distilling such a mixture as the control of the heat source is a troublesome
affair, trying to maintain vapour production while minimising foaming to a level which won't cause the mixture to overflow.
On one occation I used a separatory funnel instaed of a round bottomflask to recieve the distillate. I tapped off fractions of the acid. Definate differences in colour were noticed.
The acid distilled soon after the initial red fumes cleared were the least coloured. Colouration intensified only slowly as the distillation continued.
All the acid batches produced by this method gave off large amounts of white fumes, even when chilled to 0 deg or -5 deg C. The measured density was always around 1.50
g.cc^-1
The Order October 15th, 2007, 05:56 PM

A journal article exists, studying the solubility of calcium sulfate dihydrate, or gypsum, in nitric acid:
Abstract The solubility of gypsum in 0-30 wt % nitric acid solutions at 20C was studied. The data were compared with the results obtained at 60C.
The journal article appears in the Russian Journal of Applied Chemistry, and can be purchased here:
http://www.springerlink.com/content/mm823x123582j158/
Although I am too cheap to buy this article at the moment, I would be quite interested to know the results. From everything I've gathered so far, calcium sulfate and nitric acid
do not form any sort of matrix of crystals when existing together in solution/slurry.
If equimolar parts of Ca(NO3)2 and H2SO4 were combined (calcium nitrate in saturated solution), I wonder if, after cooling to discourage solubility, the gypsum could then be
filtered through diatomaceous earth (filter sand) placed in a piece of fiber-glass cloth (the kind used for autobody, boats ), and this inside of a glass/plastic funnel which is
directed into a glass bottle.
This method, if practical, could offer an easy OTC method for nitric. If one were to start with say, canning lime (Ca(OH)2) and instant cold-paks (NH4NO3), they could then
evaporate off the ammonia water, and be left with relatively pure Ca(NO3)2, especially if excess lime was added, then filtered before evaporating. Of course, the aqua
ammonia could also be distilled off and salvaged, but of course if such equipment to do so were present in the first place, then distilling nitric would be the first course of action.
Any thoughts?
megalomania October 16th, 2007, 03:20 PM

Well, look at the handy picture I just found. What a serendipitous coincidence...
Solubility of Calcium Sulfate Dihydrate in Nitric Acid at 20oC

Russian Journal of Applied Chemistry, Vol. 76, No. 1, 2003, pp. 156 3157. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 1, 2003, pp. 162-163.
http://img139.imageshack.us/img139/5523/journalmr3.th.gif (http://img139.imageshack.us/my.php?image=journalmr3.gif)
Enkidu October 16th, 2007, 08:32 PM

A journal article exists, studying the solubility of calcium sulfate dihydrate, or gypsum, in nitric acid:
If equimolar parts of Ca(NO3)2 and H2SO4 were combined (calcium nitrate in saturated solution), I wonder if, after cooling to discourage solubility, the gypsum could then be
filtered through diatomaceous earth (filter sand) placed in a piece of fiber-glass cloth (the kind used for autobody, boats ), and this inside of a glass/plastic funnel which is
directed into a glass bottle.
Any thoughts?
You're right, gypsum isn't very soluble in concentrated nitric acid. Unfortunately, there's no gypsum in a calcium nitrate / sulfuric acid solution.
First, you'll have very little water in your solution, assuming you're using the theoretical 98% conc. sulfuric acid. So, CaSO4.(H2O)2 isn't likely.
You won't even have any calcium sulfate (CaSO4) in your solution. You'll have calcium bisulfate - Ca(HSO4)2.
Look at the pKa's for nitric acid vs. a bisulfate. Unless you begin removing nitric acid from the equation, you're not getting any sulfates.

Improvised Manufacture of Nitric Acid > Concentrating HNO3 by decomposing HNO3 - Archive File
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HMTD Factory
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From:
Registered: FEB 2001
posted 03-06-2001 03:57 AM
--------------------------------------------------------------------------------
I guess explosive raw material can be discussed here.
Some idea came up this evening :
1.HNO3 can be made with water and NO2

2.HNO3 will decompose into NO2 in contact with formaldehyde
3. What if a drop of formaldehyde drips into 60%HNO3, fumes NO2, which then bubbles into
another bottle of 60%HNO3?
The decomposed HNO3 is sacrificed, given out

NO2, which concentrated another bottle of HNO3. Excess gas that is not absorbed fast enough can go into another bottle.
Bottles can be cool bathed for better absorbtion.
In industrial process, NO2 bubbled through low conc. HNO3 can lift the concentration to, say, higher than 98%.
Damn I should have found out this when I had

access to some nitric acid.
green beret
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Posts: 101
From: Australia
posted 03-06-2001 05:43 AM
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I also would like to hear any methods of concentrating nitric acid.
Morrigan
Frequent Poster
Posts: 81
From: The Netherlands
posted 03-06-2001 09:52 AM
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If this works than that would be great. It would mean that no sulfuric acid has to be wasted. This can be used in the nitration
instead. And since you don t lo ose a lot of actual HNO3 it would almost be too good to be true . Anyb ody knows o r this works?
Mr Cool
Frequent Poster
Posts: 991
posted 03-06-2001 02:46 PM
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4NO2 + O2 + 2H2O -> 4HNO3
Therefore oxygen will also be needed. The above reaction is how HNO3 is made industrially. I think this is a pretty good idea,
but surely some of the original HNO3 will react with the formaldehyde, releasing NO2 as a product, like when copper reacts with
conc. HNO3?
If we could find a way to break it down with catalysts, or maybe you could heat it to break it down without boiling off any water
and diluting the HNO3 in the second flask, then that would be better.
HMTD Factory
Frequent Poster
Posts: 225
From:
posted 03-06-2001 04:38 PM
--------------------------------------------------------------------------------
Actually oxygen is not involved. When NO2 reacts with water it will produce HNO3 and HNO2. HNO2 can self react to produce
HNO3 and some byproduct(NO and some water).
Beware that when HNO3 is reduced to low concentration, copper will not produce NO2 anymore but will produce NO instead.
Formaldehyde itself is a catalyst.
2NO2 + H2O -> HNO3 + HNO2(absorbtion)

3HNO2 -> HNO3 + 2NO + H2O(self react of HNO2)
----------------------------
net :
3NO2 + H2O -> 2HNO3 + NO
The first flask will be filled with 60% HNO3 and a drip of formalin. it will fume out NO2
in large quantity. Gas is guided into a second flask of HNO3, excess gas not absorbed goes to the third flask of HNO3, excess
gas goes to the fourth...etc.
When the second flask is concentrated, it can be removed for use. The original third flask
will be the second, fourth become third, a new flask of raw HNO3 will be the fourth...
The process will be encouraged under low temperature and high pressure. The first flask will experience the highest pressure,
the second will be the second highest, third the third, foruth the foruth. (due to the liquid pressure need to be overcame in
each flask.)
Using NO2 to concentrate HNO3 is a process not used widely in industry because boiling HNO3 and H2SO4 is cheaper.
Another way to concentrate HNO3 involving H2SO4 is to make weak HNO3 into a salt say
NaNO3. The salt then react with H2SO4 to produce HNO3, which can be distilled out to seperate with Na2SO4 and remaining
H2SO4.
Mr Cool
Frequent Poster
Posts: 991
posted 03-07-2001 04:52 PM
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Oxygen makes it much more efficient, because it will oxidise the NO produced, turning it into NO2, which will dissolve and
make more HNO3. That is why it is used in large scale production.
Using NO2 is not used to concentrate HNO3, it is used to make it in the first place, because it is a great deal cheaper on an
industrial scale than using H2SO4 and a nitrate.
So the formaldehyde isn't used up at all? That's good.
HMTD Factory
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Posts: 225
From:
posted 03-08-2001 03:54 AM
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I know it is used to produce HNO3 but in the previous context NO2 is used to "lift the concentration" of HNO3 so we can call it
"concentrating".
Mr Cool
Frequent Poster
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posted 03-08-2001 04:07 PM
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Yeah I know what you mean.
I still say adding O2 as well is a good idea.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 03-09-2001 09:01 AM
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Heh guys, enough dreams or talk about nothing... let us think a bit:
HNO3 with NO2 should give conc. HNO3 following what you all say!!!!Bullseyesshit
Then enlight my stupid constatations with your big knowledge:
*why the process to make HNO3 from NO/NO2/H2O/O2 can only reach low conc. HNO3 (5%) and that it needs to be distilled to
get the 69% HNO3??????
*If NO2 with HNO3 would turn into conc. HNO3 spontaneously; then why the hell are we so concerned by a little NO2 in our
HNO3 when making let's say PETN, NG, RDX,...red HNO3 should not exist then and thus shouldn't be a problem to us!!!!
Let's hope you got the point!
Think twice before dreaming or affirming things!!!!
------------------
HMTD Factory
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Posts: 225
From:
posted 03-10-2001 01:41 AM
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Because the dissloving of NO2 in water is a reversable process. If the environment favors on direction, the balance will shift.
Sometimes the shift is so insignificant it is
too slow for mass production.
One reason that in industry HNO3 is only made to 70% is that "They can't afford to wait that long" to use one single process.
concentrating HNO3 with H2SO4 (stage 2) will be more cost effective than blowing NO2 into it.
I hope you got the point.
Mr Cool
Frequent Poster
Posts: 991
posted 03-10-2001 08:15 AM
--------------------------------------------------------------------------------
It does not need to be distilled if the conditions are correct. If it needed to be distilled from 5% in industrial processes, this
reaction would not be used because it would be too costly. But it is used, so distillation is unecessary.
NO2 with HNO3 will not turn into conc. HNO3. None of us have said that it will. It needs water and oxygen, and conditions that
favour a reaction.
Like HMTD said, I hope you get the point.
I thought you were better than that.
Edit: this is why HNO3 below a certain conc. is always colourless, not red or brown. The dissolved NO2 will gradually react with
the water in it and O2 from the air to make HNO3. However, high conc. HNO3 does not contain enough water to react all of the
NO2.
[This message has been edited by Mr Cool (edited March 11, 2001).]
firebreether
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From:
posted 03-21-2001 04:35 PM
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You could always just take 70 % HNO3 and distill it the way you would for making HNO3 from KNO3 + H2SO4. like by vaccuum
distilling it. this should work (i think) because the HNO3 has a lower BP and therefore would boil before the H2O that it is
diluted with.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-04-2001 11:18 AM
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I see your points now but stil in industry they don't make 70% nor 100% from that process since you can only acheive a very
low concentration without distillation!
------------------
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
posted 04-04-2001 03:37 PM
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I don't know if this is a stupid idea, Philou, but I don't suppose you recommend electrolysing a low concentration of nitric acid
to drive off the water, thus concentrating the nitrate, do you ? The electrodes would have to be graphite, of course, but this
method, if it did work, would save us all the hassle of screwing around with NOx gasses and sulphuric acid.
CragHack
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From:
posted 04-04-2001 03:59 PM
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that might work in theory but you have to consider the effect the electricty would have on the H+ and the NO3- ions that are in
the solution. now that i brought the question up, would electrolyzing (for lack of a better word) have any effect on the other
components (other than the water) when) in the acid?
------------------
...
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-05-2001 07:49 AM
--------------------------------------------------------------------------------
That would cost a lot of energy; but yes, virtually it is possible, since all voltages and intensity are available quite easily from
transformators, and that at certain voltage only certain reactions occurs.
------------------
HMTD Factory
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Posts: 225
From:
posted 04-06-2001 02:28 AM
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If HNO3 do not decompose under electrolysis in aqeuous solution...like H2SO4...
But the electrode must not be graphite.
HNO3 can oxidize graphite. (Powder factory workers use HNO3 to remove micro carbon particles trapped inside their body
tissue, finger nail for example.)
Bitter
Frequent Poster
Posts: 290
posted 04-06-2001 09:53 AM
--------------------------------------------------------------------------------
What do you suggest then ? Metals can't really be used otherwise they will react (don't forget it's incredibly strong acid we're
making).
I don't think it is going to be appropriate to use platinum and gold and similar metals as electrodes due to cost, at 99%
volume, these metals will probably begin to react with the acid anyway.
HMTD Factory
Frequent Poster
Posts: 225
From:
posted 04-06-2001 12:39 PM
--------------------------------------------------------------------------------
No, platinum or gold don't react with HNO3 at
whatever concentration. Unless somebody is
drunk enough to add some HCl into HNO3.
Why will somebody need a thick rod of platinum or gold for electrode?
Maybe it's not well-known that platinum plated needle electrode is available from lab suppliers...These electrodes really go a
long way...
Marvin May 19th, 2003, 09:28 AM

The action of formaldehyde on nitric acid is not catalyctic, it is a reducing agent. The mixture probably liberates NO2 and CO2.
PHILOU I think was confused by the very old arc process, in which the 2% of NO2 was very difficult to produce az acid. In the
early stages in germany, the weak nitric acid was used to make sodium nitrate, which was then distilled with conc sulphuric to
produce fuming nitric acid. They built a concentrator plant based on magnesium nitrate to solve this problem. Since the
Ostwald process took over, conc nitric acid is not a problem, as neerly pure NO2 can be produced. 99% nitric can be produced
in a batch step with 50atm of oxygen, as has been discussed elsewhere, even miniscule amounts of NO2 in air (eg 0.1%) can
be used to make fairly conc nitric acid 30-50%, this is not practical on an industrial scale though. Electrolysis doesnt work how
youd think it would, as its impossible to liberate hydrogen from conc nitric acid (It gets reduced instead), concentration has to
be achieved by crossed gas liberation, and by ionic mobility differences.
I dont like NO2, and NO2 doesnt like anyone. Forming it in order to concentrate nitric is the long way around a short problem,
and likley to pose much more of a health risk than simply distilling az twice from equal volumes of conc sulphuric....
ProdigyChild September 16th, 2004, 06:44 PM

Some members think 'industrial' and use their easiest way to create highly concentrated nitric acid. Others try to reduce the
need for critical chemical, i.e. chemicals that could raise the interest of some do gooders searching for 'potential terrorists'.
So even it's easy to use sulfuric acid for the purpose easily, it's nice to have other options, no matter, if a bit more poisonous
substances are involved. If to avoid danger, then avoid explosives :)
I've read above, that highly concentrated NO2 or even liquid NO2 DOES react to higher conc. nitric. Even better, if the right
amount of O2 is present at the same time (and the right amount of water).
Not that difficult really! From dilute HNO3 you can produce Fe(NO3)3, dry it at moderate heat. Further heating causes:
Fe(NO3)3 => 1/2 Fe2O3 + 3 NO2 + 3/2 O2
That's exactly the right ratio for turning NO2 and O2 + Water into HNO3!!
I've already decomposed this brown salt in very small amount and it works wonderful! Not more than 200-300° required,
as far as I can estimate. (test tube over candle!)
Feels similar to destillation of HNO3, except you distill over a gas mixture into low conc. HNO3 (or even water). Not difficult to
even produce some pressure, is it?
And I really wonder, if this process involves more danger due to NO2 compared to destillation. Cooling the acid would
condense liquid NO2 on its surface...
I've read that alkali metals decompose like this:
NaNO3 => NaNO2 + 1/2 O2
We all know AN's decomposition(s)!
ALL OTHER salts should decompose like in the formula for iron salt above - according to one of my chemistry books. So
maybe Ca(NO3)2 or Al(NO3)3 would also do the job.
Is there a catch somewhere, why this can't work as described??
Fucking hell, you could possibly build the apparatus out of steel, because
- **cold** conc. nitric does not dissolve Fe
- dry NO2 + O2 possibly, neither, not even in heat
==> High pressure reactor, closed by welding :D
meselfs September 16th, 2004, 09:43 PM

The pressure needs to be 50 bar, I've heard. This is basically impossible for someone without access to a some machinery, eg
lathe & mill.
Steel I would never, ever trust with cold nitric acid, but according to Merck NO2 may be stored in steel reliably if the moisture
content is less then 0.1%.
But note this: aluminum is not attacked by nitric acid. Creepy, aye?
DF90 June 20th, 2007, 01:39 PM

Group 2 nitrates (for example Ca(NO3)2) decompose like this:
Ca(NO3)2 -> 2CaO + 4NO2 + O2
Not sure if this is still an ideal NO2/O2 mixture for dissolving in water/dil. nitric acid.
DF90 June 20th, 2007, 01:54 PM

I completely forgot why i came onto this thread last time I posted :confused:
Basically the idea was making 100% nitric acid, by reacting lower concentration nitric acid with phosphorus pentoxide. The water
in the lower conc. acid will react first to give phosphoric acid (H3PO4) Once all the water has reacted, the phosphorus pentoxide
then reacts with the nitric acid:
6HNO3 + P2O5 -> 3N2O5 + 2H3PO4
The N2O[sub]5 can then be separated (no idea on how to do this experiment practically, just the theory :D), and dissolved in
an equimolar amount of distilled water, yeilding 2 moles of 100% Nitric acid for every mole of N2O[sub]5 dissolved. The only
downside of this method is obtaining the phosphorus pentoxide and the fact that it cannot be regenerated from the
phosphoric acid produced in the reaction, unless of course you react the phosphoric acid with calcium carbonate, then heat the
tricalcium phosphate produced with carbon and sand to over 1000C to distill off white phosphorus, which you can then burn in a
sufficient supply of oxygen to yield phosphorus pentoxide again....
209 June 21st, 2007, 03:17 AM

Probalby one of the most widely known method of producing nitric acid (to us chemists at least) is the H2S04 + KNO3. I have
got buckets of KN03. Sulphuric on the other hand creates a small problem. I had less that 500 mills of pure H2S04 left and I
can't afford to waste it on Nitric. I have got pretty much infinite amounts of drain opener that has a very large concentration of
sulphuic, would this work to make nitric?
If this works, great! Or will I just end up with a liquid that is worth jackshit and a bunch of funky colours? Anyone know what the
outcome concentration on the nitric would be from 94% Sulphuric?
+++++++++
These questions have been asked countless times, and the answers available to anyone who bothers to UTFSE.
NBK
ETCS (Ret) September 6th, 2007, 10:52 PM

The Magnesium Nitrate procedure for distilling high percentage Nitric Acid is workable, however it requires large quantities of
anhydrous Magnesium Nitrate.
Fortunately, Magnesium Oxide is very inexpensive and low percentage Nitric Acid is relatively easy to make on a small scale.
There are new processes which have been patented for the electrolytic dehydration of Nitric Acid which may be possible to
implement on a laboratory scale.
Search "nitric acid dehydration" and you'll find several links to the patents which make very stimulating reading.

It is customary to provide a patent number if you have it. How recent is recent for that electrolytic method? I get over 15000
results using nitric acid dehydration, I don't want to spend weeks wading through that many results since all of them I browsed
so far are false positives unrelated to nitric acid production.
tmp September 9th, 2007, 10:18 PM

Mega, I found 2 patents related to anhydrous HNO3 production via
electrolytic cells. In fact, if the patents are correct, N2O5 in HNO3 can also
be produced. I found patents 5181996 and 6200456 to be very interesting
reading to say the least.
http://www.patentstorm.us/patents/6200456-description.html
The date on 6200456 is March 13, 2001. Because I'm a fan of electrolysis
in general(chlorates/perchlorates) this may be my next project. :D:D:D

That's what I was looking for... Check out the related class of patents, there are good dozen that seem promising: http://
www.freepatentsonline.com/CCL-205-553.html
ETCS (Ret) September 11th, 2007, 11:16 PM

Mega, Tmp,
Sorry about not getting back to you with amplifying data - my phone line has been down for several days until ATT was able to
repair it today. Thanks tmp for the yeomans input with your search results.
I know that searches can result in a lot of extraneous garbage so I should have mentioned that I use the Scroogle scraper
which automatically filters most of the garbage out.
Azido December 10th, 2007, 11:17 PM

Say someone was low on H2SO4, but had an excess of nitrate salts (and water hopefully), could this method maybe save
some valuable resources? Nitrate Salts decomposed to produce NO2, which is subsequently dissolved into water to form the
68% azeotropic acid, which is then concentrated using vacuum distillation with H2SO4? Or is that just me getting excited..
penguin6636 January 1st, 2008, 11:55 PM

If NO2 will dissolve into HNO3 concentrating it, would NO2 suspended above HNO3 in a reaction vessel and brought below its
boiling point react to concentrate the HNO3?
megalomania January 2nd, 2008, 10:11 PM

NO2 reacts with water to form HNO3, so any means of getting the gas to contact water will work. The boiling point of NO2 is
21.1C, so you could add liquid NO2 to water. The reaction forms NO, which escapes the liquid, and then reacts with air to form
more NO2. Industrially they use either flowing water or water spray to mix with NO2 and air because this is the most efficient
way found so far.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Why does
my nitric acid not condense?
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blindreeper June 7th, 2003, 05:22 AM

After making a still I tried to distill some nitric acid. But I got no acid!
I used a 500ml Pyrex brand Erlenmeyer flask as the distilling flask and a 250ml Pyrex brand long necked flat bottom balloon flask as the reciver.
********|-----------------------------------|********/-----\
***/------------------------------------------------ ----- ** /
**/ /----------------------------------------------- ------\_____/
**| |****|_____________________________|************** *
**| |
**| |
**/**\
*/*** \
/______\
^ ^ ^
HEAT
Ignore the * its just to get the pic half decent!
Ok thats my crappy picture. The condenser was on an angle downwards. Tube was just a flourecent tube (light) that was bent and had a 40cm PVC water jacket around it
which had a constant water supply from the bottom of the "condeser" out of the top of it. I put in 32g sulfuric acid (boiled from a batter, I know it was conc. cause I left which
was very stupid and came back to find the lab full of sulfuric acid gas and a beaker billowing of the gas.) and 68g of 13-00-46 KNO3 (put the prills in water and boiled the
water off and dried them). Then I put the KNO3 in the flask. Turned the water on and left that running for 5 minutes to check from problems before I started. The tube was
arounf 1 inch round and was sealed in the 500ml flask with teflon tape. I added the sulfuric acid and gave it a swirl (the acid was at 20 C as that was the outside temp and it
was boiled down weeks ago and stored ina sealed container) Then I connected the flask and put it on my hotplate at 85 C.
There was some red NOx in the flask. IAfter about 10 min of heating there was visible HNO3 vapor in the round botton flask. Note: the RB flask was not sealed in there the
end was just placed over the end of the condener.
What I want to know is why the HNO3 didn't condense? The condenser was 400mm long!
Some reasons I think why the distillation didn't work is that I didn't let the nitrate and sulfuric react (I found this out today, I attempted this 2 days ago)
Arthis June 7th, 2003, 06:12 AM

First, nobody especially likes those crapy pictures. So you should an account on 50megs.com or anywhere to host some decent mspaint made pictures.
Second, starting a new thread about a distillation problem instead of replying into the topic about HNO3 distillation is not what a (especially new) member should do.
Then let's see the problem.
There is no real reaction between HNO3 and sulfuric acid. (same and same explanations again) . HNO3 forms an azeotrope with water, which mean the max conc. you can get
while distilling HNO3 alone is 70% (azeotrope point). At this concentration, the mix comports like a new compound, with special ebullition point, etc. Adding sulfuric acid just
breaks the azeotrope as H2SO4 is very hygroscopic (high conc., say ~90-100%). Once the azeotrope is broken, you can distill your nitric acid as its ebullition point is low (~64-
67C if I remember).
In your case, with KNO3, you need to make it well dissolve in the sulfuric acid for the nitrate ions to be dissolved in acid.
About your distillation system, the HNO3 fumes will condense in contact with the surface of the condenser, so maybe your condenser radius is too wide, even if it's long. The
water in a condenser should go from down to up. Maybe the flush of water is not high enough, then the inside part of the condeser is not well cooled down, and the gas get
out of the condenser with a higher temp. than 64C.
blindreeper June 7th, 2003, 09:03 AM

I apprehsiate the help arthis but I am not that new a member. Secondly this is about the HNO3 not condensing even thought there was ample space for condensation. Sorry for
posting a new topic delete if neccesary.

There's way too much KNO3 to H2SO4 here.
What temperature did you distill at?

Not the temperature in the flask, but the temperature just before the condenser intake.
If you put the hotplate on 85C that wouldn't evaporate much HNO3 as it's boiling point is somewhere around 80C (for pure HNO3 gas).

Improvised Manufacture of Nitric Acid > nitric acid %? - Archive File
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^ B a p h o m et^
New Mem ber
Posts: 31
From : am m an,jordan
posted 04-30-2001 02:27 PM
--------------------------------------------------------------------------------
hail all...
d o e s a n y o n e know what is the % of the HNO3 that goldsm ith use ?
because I have a friend who works with gold(se lling ,m aking rings and earings ...etc)and he is going to sell m e 40 liters of
nitric acid but he doesn't know what is the % of the acid .
s o p lz if anyone know anything about this sub tell m e
------------------
{6@pH0m3t}
do what thou wilt shall be the whole of the law...
ALENGOSVIG1
Moderator
Posts: 766
From : V a n c o u v e r , C a n a d a
posted 04-30-2001 02:39 PM
--------------------------------------------------------------------------------
m oving to misc.
if yo u know the exact am ount in a container you could find its weight (density). then just find the density of given cncentrations
i n a b o o k . a n d m a t c h it up with yours.
------------------
technology is a wonderful servant, but a bitch o f a m aster.
Explosives Archive
10fingers
Freq uent Poster
Posts: 411
From : U SA
posted 04-30-2001 07:55 PM
--------------------------------------------------------------------------------
Nitric acid is generally sold at 68% to 70%. This would h ave a weight per milliter of 1.43 to 1.45 gram s . P u r e 1 0 0 % a c i d h a s a
specific gravity of 1.52. All you need is a accurate scale and an graduated cylinder to determine this.

Goldsmiths would use it for etching silver, which m e a n s t h e c o n c e n t r a t i o n s h o u l d b e a t l e a s t 7 0 % .
M a y b e t h e y e v e n u s e i t t o m a k e a q u a r e g i a , d i s s o l v e t h e g o l d a n d t h e n d e p o s i t i n g a f i n e g o l d l a y e r b y d e c o m position?

Improvised Manufacture of Nitric Acid > Concentrating Nitric Acid - Archive File
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Demolition
Frequent Poster
Posts: 158
From: Australia
posted 02-15-2001 01:17 AM
--------------------------------------------------------------------------------
I recently brought 2.5 litres of 70% Nitric Acid for $20 bucks.I am hoping to make RDX but as the concentration is not high
enough I can not.I've read that by adding concentrated Sulfuric Acid to the Nitric Acid it will distill the Nitric Acid and leave a
concentration of about 95% to 99%.Is this correct and would it be sucificent enough to make R.D.X.All help would be greatly
appreciated.
Demolition
wantsomfet
Frequent Poster
Posts: 236
From: EU
posted 02-15-2001 06:02 AM
--------------------------------------------------------------------------------
If you have proper destillation eqipment, it's no big thing, just distill the HNO3 under vacuum.
------------------
for best catfood visit:
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Demolition
Frequent Poster
Posts: 158
From: Australia
posted 03-08-2001 06:12 AM
--------------------------------------------------------------------------------
quote:
--------------------------------------------------------------------------------
To concentrate nitric acid you mix it with twice it's volume of concentrated sulfuric acid in a distilling flask. Distill it at as low a
temperature as possible. You may have to do this twice to get very highly concentrated nitric.
--------------------------------------------------------------------------------
So does this mean if I want to concentrate 100ml's of 70% Nitric Acid I add 200ml's of concentrated Sulfuric acid and then
distill.
Could it distilled without a vacuum source?
Would it be sufficient enough to make RDX?
All help is greatly appreciated
Demolition
ezekiel
Frequent Poster
Posts: 110
From:
posted 03-08-2001 03:14 PM
--------------------------------------------------------------------------------
no.
not strong enough.
you need pure (that's 100%) nitric acid with minimum impurities for a decent yield.
You may get no yield.
And as for that distillation shit,
you need a vacuum pump (expensive) and jointed glassware (even more expensive) but if anybody wants to borrow mine
then come over.
Adding sulphuric acid is a bummer unless you have a pump - coz when you try to distill the acid out it will decompose.
you wil get a product, but it will be impure (NO2, NO, N2O etc etc).
If you do not have pure acid the reaction will often not happen.
i think about 90% acid by weight (I forget the mass...) is about sufficient if you can't get anthing else.
Oh and BTW red nitric acid is not suitable as you will produce instable shit that is crue and useless.
------------------
Ezekiel
'Things bad begun make strong themselves by ill'

blackadder
Frequent Poster
Posts: 313
From: London
posted 03-08-2001 04:03 PM
--------------------------------------------------------------------------------
Add KNO3 to some 90-99% H2SO4. This way you will obtain 100% pure fuming HNO3.
Look in KIPE for it, read the "RDX manufacturing" section, it has the instructions there.
ALENGOSVIG1
Moderator
Posts: 766
From: Vancouver, Canada
posted 03-08-2001 08:16 PM
--------------------------------------------------------------------------------
You will not get high purity Nitric from kno3 + h2so4 easily.Y ou'll only get high purity acid if you do not overheat, which is
actually quite difficult. If it starts to boil, water will evapourate and condense in the colling coil. You are then left with low purity
acid. Once it starts to boil it will actaully take about 1 min to stop. you must also start off using extrememly pure h2s04. BTW,
technically, there is no such thing as 100% nitric acid.
[This message has been edited by ALENGOSVIG1 (edited March 08, 2001).]
Cricket
Frequent Poster
Posts: 160
From: USA
posted 03-08-2001 09:24 PM
--------------------------------------------------------------------------------
I don't got much time so I can't go in depth. Somewhere, sometime, in a land far, far away, Megalomania had a topic about
how it is possible to make up to 120% (I believe) nitric acid. Just do a search, it should show up even though I haven't saw it
in a long time. It does require some equipment.
ALENGOSVIG1
Moderator
Posts: 766
posted 03-08-2001 10:03 PM
--------------------------------------------------------------------------------
Interesting. i always though that the nitric absorbs water.
Jumala
Frequent Poster
Posts: 200
From: Germany
posted 03-08-2001 10:23 PM
--------------------------------------------------------------------------------
Hallo Demolition,
at first, nitric acid with more than 98-99% is impossible and any stuff cannot have more than 100%. Im not a chemist but
nitric acid needs a little bit of water to be a liquit acid.
(For example: The max. concentration of HCL is 38%)
I think it will be more complicated to concentrate 70% acid up than making new acid from H2SO4 and nitrate.
In my book (Scheidt/Flrke 1942)nitric acid is made without vacuum. It works with a good yield of fuming acid. You need
glassware with NS 29 plugs (erlenmeyer flask, liebig cooler). Rubber, PVC or cork isnt acid resistent.
Perhaps you can concentrate your acid up with the same method by destilling H2SO4 + nitrate and put the arising NO2 into the
weak acid.
ezekiel
Frequent Poster
Posts: 110
From:
posted 03-09-2001 11:48 AM
--------------------------------------------------------------------------------
Ah, so many interesting references!
I'm afraid to say that you can get 100% nitric acid.
Just in the same way that you can get 100% water.
Or salt.
Or wood.
just becasue you have enver ahd it does not mean it does not exist.
Then again, you could be right and hundreds fo years of chemistry and physics is suddenly falsified!
Of course you can get nitric acid from a nitrate salt and sulphuric acid. But it is not pure, not even remotely.
Pure nitric acid, for those still unconvimced, is a steaming liquid. Hence the term "fuming acid". The acid fumes when there are
not enough water molecules to dissolve the gas. Thus some is released. 100% acid will fume alot, as there is not water.
when megalomania spoke of "120% nitric acid"; what he actually said was 120% sulphuric acid.
Sorry guys.
And even then it was only a metaphor. He said it was 120% becasue it was a chemical that could produce 1.2 times of
sulphuric acid.
The chemical was oleum I believe. It is essentailly pure (that's 100%) sulphuric acid with alot of sulphur trioxide dissolved in
it.
And, finally yes you ca nget over 100% of something. Didn't you ever do GCSE level maths?
------------------
Ezekiel
'Things bad begun make strong themselves by ill'
no_name_available
New Member
Posts: 25
From: germany (?)
posted 03-12-2001 04:38 PM
--------------------------------------------------------------------------------
hi,
if i want to synthesise HNO3 by distilling H2SO4 with NO3-salt, which of the following reactions will happen ? i am sure #2) will
do it but i also read #3) somewhere - which is comparable to #1) - which wont work.
1) 1 H2SO4 + 2 KNO3 -> 1 K2SO4 + 2 HNO3
2) 1 H2SO4 + 1 KNO3 -> 1 KHSO4 + 1 HNO3
3) 1 H2SO4 + 2 NH4NO3 -> 1 (NH4)2SO4 + 2 HNO3
4) 1 H2SO4 + 1 NH4NO3 -> 1 NH4HSO4 + 1 HNO3
Thanks for all replies.
HMTD Factory
Frequent Poster
Posts: 225
From:
posted 03-12-2001 08:50 PM
--------------------------------------------------------------------------------
In previous context, ammonium cation will behave like potassium cation. In fact, in most cases an ammonium ion emulates a
potassium ion.
They all can happen depend on quantity of H2SO4.
Mr Cool
Frequent Poster
Posts: 991
posted 03-13-2001 12:56 PM
--------------------------------------------------------------------------------
When he said 120% acid, I thought he meant HNO3 with a load of NO2 dissolved in it, kinda like the HNO3 equivalent of
oleum.
Dhzugasvili
Frequent Poster
Posts: 64
From:
Registered: APR 2001
posted 05-12-2001 09:46 AM
--------------------------------------------------------------------------------
This is what I did: I bubbled NO2 through 70% nitric acid. I managed to get the nitric in the decomposition vessel to
decompose by adding formaldehyde, 40%. the receiving vessel was in an ice bath and tubing was glass. Formaldehyde was
added rapidly sometimes and nitric fumed NO2 in excess. The product in the receiving vessel was a deep green colored nitric
acid, why the fuck is it green? Is it supposed to be, heck, it fumes alright!
Kroways
New Member
Posts: 19
From: Czech Republic
posted 05-12-2001 06:59 PM
--------------------------------------------------------------------------------
ezekiel wrote:
----------------
I'm afraid to say that you can get 100% nitric acid.
Just in the same way that you can get 100% water.
----------------
I'm afraid you are wrong. There is something which they call dynamic equilibrium in the fuming nitric acid. This equilibrium
apply to HNO3 and all types of nitroxen oxide and its di/oligo/mers. It is dynamic because the composition of the acid is not
constant. It depends on current temperature, pressure, presence of light etc.. This causes the colour changes, which
accompany temperature changes etc. There will always be a small amount of substances other than HNO3. The only form of
absolutely pure HNO3 is(in my opinion) an ideal crystal at the temperature 0 K(-273.15C)
On the other hand 100% pure water is quite normal. It will never be 100% practically, but number of 9's(99,99...) can be high
even at the room temperature. You just redistill it so many times in absolutely pure tin apparatus that almost nothing is
dissolved in the final product. The conductivity of pure water is VERY low, because only a small number of ions exist there. For
example it is VERY difficult to obtain pure water with pH 7 by normal distillation. pH of normal distilled water which you buy at
the gas pump is ~5-6, because of CO2 dissolved in it.
So this is for you to better understand HNO3. It is a kind of substance, which is not as stable as others. This is the fact, which
is to be counted in.
ezekiel wrote:
-----------------
The chemical was oleum I believe. It is essentailly pure (that's 100%) sulphuric acid with alot of sulphur trioxide dissolved in
it.
-----------------
Another nice example of dynamic system. Have you ever seen oleum? They told us it is SO3 dissolved in H2SO4 at the
elementary school The reality is different... you can find several different types of molecules, which co-exist here(SO3,
H2S2O7 .. i don't know them all, but can look in some wise book). Therefor the only reason why you can call it 1xx% H2SO4 is
the fact, which you have already written. It is capable to produce 1xx% H2SO4, when water is added.
ezekiel wrote:
-----------------
And, finally yes you ca nget over 100% of something. Didn't you ever do GCSE level maths?
-----------------
I don't know, what 'GCSE level' is, but you are right. 150g of pure water is 150% of 100g pure water. If you earn 30$/hour and
me only 10$/hour, you earn 300% of my wage. But when talking about concentration, it is always lower or equal to 100%. It is
quite simple: c=A/(A + B + .....). Now use your level of maths: can "c" be higher than 1? You are a 101% dummy, aren't you
So don't pontificate others, if you aren't sure what you are talking about...
SantasL.Helper June 17th, 2003, 02:25 PM

Originally posted by megalomania
Demolition
On the other hand 100% pure water is quite normal. It will never be 100% practically, but number of 9's(99,99...) can be high
even at the room temperature. You just redistill it so many times in absolutely pure tin apparatus that almost nothing is
dissolved in the final product. The conductivity of pure water is VERY low, because only a small number of ions exist there. For
example it is VERY difficult to obtain pure water with pH 7 by normal distillation. pH of normal distilled water which you buy at
the gas pump is ~5-6, because of CO2 dissolved in it.
No, water has a very low conductivity cause it is an amfolyte. The very low conductivity IS caused by the very low presence of
ions but those are caused by the reaction H2O <--> H3O + OH which is balanced far to the left. So even 100% pure water
would still have a very low conductivity.
As this is an archive file i suppose nobody has been talking about this subject for ages, but i read it an just felt like posting
my first post....
Hello you all.

-> The conductivity of pure water is VERY low, because only a small number of ions exist there.
->No, water has a very low conductivity cause it is an amfolyte. The very low conductivity IS caused by the very low presence of
ions but those are caused by the reaction H2O <--> H3O + OH which is balanced far to the left.
Ehm, you managed to say exactly the same thing and to sound like a smartass.
Congrats on your first post, since it's highly irrelevant too.
Distilling HNO3 + H2SO4 will usually achieve a higher purity, because this mixture boils more uniformely since there is no
clogging (from KHSO4) in the distilling flask. So, no bumping boiling and much less decomposition.
I've had numerous bad experiences with a water aspirator vacuum pump because of fluctuating water pressure, meaning that
water got sucked back in the receiving flask.
IMHO, if you're not concerned about water usage, use an aspirator and turn the tap WIDE open.
The bloody thing consumes about 400l/hr....
Oh and use one with a flowback protection valve. Nothing sucks like having distilled for hours and then in a moment of
unawareness turning off the tap water, resulting in a load of water getting sucked into your freshly distilled HNO3.
SantasL.Helper June 18th, 2003, 04:53 AM

Originally posted by vulture
->
->
Ehm, you managed to say exactly the same thing and to sound like a smartass.
Congrats on your first post, since it's highly irrelevant too.
Thought he was talking about the water not being pure cause there were substances like salts in it in very low concentration
what caused the conductivity. I just said that even if there weren't salt ions disolved in the water, the water would still be
conductive.
Thanks for not overflaming me though, first posts are always a bitch... I'll try to keep up with your knowledge guys...
Mendeleev November 3rd, 2003, 12:58 PM

Can anyone describe to me in detail how to set up the vacuum pump distillator :confused:? I don't need to know how to make
the actual pump, I just want to know how to connect it to the distilling rig, and furthermore where to connect it to; the initial
flask, the receiver, where?
Thanks
SantasL.Helper November 3rd, 2003, 05:03 PM

You can connect the vacuum source to a vacuum adapter that's located between your receiving flask and the condensor. If i
remember right, you just connect a tube to the adapter. The tube is attached to the vacuum pump.
I've seen pics of the setup before but don't remember where... "bah" :( and as i don't have a vacuum setup myself i don't
know it very precisely.
Believe there are pics of such kind a setup on rogue already though...
Milamber November 3rd, 2003, 07:58 PM

Check out this link
https://www.rhodium.ws/chemistry/equipment/pictures/distillation_big.jpg
Nice picture that should tell you all you need to know to set it all up.
Mumble November 4th, 2003, 07:00 PM

If you have an actual vacuum pump, you really should set up a wash bottle or two between the vacuum pump and the
apparatus. You don't want NOx getting in your pump and messing up anything. If you have a water aspirator its really not a
problem. It may eventually corrode a small amount after running a lot of NOx through it. It will look like this http://
albumen.stanford.edu/library/monographs/monckh/060.gif The short tube goes to the vacuum source, and the long tube goes
to the apparatus. Make sure the longer tube goes close to the bottom. Any solid glass container will work, use the same basic
setup though.
To prevent the suck back of water like Vulture had mentioned, install two on your line. The first should be empty, and the
second should have the water. Now, when I say prevent, I mean prevent from getting in the recieving flask. That is mainly only
a problem with aspirators though. Actually you could use an empty jar on the line to collect any water sucked back through the
aspirator. It was unclear if water was sucked back through the aspirator or wash bottle in Vulture's post. The empty jar is all
you need with an aspirator though. Keep the tubes shorter too, like only half way down for the longest.

Thanks for all the help guys :D, but I've come up with yet another question. The two most widely discussed methods of nitric
acid distillation on the forum are HNO3 + H2SO4 vacuum distillation and KNO3 + H2SO4 heat distillation. The HNO3 + H2SO4
vacuum method has been said to give a more pure product. Well, I was wondering if you could achieve the same purity
product doing the KNO3 distillation method if you did it under a vacuum like the HNO3 + H2SO4?

If people have the use of a vacuum still then they use it for XNO3/H2SO4. Vacuum isn't restricted to HNO3/H2SO4.
knowledgehungry November 5th, 2003, 06:31 PM

Vacuum merely allows the distillation to be carried out at lower temparatures, thus less HNO3 decomposed and NOx formed.
HNO3+ heat--> H2O+NOx. I know many people here now this(at least they should) but im just clarifying since we have had
such a rapid increase in newbies.
McGyver November 6th, 2003, 02:42 PM

If a vacuum pump is necesary, maybe it can be made out of a PC fan. You would just need to get some hose for the right
diameter. A vacuum cleaner motor would probably work the best.

Sorry, there's no way a PC fan is going to pull a useful vacuum.
Ezekiel Kane November 6th, 2003, 10:59 PM

McGyver: I've stacked a few Sunon 80mm fans along the front of my Enermax FS-710 case for intake, and still barely get
enough pull to stick a piece of paper along the front of the computer. Even those huge ~200 mm Delta fans wont pull enough
to vacuum distill nitric acid. Just get a used vacuum pump.
Guerilla November 7th, 2003, 10:46 AM
Get a vacuum aspirator, its cheap and decent for distilling HNO3 (~700mmHg with a water flow of 6l per minute). If you want to
save water, just recirculate it with a separate pump and you are only consuming electricity. Its of course a better option too, if
the flow from your faucet is weaker than that of the external pump.
McGyver November 7th, 2003, 11:27 AM

I have a PC fan for the CPU which spins faster then 5000rpm, the noise takes time to get used to. Im sure it would suck some
of the vapor out if the hose and the fan are air tight. This will probably only work if the fan is directly connected to the flask. It
wont work as well... but it should work a little.

I'm afraid that speed and noise don't qualify a vacuum source :)
Feel free to try it, we're just letting you know that you'll probably be dissapointed with the results. You could always attach a
simple tube to the fan via some paper/tape ducting and see how far you can lift water up the tube. That'd give you a vacuum
rating.
An old vacuum cleaner would be far superior IMO. Aspirators are also cheap and easy to make.

How well will this distillation apparatus work: http://scientificsonline.com/product.asp?pn=3081474 This is obviosly without
vacuum, so can anyone give me an estimate of the achievable concentration by KNO3 + H2SO4 distillation? Can anyone also
tell me where they buy their glassware, e.g. vacuum adapter, 3-way adapter, etc. for the distialltion rig on this link: https://
www.rhodium.ws/chemistry/eq...llation_big.jpg that Milamber showed me?
Mumble November 11th, 2003, 12:40 AM

I got my 3 way adapter and vacuum adapter from www.unitedglasstech.com They seem to be pretty nice. Prices are not bad
compared to elsewhere. I got two 1 L flasks and a 400mm liebig condenser from a guy I know. Then I had to go and break
my condenser. So I need to get a new one or try to melt it together. Occasionally you can find some idiot who has no idea
what he has, selling 600mm fractionating columns for $10 on ebay. Probably goes with all the other supplies.
As far as the apparatus in the link, I don't think it would work for nitric acid. The rubber stoppers holding it all together will be
dissovled by the hot Nitric vapor. If you could tool your own teflon stoppers it might work. The condenser doesn't look to
efficient either though. You're best bet for nitric acid is all glass if you want an "official" apparatus. If you just want nitric acid,
you can probably rig one up. I know there plenty of info about that in this section.

Tis' I once again. This time I was wondering if there are any OTC sources of urea. Will piss work? By the way mumble, thanks
a lot for the glass site, its great :D.
blindreeper November 15th, 2003, 10:36 PM

Mendeleev, are you being serious asking if there are any OTC sources of urea? Check the Great OTC Survey thread. But since
I havn't linked it for you I will tell you anyway. In most supermarkets and garden shops sell 5kg bags for about $10. The
other is in instant cold packs, its either NH4NO3 or Urea :)
Mumble November 16th, 2003, 03:10 AM

Personally all I can get around here in cold packs is Urea. I would recomend going the fertilizer route. It much more cost
effective, and there is no diference in purity. It should say 46-0-0. Its the highest nitrogen % of all common fertilizer sans
liquid ammonia.
Its just a personal thing, but if you're going to use it to remove NOx from the nitric I purify it first. If I don't it gets darker that
it was initially. It seems like there is a large amount of dirt mixed it. It makes a dark brown solution. It is fairly easily
removed by filtration, then recrystalisation. The urea is only slightly yellow tinted afterward. After purification is just fine for
removal of NOx and makes it nice and clear.

Strange that you urea is an off colour. My bag I got was 5 kg full of the whitest white prills. It forms a totally clear solution with
water when I made urea nitrate. Back to nitric acid now...
Mendeleev November 21st, 2003, 12:44 PM

Since a vacuum pump reduces the temperature needed to evaporate nitric acid, at what temperature should I heat the acid if I
am doing distillation with a water aspirator?

I was also wondering what is the maximum practically attainable concentration of nitric acid without a vacuum.
Rosco Bodine November 26th, 2003, 08:39 AM

What is the highest attainable concentration of nitric acid for
an atmospheric distillation would exceed 97 per cent , because
97 per cent is attainable as the predictable result using drain
cleaner grade 92.5 per cent sulfuric acid and once recrystallized
sodium nitrate fertilizer for the precursors . For example ,
from 600ml of drain cleaner added to 600 grams of sodium nitrate
in a two liter round bottom flask and mantle , distilling into an ice water
cooled 500mm Graham condenser equipped with a 500ml receiving
flask which is vented by an interposed side takeoff vacuum adapter ,
equipped with a vent line to carry away any fumes fitted to the tubulature ,
the product will be 375 grams of D. 1.501 pale yellow nitric acid (97 per cent)
The yield on a percentage basis is about 84 per cent at this point
( based on sodium nitrate ) , but pushing the reaction to completion
results in an elevation of temperature and a reduction in the quality of
the acid distilling over , so the distillation is generally terminated
early if the quality of the product obtained is more important than
maximum yield . The dynamics of the reaction are predictable , so
the heat should be brought up slowly and when the mixture does
begin to boil , the heating should be reduced because the reaction
proceeds from its own heat to an extent , and it is easy to overshoot
the boiling point and create a boilover if the reaction is hurried in
the early part of the distillation . Excessive heating is not required
and must be avoided , low and slow heating just sufficient to produce
a smooth distillation is necessary for producing good results .

NH4NO3 works for nitric acid distillation, just as well as KNO3 right? Because I have a much more plentiful source of NH4NO3
than I do KNO3. Thanks.
Blackhawk November 29th, 2003, 12:31 AM

Any common nitrate salt should work, afterall you are just going from
xNO3 + H2SO4 - HNO3 + xSO4
It's not particularly important what 'x' is
babou007 November 29th, 2003, 11:31 AM

That's wrong, BlackHawk
H2SO4 + XNO3 = HNO3 + XHSO4
Rosco Bodine November 29th, 2003, 06:39 PM

Mendeleev ,
Excellent question about substituting ammonium nitrate .

I have half the answer .
For making azeotropic nitric acid 68 per cent which

distills at about 120 Centigrade, Ammonium Nitrate
is actually preferred . There is added to the mixture
sufficient water to account for the water to be contained
in the azeotropic nitric which will result , plus a few
more per cent of theory because the dehydrating action
of the sulfuric tends to disrupt the azeotrope in favor
of more concentrated nitric being produced . A nearly
100 per cent yield of azeotropic nitric acid 68 per cent
is the result from a very smooth and rapid distillation
where the residual mixture remains a liquid
having no precipitated acid sulfate salts at the
120 degree C temperature of distillation .
However , I have never tried to distill more highly concentrated nitric using ammonium nitrate . It may work fine , but there are
some concerns about decomposition using ammonium nitrate under the more extreme
conditions which has inclined me to prefer use of sodium nitrate instead .
Maybe someone else here has experience with producing higher concentrated nitric directly from relatively anhydrous mixtures
of sulfuric acid and ammonium nitrate. It may or may not work the same as when using metallic nitrates .
I would also like to know the full details of anyones experiences using ammonium nitrate .
If there are any decomposition issues with distilling higher concentrations from ammonium nitrate , then there could be used a
two step distillation , where the azeotropic nitric acid is first made using ammonium nitrate , and then mixed with sulfuric acid
and distilled a second time to increase the concentration further to 98 per cent or better .
Microtek December 5th, 2003, 06:30 AM

Before I began to concentrate 62 % HNO3 with H2SO4, I used AN. It gave a reasonably good product which worked for
producing RDX without removing NOx. That said, it did contain quite a lot of NOx ( much more than when using 62 % HNO3 ),
but I cannot say how it compares to distillation of NaNO3/H2SO4, as I have never used metal nitrates for nitric production.
Rosco Bodine December 5th, 2003, 11:09 AM

Microtek ,
When you distilled nitric acid from sulfuric and AN , what

concentration and grade of sulfuric did you use ? Did you
density test the nitric to determine its concentration ?
Were there any problems of surging , or evidences of
decomposition ?
I have distilled nitric several different times using good

equipment and careful control and it is normal for the
nitric to have a bright lemon yellow color , almost a dayglow
flourescent , yet pale yellow colored tint , if that makes sense .
The color is like that bright "Easter yellow" on the little sugar
coated marshmallow candy chicks that are sold for childrens
Easter baskets . The same effect as the bright yellow of picric acid
solutions . If the distillation is hurried , the color intensifies to
a distinctly red rust color . I would speculate that the same
impurity is responsible for both the red and the yellow tints
and it is simply a matter of the concentration of the impurity .
Anyone who has worked with dyes has probably noticed that
concentrated yellow dyes appear more red than yellow , yet
when diluted in solution appear quite distinctly yellow . The
color property is related to the state of subdivision of the color
producing component in solution . Lead styphnate crystals are reddish brown , but drop a few crystals into hot water and the
dilute solution is bright yellow . This illustrates the effect of color density causing an actual color shift with concentration .
The yellow colored nitric is produced when either azeotropic nitric acid
is produced from drain cleaner 93 per cent sulfuric and AN plus water sufficient for the azeotrope , or when 97 per cent nitric is
produced using sodium nitrate and the undiluted drain cleaner sulfuric . In spite of the coloration , both concentrations of nitric
seem to be adequately pure for use in synthesis without further purification . The products I describe are the result of
distillations at normal atmospheric pressure , done in a closed but vented system . Comparison with vacuum distillation
showed no improvement significant enough to warrant the added trouble of vacuum distilling so
I always distill at atmosphere to keep things simpler .
A few times I have seen it mentioned that adding a small amount of silver nitrate to the nitrate acid mixture at the beginning
of the reaction improves the process . The method
is supposedly ancient , going back to the alchemists . I have not tried the use of silver nitrate as a catalyst for the process
so I can't say if this is effective nor do I understand how such
a silver catalyst may work to improve the process . If anyone else has any information regarding the usefulness of silver
nitrate , please share any details . Thanks .
Rosco Bodine December 6th, 2003, 03:58 PM

There is a German patent which describes the production of nitric acid
from ammonium nitrate and sulfuric acid . The English translation
of the patent could be very helpful information for this nitric acid
special project section if anyone can do the translation .
See DE280967
SantasL.Helper January 10th, 2004, 06:35 AM

Guys, on distilling nitric acid a couple of weeks ago, one of my stoppers located on the top of my distilling flask melted away
due to the nitrous oxides. Resulting in now an open output/input hole being there. Is there a matterial other then glass that i
can fill that little hole up with that won't be attacked by the nitric acid gasses nor nitrogen dioxide gasses?
blindreeper January 10th, 2004, 09:29 AM

Not much besides glass resist nitrous oxides and nitric vapour. If the hole is where the still head is located and the
thermometer is inserted (top of still) could you not just go and buy some plumbing tape (poly tetrafulroethylene aka teflon)
and wrap the thermometer with it to make a plug? Or if it's a differnt place, I am sure you can make some sort of plug/ball of
teflon tape to make a plug. PTFE tape is cheap ($1.50 AU) for a 10m roll 1cm wide, may be a good option.
Mumble January 10th, 2004, 06:24 PM

Make sure to get enough layers on the stopper if you're going the wrapping method. When I was distilling with a teflon
wrapped stopper back a few months ago, the nitric acid would actually soak into the teflon. Now my stopper is rubbery on top
like it should be, and rock hard on the bottom, where it would of had contact with the nitric vapors. There wern't a ton of layers,
but there were still enough to protect from melting. It fits in the top nicely now though.
Mendeleev January 11th, 2004, 08:47 PM

A good place to buy cheap vacuum pumps is www.sciplus.com they're in the motors, blowers, pumps section. $10-30. Could
anyone give me an assesment as to how effective they would be?

How long will the teflon layer on the stoppers resist the vapours? And isn't it going to leak into my mixture?

The teflon should resist the Nitric for quite a while, heat is what does the teflon in in my experience.
gliper January 14th, 2004, 08:24 PM

I had a doller store tefflon pot and my 85% wild guess sulferic eat right through the non stick lare in 12 seconds. As I don't
wont to wrek more expencive pans I just use glass now Takes longer but cheaper.
Mumble January 14th, 2004, 10:39 PM

All it takes is a minute scratch, and the sulfuric can get underneath the coating. This would cause gas production, removing the
layer from the pan. At the dollar store, I doubt they have the utmost quality teflon lined pans in the first place. Are you
absolutly positive it was teflon to begin with? One might try a spray on teflon product for lawn mowers I believe. Well, thats
what ours is for. Keeps the grass from sticking to the underside. Anyway, you could spray on 5 or so layers. This might even
work with an el cheapo pan from goodwill.

I've distilled my 53% nitric acid up to a higher concentration by distilling it twice with a double amount of concentrated sulfuric
acid. I distilled it at about 80 degrees celsius gas temperature under normal atmospheric presure.
Problem: my gained fuming red nitric acid's volume was 83 ml and weighed 131 grams thus having a specific weight of about
1,578 kilogram/liter. Now 100% nitric acid has a specific weight of about 1,52. How on earth can my acid be 1,57?!?!
Dave Angel January 15th, 2004, 10:04 AM

Santas, if it's not down to error in measuring equipment, then it could be that the dissolved NOx is raising the mass of the
acid. I believe that the 1.52g/cm3 is the data for white nitric acid.
simply RED January 16th, 2004, 07:54 AM

The measurement is not wrong...
Every method used has error. Positive or negative. Only very good methods have 0,0X accuracy. So you must conduct your
measurement very much times and apply statistic.

I'd go for the raise of weight by the NOx as expected, acid was dark yellow and fuming brown/yellow gasses
Dave Angel January 16th, 2004, 01:08 PM

I've just been doing a bit of searching and found that 100% pure anhydrous white nitric acid should have a density of 1.522
kg/m3, mp -41.6C, bp 84.1C, and should be kept below 0C to prevent decomposition into NOx and water. I think I'm gonna
start storing my nitric in the freezer.
A definition of red fuming I found was where the product contains 'more than 17% NO2 with a density of more than 1480 kg/
m3'. The trouble is this could be 70% HNO3 or 100% HNO3 with dissolved NOx so I'm now not sure if dissolved NOx raises or
lowers the density.
I guess the best method to be sure of your concentration would be to get it as white as you can and then measure the
density.
knowledgehungry January 17th, 2004, 09:30 AM

Dissolved NO2 raises density IIRC.
hodio January 19th, 2004, 09:05 PM

Have you ever heard of distilling the azeotropic 68% nitric acid by extractive rectification using Mg(NO3)2 - Solution? Nitric acid
with a concentration of 99% HNO3 and more can be produced colourless and free of NOx.The column operates at atmospheric
conditions.I dont know the specifics of the process but it sounds very interesting to me.It's called MAGNAC-Process .
snuk5 January 23rd, 2004, 06:33 PM

A little about vacuum pumps for the purpose of distillations:
I have a nice single stage rotary vane pump from Brandt, but I would not dream to use it for distilling nitrous and acidic
vapours. (Should only be done using a special oil)
So that would leave the old water-jet pump. I had two models. A modern PE injection moulded job and an old machined brass
contraption. Both used vast amounts of water.
So I took the brass one and soldered a piece of that thin copper tube that one finds in a fridge, in the jet part. And in the
outlet, I soldered a slightly wider tube that I tapered to widen at the upper end.
After a bit of experimenting with the distance between these parts I found that the vacuum was as good or better, as
obtained with the original version, whilst using les s than 20% of th e water. (less than 3 millibar above the theoretical vapour-
pressure , at the particular water temperature)
If the pressure is high enough and with the appropriate orifices, the ultimate vacuum is independent of the rate of water flow.
The only thing that increases with increased water consumption is the rate of gas removal. (No objection if you have no leaks
or excessive generation of gases in situ.)
So if you want to save a lot of water and wait only a minute or so longer before starting the distillation, modify your pump!
snuk5 January 24th, 2004, 02:13 AM

With reference to getting vacuums from using CPU fans, vacuum cleaners, modified bicycle pumps or attaching your
distillation to yo ur cars carb and revving your engine etc., I wo uld like to mention that it requires a serious vacuum to get a
meaningful depression in your boiling pnt.
Doing the job on Mount Everest would be better than most of the above and would still be pretty useless (especially
considering the input of the cost of your sherpas to schlep it all up there - lol)
I ve got a ne at little boiling point pressure nemograph that shows the re latio n between the boiling point at atm. pres sure
and the expected boiling point at any prevailing vacuum. (down to .005 millibar).
If you have a known boiling point an d a ruler, yo u ll be able to interpolate what to expe ct. I ve found it a grea t tool!
I must have it scanned and on a CD somewhere; if anybody wants it, drop me a line.
Speaking from memory, I recall that the partial vapour pressure of water (@ 20 degrees) is around 17 millibar, so an ideal
water-jet pump would give you the same vacuum.
17 millibar = {(1033 .6 17) / 1033 .6 } * 760 = 748 mm Hg.
Such a vacuum would allow one to boil water at a tempe rature of well 20 degrees of course!
snuk5 January 24th, 2004, 03:42 AM

About Oleum.
I ve got still a lite r of the stuff (Carlo Erba, AR grade cost a blooming fortune)
(When bought by the 200 liter it is way cheaper, but that was too rich for me.)
They call it oleum becau se tha ts the Latin word for oil it is way thicker than n ormal 98% H2SO4.
This stuff is seriously greedy for water! I bought it at the time for making acetone dicarboxylic acid and got some in my face
when things went wrong. My method for ducting off the carbon m o n o x i d e g a s did not work o ut so well (Thanks to the glasses
and bicarb I still have eyes and a face! Maybe the fact that it was very cold and had a lot of citric acid in it helped as well)
Anyway the next time it went OK.
I digress; oleum is made by dissolving SO3 into H2SO4, SO3 being the Acid Anhydride of H2SO4. Now what has this to do with
concentrating HNO3?
Well adding oleum to your nitrating mixture instead of 98% H2SO4 puts less strict criteria on the concentration of your HNO3.
One hundred gram of oleum (20% SO3) will draw water out of HNO3 (aq) to the amount of 6.5 gram, so as to get to the
strength of 98% H2SO4.
Or what of cooling azeotropic HNO3 and simply bubbling in SO3?
If we d be able to get a che ap and reason ably readily available source of SO3, we could forget abou t concentrating HNO3. (If
pig s . etc)
SO3 is made by leading SO2 + O2 over hot vanadium pentoxide. (Electrically heated stainless steel pipe?) Any unoxidized
SO2 would simply not dissolve and escape.
SO2 is dead easy to make
Anybody has some vanadium pentoxide?
Should I dissolve my drop forged tool set in HNO3 and extract the vanadium?

If you bubbling SO3 in azeotropic HNO3 and suppose you get the 32% of water (azeotropic) out to form H2SO4 you gonna
have a lot of problems,like a very efficien cooling system and dont forget that SO3 can be very dangerous .If you find a easy
way to make pure SO3 (which i doubt) i would
cool it to get it solid in an ice bath,but I would put it in my H2SO4 98%.
Now the reaction of making SO3 from SO3 is:
SO2+1/2O2=SO3 and is prepared at 400 c in presence of vanadium(V)oxide catalyst
in lab can be made distilling a mixture of concentraded sulfuric ac. and phosforus(V) oxide .
In both cases it sound very nasty to me,and i have to say that im jealous you have pure oleum for your synthesis!
vulture January 24th, 2004, 03:38 PM

Vanadiumpentoxide is bloody expensive. The trouble is, you need a thin active layer disposed on a large surface of Al2O3 for
example. This isn't much of a problem with elemental metals, because that can be done by hydrogen reducing etc... But V2O5
is a insoluble oxide and thus won't be easy to deposit in a uniform way.
Or what of cooling azeotropic HNO3 and simply bubbling in SO3?
Ever looked at the hydration enthalpy for SO3? Your HNO3 solution will boil and decompose in seconds and explode in your
face if you're looking funny at it.
Marvin January 24th, 2004, 08:49 PM

A little platinised rock wool would probably work wonders here instead of vanadium pentoxide. SO3 tends to form a thick mist
with water, rather than dissolve, I suspect it might do this with nitric acid also. Its dissolved in conc sulphuric industrially, and
this is diluted with water later to get back more conc sulphuric. The biggest problem I see though is that instead of simply not
dissolving, any SO2 not oxidised will reduce the nitric acid, something less than desirable. I think dissolving SO3 into conc
sulphuric is by far the best bet. Maybe in small amounts freezing out the SO3 would be possible and adding this to highly
chilled nitric. Rather exothermic though as vulture has said.

In one of my (few) posts about nitric ac. i pointed out a metod to obtein conc. nitric acid using magnesium nitrate,since that i
did some searching and i found more specific data:
CONCENTRATION OF NITRIC ACID USING MAGNESIUMNITRATE TRIHYDRATE
A warm solution of 69.7 grams of magnesium nitrate trihydrate and 50.6 grams of 70% aqueous nitric acid is cooled stepwise
and filtered at each temperature point. Solid magnesium nitrate hexahydrate is recovered in the following amounts: 35.31
grams at 35.degree. C., 12.05 grams at 20.degree. C., and 6.18 grams at 0.degree. C. The recovered 98% nitric acid filtrate
(16.42 grams) is suitable for use in aromatic nitration reactions.
Unluckily in this moment i cant attempt to get it done(my lab has gone!but Im working to rebuild)
so i would like to know if it's suitable in field labs.
powdermunkey January 26th, 2004, 01:15 PM

A cheap and easy source of useable vacuum pumps is old refrigerators. The pumps will pull a very useable vacuum- typically
down to about 10 mT. I go to a metal recycling center and buy pumps for about 62 cents a pound. Nitric oxides will eat the
insides of the pump eventually. Would it be feasible to put a container of slightly moistened baking soda ahead of the pump,
to catch the fumes? Also, isnt polyethylene resistant to HNO3 and its vapor, so that I could cut a plug out of a PE cutting
board, for instance? What sort of protective gear is advised while distilling concentrated acids? Thanks all. P Munkey.
Dave Angel January 26th, 2004, 07:25 PM

I use a solution of sodium hydroxide in water to bubble my fumes through, that works well but remember to use a buffer flask
in case of suck back!
As for safety gear, always wear your goggles. I also put my respirator on when disconnecting the flasks after distillation and
use nitrile gloves to handle the cool parts, thermally insulated gloves to handle the hot flask. If you don't have a lab coat then
some old clothes will do. Standard lab safety equipment really.
vulture January 27th, 2004, 01:18 PM

Hodio, that is rather interesting. I did know that Mg(NO3)2 is used to break the azeotrope (more easily recycled than H2SO4)
when distilling, but I didn't know it could be done this way.
I assume anhydrous Mg(NO3)2 will work even better?
EDIT: If you really want to try the SO3 method, it might be advisable to produce it by calcinating a sulfate.
snuk5 February 13th, 2004, 04:38 PM

H m m m , I have to confess that I m q u ite convinced that the p roduction of SO3 is better reserved for the prod uction of oleum -
when one can t buy it. (Or affo rd AR grad e!).
At an y rate if we d o a bit of molar math s, wed find out that the merits are but relative. H2O is but a light molecule and it
takes a lot of Oleum to convert it to H2SO4.
I was just bouncing off an idea that was not well thought out. The comments made in reaction to my post have been duly
noted. Even a less than perfect idea can lead to useful comments!
Having said that, I do not think that the strongly exothermic nature of the process is an objection. With enough lengths of
high grade stainless steel (eg.316L) coiled tube, and cooled water-flow any amount of heat can be dispensed with.
BTW. I found this a nice way of cooling the acid mixture when making larger amounts of NG. To aid the bending, I packed up
10 mm tube of stainless steel tube with salt and stoppered the ends. Then I coiled it in a coil of about 115 mm diam. Then I
flushed out the salt with a smaller tube. Use soft / annealed (pref. seamless) tube.The Stainless steel did not perish, due to
the moderate / lower temperatures and the high concentration of the acid. In fact I used even a stainless steel pot as my
reaction vessel.
Regarding the HNO3 concentrating; the MgNO3 process is one of the preferred methods in industry. They actually like to use it
in the form of a saturated solution (i.e added water!) as this is easier handled than solids.
I reckon that for the home lab both the H2SO4 and the KNO3 methods are also quite acceptable but they have their
drawbacks in the equipment department: Good and big glass is expensive and it breaks! The niter-cake (K2/HK-SO4 residue)
is difficult to remove at the end of the distillation). The need for a vacuum necessitates both a vacuum pump and leak-free
(ground glass) joints etc.
I have never tried it myself, but if I d needed fuming nitric acid now, I d try the methelene chloride extraction m ethod.
Can anybody give details about their experience with this process?
JoeJablomy February 15th, 2004, 09:51 AM

I've never dealt with these guys, but they seem to sell some interesting stuff, including the aforementioned vanadium
pentoxide.
http://www.micronmetals.com/vanadium_pentoxide.htm
vulture February 15th, 2004, 11:38 AM
I have never tried it myself, but if I d needed fuming nitric acid now, I d try the methelene chloride extraction m ethod.
Can anybody give details about their experience with this process?
Please, don't make yourself suffer from fatigue caused by searching:
http://www.roguesci.org/theforum/showthread.php?t=3157
:rolleyes:
Jetex Kid February 15th, 2004, 10:33 PM

The information on magnesium nitrate may be found in US Patent 5,012,019, along with good news, such as that MN+6H2O
regenerates to reusable MN+3H2O at between 120C and 140C.
Also, MN is inexpensive and available at pyrotechnic houses if you are not a DIY type. I suspect that completely dehydrating
MN would damage the basic molecule, perhaps driving off oxygen. Otherwise, it might rival P2O5.
Regarding the creation of new nitric acid via the sulfuric acid-and-nitrate route, it is difficult to distill sulfuric from the final
mixture of sulfuric and nitric acids. If one used pure sulfuric acid and an excess of nitrate, the only liquid present at the end
would be NA, thus eliminating distillation. Comments?
vulture February 16th, 2004, 06:58 AM

is difficult to distill sulfuric from the final mixture of sulfuric and nitric acids.
Huh? What's your point? Nitric acid is much more volatile than sulfuric acid and thus the NA will distill over, not the sulfuric acid.
Using excess nitrate will cause a nice goo to form in your heating flask along with horrible bumping.
akinrog February 19th, 2004, 03:20 AM

Maybe somebody else suggested this before. (I searched forum but could not find anything directly describing this.) I saw this
method on rhodium's site (http://www.rhodium.ws) though I don't know exact URL.
Although it was not covered in the rhodium's site, in past SO3 was prepared by heating Fe2(SO4)3 to decompose it to FeSO4
to give off SO3. Reaction is something like this
Fe2(SO4)3 -> 2 FeSO4 + SO3 + 1/2 O2.
At rhodium's site, SO3 is prepared by using KHSO4. First it is heated to give of H2O (which is discarded) and Potassium
Pyrosulphate (which remains in heated flask) and then further heated (this time more vigorously) to give off SO3. The SO3
released was collected in a flask cooled by some sort of cold bath. SO3 may be used to create oleum which is as far as I can
see highly wanted by some members. ;)
IMHO, iron tri sulfate procedure is more feasible for me which during my high school years is contained in the chemistry
textbooks, as far as I remember. Since you may use cheap battery acid to create iron trisulfate, dry it and decompose it into
SO3 by heating. Since obtained Ferrous sulfate is recyclable, you may use it for obtaining ferric sulfate again and decompose
it into SO3.
HTH
Roy Paci February 23rd, 2004, 06:46 AM

So sorry for the stupid question, this is my first post. I distilled nitric acid. But it gelatinizes cotton only when it is mixed with
98% nitric acid. So I guess it is not enough concentrated, even for alchool nitration, am I wrong? It is clear orange and it
fumes very light yellow/orange vapours. Thank you for any comment or suggestion.
simply RED February 23rd, 2004, 07:32 AM

and it fumes very light yellow/orange vapours?
Really? At what temperature?
At 0-10 degrees Celsius 95% HNO3 fumes VERY intensively forming totally white fumes. Opening the jar means filling the
room with fumes. It is impossible to make RDX with such acid where other people live.
At 10 degrees "absolute" nitric acid fumes red. Opening the bottle releases red cloud in front of your face! Never keep such
acid at room temp!
Roy Paci February 23rd, 2004, 06:37 PM

Thanks red!
An increase of the WHITE fumes(fumes seem more effectively white) occurs when organic stuff and whatsoever get close to the
surface of my acid. Do you think that checking the density would be a reliable way to get a correct measurement of the purity
of the NA?
Unfortunately I got my knowledge about red, NO2 fumes :eek:
nous February 23rd, 2004, 09:11 PM

which i came across from my fellow bees from the hive..
Nitric acid
Into a 250ml flask with stirbar, set up for distillation, were carefully1 introduced 122g 93% H2SO4 (1.16mol), 100g NaNO3
(1.18mol) and 74ml H2O. The flask was heated on oil bath with stirring and a yellow liquid was distilled off (128C)2. When the
distillation speed slowed considerably and the temperature in the stillhead dropped below 100C a first fraction was taken
(96ml, 126.85g), 37ml H2O where added and a second fraction was distilled off (36ml, 37.83g). Both fractions were titrated
against NaOH to give 10.8mol/l resp. 1.3mol/l3. The two fractions were combined and diluted to 382ml to give 382ml of an
18% HNO3 solution. (Yield: 92% from NaNO3)
Notes:
1: And I mean carefully, this gets _very_ hot.
2: At first some nitrous oxides (orange gas) are produced. But the amounts are so small that there is no danger whatsoever.
3: 4g NaOH were dissolved in 1l H2O to give a 0.1N solution, 1ml of reaction mixture was diluted to 100ml and 10ml of this
solution were titrated against the NaOH solution. Usually the NaOH itself would have to be titrated against an acid of known
concentration, but the results fit very well with the measured densities.
simply RED February 24th, 2004, 10:45 AM

nous, this is not for here, this is for a thread: how to get diluted HNO3!
Yes, correct masurement of the HNO3 density gives reliable data about ist concentration +/-3-4%.
Mendeleev April 2nd, 2004, 02:24 AM

I recently came upon a pdf describing an industrial process for production of +98% nitric acid without distilling with sulfuric acid.
The Ostwald process is a three step for making nitric acid out of ammonia and oxygen:
4 NH3 + 5 O2 ---> 4 NO + 6 H2O

2 NO + O2 ---> 2 NO2
3NO2 +1 H2O ---> 2HNO3 + 1 NO
This yields around azeotropic acid. However the DSN (Direct Strong Nitric Acid) method stops at the second step, producing a
lot of NO2 and some dilute HNO3. The NO2 is then condensed, pressurized and cooled forming N2O4, which reacts with oxygen
to give nearly anhydrous nitric acid. The pdf describing it is www.epa.gov/ttn/catc/dir1/nitric.pdf . My question is this, N2O4 and
O2 will give two nitrate groups, where do they pull the hydrogen out, or did the paper simply omit that part? Also, it mentions
that the DSN process is not commonly used in the United States. Why?
akinrog April 2nd, 2004, 04:17 AM

The pdf describing it is www.epa.gov/ttn/catc/dir1/nitric.pdf.
Sorry but this link does not work for me.
Can you check it please? I want to examine the pdf.
pdbm April 2nd, 2004, 08:36 AM

Has not anyone tryed N2O5 + H2O = HNO3 + heat
u just need to get the amounts right, but Not many people have N2O5?
:confused:
Mendeleev April 2nd, 2004, 12:52 PM

I just tried it and it worked fine, it begins to automatically download the pdf.
tiac03 April 5th, 2004, 12:46 AM

I don't know how useless this information is but I was reading a chem book and it had a table of acids.. so since we or you's
are talking about Nitric acid I figured I would post the information from the table.
Density g/ml at 20 deg C [1.50]

Melting point deg C [-42]
Boiling Point deg C [86]
Solubility in water Infinitely soluble
Amount in concentrated solution wt % [69]
I know I am probably stating stuff y'all know but figured it is better to post something twice (or more) than never at all.

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Arthis
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From:
posted 05-09-2001 02:45 PM
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Humm, well I know this type of topics is frequent but I just tried since I managed to have a distillation set (in fact to complete it), and I remembered that nitric acid was a
good thing, useful thing to make with it, instead of alcool (I don't drink, and it smells bad when distilled). So I just tried tonight, a while before taking my shower and go to
bed, very fastly. I didn't cooled the gas I got, but I would like to know if everything's OK.
When I heat NH4NO3 with 95% sulfuric acid, I get white gases, which come up the Vigreux' column, then go threw the cooler (I didn't make water go into it because I need to
make a system for it). The white smell acid; And there is liquid which go down the column (normally it means that the column isn't at the good temperature, like a chiminea).
this liquid is red. So, I know that I must cool, and all that, but before make all that, I just would like to know if the reaction is good, I mean if I'll get HNO3 if I cool.
And what is the red liquid ? concentrated nitric acid should make red fumes, but I never heard about red acid. What would be the formula of the white coulds ?
Thanks.
FadeToBlackened
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Posts: 201
From: Hell
Registered: MAR 2001
posted 05-09-2001 05:39 PM
--------------------------------------------------------------------------------
Red liquid. Sounds like red fuming nitric acid to me. An excess of NO2 (red gas) dissolved. I dont know what the white stuff is.
zaibatsu
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From: England
posted 05-10-2001 02:35 AM
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is the white stuff H2SO4?
Bitter
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posted 05-10-2001 09:50 AM
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COuld it be a little gaseous ammonia (NH3)?
Arthis
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From:
posted 05-10-2001 11:44 AM
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What's the reaction when you distillate AN and sulfuric acid ? I think HNO3 is gaz then is cooled into the aqueous form.
Do you need to make the gazes you have bublle into water ?
FadeToBlackened
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From: Hell
posted 05-10-2001 05:21 PM
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I believe NBK2000 has said that pure ammonia can make white smokey stuff, so i suppose it could be. Sulfuric acid is supposed to make white smoke if it gets too hot, though.
Arthis
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From:
posted 05-11-2001 12:04 PM
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I tried to make nitrix acid again, with water in Liebig's tube to cool the gases. I obtained red gases, as I waited. Vigreux's column was wet because it hadn't dried since I
washed it, and I obtained yellow liquid, not very acid compared to my 57 % nitric acid. Hum, I tried again and as Vigreux's column wasn't wet any more, red gases didn't cool
enough or I don't know but I couldn't obtain any liquid: the gases instead of condensating, get in the beaker and "fly" away. So I tried to make red gases bubble in the yellow
lliquid, but I couldn't obtain anything. I don't know what to do else.
What is wrong ? Has anyone tried before, and it worked ? Any advice ?
And would anyone know the reaction which happens ?
I use AN with sulfuric acid. Need I to use salpeter or sodium nitrate ? Are the red gases NO2 ?
Many questions, hope someone can answer. Thanks.
FadeToBlackened
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From: Hell
posted 05-11-2001 05:20 PM
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I would say yes, the red gases are NO2 (or possibly NO).
10fingers
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posted 05-13-2001 08:20 AM
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Arthis
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From:
posted 05-15-2001 11:18 AM
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I searched in the Forum but couldn't find any topic where it's said how to purify it. How do you do ? I remember that a possible way was to put it in water, then filter, but don't
really remember. And what is the max temperature you need to distilate nitric acid ?
SATANIC
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From: australia
posted 05-16-2001 02:52 AM
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to purify ammonium nitrate, add water until it is all dissolved, and filter out any solids that won't dissolve( chalk etc. in fertiliser grade- as fire depressant) then heat until the
water has completely evapourated, this leaves the AN in long crystals, which are also easier to crush.
DarkAngel
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posted 05-16-2001 04:34 AM
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http://theforum.virtualave.net/ubb/Forum5/HTML/000621.html
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DarkAngel
For explosives and stuff go to Section1 http://www.section1.f2s.com And http://run.to/section1

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Arthis
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From:
posted 05-16-2001 10:05 AM
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Maybe I didn't use the right search keywords.
How may you be sure that chemicals added don't dissolve ? I try anyway. Thanks
Anthony
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From: England
posted 05-16-2001 06:09 PM
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I wanted to reduce some AN prills to powder the other day, I dissolved the NA in water nad then boiled the solution with the intention of being left with a mass of dry crystals.
What actually happened was it seemed to straight from a boiling AN solution to Boiling liquid AN! I only noticed because of the huge amount of smoke coming off it. Less heat
next time methinks
Gab
New Member
Posts: 14
From: Qubec, Canada
posted 05-16-2001 10:24 PM
--------------------------------------------------------------------------------
Be careful as there is NO2 in this smoke.
c0deblue
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From:
posted 05-16-2001 11:59 PM
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Not to mention the fact that when molten AN starts giving off smoke it only has to get a little hotter before it explodes. Several texts mention that 275 degrees C is the "magic
number".
zaibatsu
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From: England
posted 05-17-2001 02:40 AM
--------------------------------------------------------------------------------
If when you heat AN you get NO2, then can't you bubble that through HNO3 to concentrate it more?
wantsomfet
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From: EU
posted 05-17-2001 06:34 AM
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Heating NH4NO3 results in formation of N2O, H2O. NH4NO3 --> N2O + 2H2O + 83 kJ.
Read this: http://internettrash.com/users/altreal/hno3/hno3usenet2.html
The german patent that is referred to by F.Z. states to use 1 mol NH4NO3 and min. 1 mole H2SO4 to ensure best reaction preformance.
http://odin.prohosting.com/~ratfuck/de280967.zip
------------------
kangaroooo.cjb.net
Arthis
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From:
posted 05-18-2001 09:02 AM
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I don't think that 275C is the magic number, otherwise it would be extremly easy to detonate some AN. Think that a cigarette is about 750C. AP would detonate it easily. And
a thermite too. We would just have to mix AN and thermit to make a powerful explosive. I think.
And who knows the reaction which occurs when you make nitric acid from N2O or NO3- ?

The white fumes are HNO3 gas ofcourse! Any NH3 fumes would be immedialty neutralized by the HNO3 to NH4NO3, so you can assume that it does not exist in free form in
these conditions.
Furthermore, using a vigreux column when distilling nitric acid is a waste of energy and a waste of nitric acid. A vigreux column is intended to separate liquids that have very
close boiling points. In this case we're only dealing with HNO3 fumes (H2O is bonded by H2SO4) and a Vigreux column will require higher temperatures which will cause more
decomposition.
NO3- in solution coming from a nitrate salt is a neutral species because it's the anion of a strong acid, therefore it will not protonate in aquatic or weakly acidic environment.
Only strong acids like H2SO4 are able to protonate it to HNO3. This reaction goes for all nitrates.
With NO2 you need oxygen and water:
4NO2 + O2 + 2H2O <--> 4HNO3

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ALENGOSVIG1
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posted 01-18-2001 02:41 PM
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is nitric acid used in developing photographs? if so, what conc. is it?
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Rhadon
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From: Germany
posted 01-18-2001 03:20 PM
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I'm pretty sure that HNO3 isn't used as a developer, but probably you can get your nitric acid from a pharmacy like I did - I asked for it in a shop dealing with colors (don't know
how shops of this kind are called, sorry), so they went to the parmacy and bought it for me. Later on I went into this drugstore myself and asked for sulfuric acid. They were
somew hat suspicious but I could make them beliefe that I wouldn't do anything illegal w ith it, so they gave me 2 liters.
Mr Cool
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posted 01-18-2001 03:33 PM
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I think 70% HNO3 can be found at large, professional art suppliers for etching copper. Ferric chloride is more common though. I've also heard of either H2SO4 or HNO3 being
sold at jewellry equipment suppliers for cleaning gold I think, but I can't remember w hich it w as!
Agent Blak
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From: Sk. Canada
posted 01-18-2001 05:22 PM
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How much did you pay for your Nitric Acid(HNO3)?
------------------
A wise man once said:
"... As He Waits For The Time When The Last Become First And,
The First Shall Become last"
--RATM
Agent Blak-------OUT!!
Anthony
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From: England
posted 01-18-2001 06:24 PM
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My Father does a bit of photography so I had a rumage through his darkroom but I couldn't find anything interesting (lots of big names). I've never heard of HNO3 being used
for developing, maybe it w as once used for etching/burning an image in some early kind of photo's, I don't know . I'll have another look tommorrow and post a list of all the
chemicals I can find and maybe someone will notice one useful for something.
Mmanwitgun
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From:
posted 01-18-2001 10:28 PM
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If some art people ask you why you need nitric acid, tell them you need it for lithography. Your supposed to mix it w ith gum of arabic or something.
~Dave
mongo blongo
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From: I live in a Creosote Bush!
Registered: JUN 2001
posted 06-23-2001 01:41 PM
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i think you can also buy nitric acid from w here carpenters get their varnish and stuff
i think ther sell nitric acid for pine firnishes or something. i also think they sell loads of usefull chemicals but i dont know if u have to be licenced to buy it or something.
one company in the uk is Fiddes & son ltd
John456
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From:
posted 06-23-2001 01:46 PM
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At an auto detailing shop near me they sell 70% HNO3 for cleaning aluminum parts before anodizing them. Its sorta expensive ($14 a liter) and they got suspicious after i
bought a couple liters so i prefer to make my own.
J
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Posts: 602
From: United Kingdom
posted 06-23-2001 02:16 PM
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It's used in Intaglio, etching copper. I think the concentration is usually 70%.
It w as used in photography, unfortunately this was about 100 years ago :-( I think some people still use it for this purpose (something to do with preparing a type of
photographic plate involving Pt IIRC), but not enough to make it a common source.
J
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zaibatsu
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From: England
posted 06-23-2001 06:38 PM
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Aqua fortis (strong waater) used to be used in photography, it is HNO3, but around 10% IIRC, so that is a possible source. I have seen it used for lowering the PH of soil though,
so it is used in a w ide variety of places.
Demolition
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From: Australia
posted 06-23-2001 11:44 PM
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I get my Nitric Acid (70%) from a local chemist for about $25 Aus dollars.
A43tg37 June 21st, 2003, 01:51 PM

Rochester Midland makes a 20% nitric acid stainless steel cleaner/passivating solution called Brite 'N Shine. I know 20% isn't much, but it can be concentrated; plus, someone
mentioned a 10% HNO3 source in this thread, so I feel it is appropriate to mention one that has 20% HNO3. The good thing about this is that unlike most "passivating cleaners"
it is (from the MSDS anyhow) only nitric acid and water; no phosphoric acid mixed in like almost all other passivasting cleaners. And it looks to be OTC. Check janitorial supply
stores, institutional supply stores, and even farm supply stores, the latter is where I first saw a bottle of this stuff just sitting on the shelf.
YayItGoBoom! October 23rd, 2003, 09:39 PM

Not sure how much this w ill help you, but silver nitrate is used in photograpy. It can easily be mixed with other chemicals to cause a double replacement reaction and precipitate
out the silver (arg I w ish I had my insoluability chart) umm to take a guess I would say Sodium Hydroxide, giving you Silver Hydroxide (filter this out) and aquaous Sodium
Nitrate (chilean nitrate, similar to saltpetre).
Also, a quick search for Silver Nitrate brings up a nice safety warning page.
Silver nitrate should never be mixed w ith ammonia compounds as it can form azides which are powerful explosives. Silver nitrate is an oxidizer and should be treated as such.
Never mix with finely particulated metals such as aluminum or zinc. Also avoid contact with organics.
http://ww w.bostick-sullivan.com/silver.htm
And I'm sure you wouldn't want to form any azides now w ould we :D .
Tuatara October 24th, 2003, 12:06 AM

Now thats just plain silly. 25kg of KNO3 cost me $25. How much do you think 25kg of AgNO3 w ould cost?
Also it would make more sense to add HCl, precipitating AgCl, leaving HNO3!
Layoff the happy cabbage for a few days!
Milamber October 24th, 2003, 03:51 AM

The silver nitrate thing could, how ever, provide another reason to buy it - you see, as a photographer, one may find it very expensive to buy silver nitrate, but one can just buy
some nitric acid and some silver bullion, w hich works out much cheaper in the long run ;)
Or, alternatively, you use it to recycle silver chloride formed in the various processes. Just something if you need an excuse to buy the stuff (you know , for those lucky enough
to know of a supplier).
In addition, nitric acid is used (get this!) as a preservative for pyrogallol, w hich is a photographic developer. The reason they use nitric is that pyro is a damn good oxidant, so
you need to store it in/with something that is stronger - you don't want to waste your pyrogallol, seeing how expensive it can be... so check around for a photography shop and
see if they have it or can get it in for you. You might find other interesting stuff there, too, so have a browse.
aikon October 24th, 2003, 02:46 PM

to milamber:
pyrogallol is an outdated chemical in photography. therefore it's not a good excuse for buying nitric acid.

Silver nitrate w ould indeed be extortionate, about 10k US for 25kg that amount. Though it should be recyclable, I havnt found a way of turning AgCl into anything useful without
needing a blowtortch. Anyone have a good method? Is the carbonate less soluable?
Silver nitrate and ammonia do not form an azide. What can ppt is fulminating silver, which at best guess is a hydrated nitride/imide. This is also explosive, but impossible to
handle.
Pyrogallol is a reducing agent. If you make it alkaline it will start absorbing oxygen from the air. An alkaline solution of its salts are a good w ay to quantativly determine the
amount of oxygen in air from loss in volume. Based on this infomation, it would make sense that keeping it acid should help preserve it.
Milamber October 24th, 2003, 11:15 PM

aikon - I guess it depends on where you go. I've been to about 3 photography shops recently, and two of them had pyrogallol. Apparently it can be used to make some fairly
cool prints, but because of the toxicity and instability, people try to dodge it. If you were a fanatic, though, I guess you'd try it!
Marvin - first, thanks for the correction about how pyro w orks... i was half asleep, and the oxygen absorption in alkali somehow twisted itself around to make pyro an oxidant...
particularly when you realise I totally forgot about the base... anyway, you're right about why the acid is needed.
I have a method lying around here somew here for reducing AgCl to Ag metal, using either zinc or glucose. The yeilds are fairly damned good - first try using zinc gave about
97% conversion, w hile glucose gave about 50%, but i was being fairly sloppy so you should be able to get better. Then you would boil the silver in concentrated HNO3. I can
find it for you if you w ould like.
kano420 November 16th, 2003, 07:59 PM

ya i'm just a beginner in this whole explosives thing but i've been getting wet behind the ears.
I had some expirence using nitric acid in a metallography class, so if your looking for an excuse to buy nitric acid
its used in metallurgy for ecthing surfaces on heat treated parts for viewing the crystaline structure of the metal
under a high powered micro scope.
-Kano
googol September 27th, 2004, 06:22 PM

Speaking of source of Nitric, here is one.
http://sargentwelch.com/product.asp_Q_pn_E_WLC97052-06_EA_A_Nitric+Acid_E_
Can someone enlighten me to the terminology used in the description:
Reagent ACS (~15.8M, ~15.8N), specificly the M and N, what do they mean?
I think the M might be moles? How strong is this acid in Percent?
Is this a good price? 2.5L for 30$ us. 70% reagent

They also mention Formula Wt. 63.01 . w hat is this; how does it compare to specific gravity.
Al-chymist.com has it for 20/L (technical,70%) or 45/L for reagent 70%.

What are the low,mid,and high prices people are seeing?
googol September 28th, 2004, 08:40 PM

I would have edited my previous post, however, the edit button is no longer available.
is it possible to enable the edit until another post is made?
The formula w eight is the sum of the atomic w eights of all elements in the formula. I thought this was the case, but I confused myself by using the atomic numbers instead of
weights.
I also found out the M does appear to be Molar solution in 1 Liter. still not sure what the N means. Also, looking a bit deeper I found the acid to be listed at around 70%. so
about the same strenth as al-chymist but cheaper. The disadvantage is I think they (sargentWelch) only ships to schools.
FU TI September 29th, 2004, 09:32 AM

I never heard that someone use HNO3 in photography. Exept silver recycling I cannot find any normal use of it there.
BTW it looks little suspicious to me that nitric acid is preservative for pyrogalol since HNO3 is good oxydative agent and pyrogalol is reducing agent.
Best info in this thread so far w as that cleaner based on 20% nitric acid:)
mtdawg July 9th, 2007, 07:35 AM

While browsing on Lab-X this AM I noticed a link to Taylor Scientific advertising an Internet special on chems-
[Link removed as potential advertising]
On a lark, I decided to try to order both H2SO4 and HNO3, a case [2.5Lx6] of each, mainly to see how outrageous the S&H would be and w hat sort of hoops w ould have to be
jumped through. Lo and behold, the order went through w ithout a hitch, and I'm now $308.49 poorer, including both the shipping [$26.++] and the HazMat [$20] fee...but I
should be receiving 30 liters of ACS acids [95-98% and 68-70%]. The pricing was about 4% higher than the link showed, but I figured it was best not to quibble for less than
$10.
I DO happen to have a DBA business name w hich I registered with Dun & Bradstreet several years back and I included it, so possibly that is the magic w ord, but other than that,
I used my real name and address and a debit card-kinda wish now I'd gotten one of the disposable cards...
Charles Owlen Picket July 11th, 2007, 11:59 AM

I knew a fellow that had a business that used HNO3 consistently (stainless steel related). He told me quite recently that technical grade 68% and lower had often been
substituted for reagent grade 70% by a major firm doing bulk sales to middle-men type companies.
It w as this fellow's insistence that several materials are regularly mis-represented by firms w hose reputations are generally quite good. Realistically this would be a one-time
fraud as it should be apparent to the end user.
mtdawg July 14th, 2007, 09:39 PM

While browsing on Lab-X this AM I noticed a link to Taylor Scientific advertising an Internet special on chems-
Received email day following order asking for copy of business license-following day phone call from company owner received, advising that the shipping quote was in error and
that the ACTUAL UPS shipping [truck] would be $111.xx, plus the Hazmat. I politely declined to pay the additional charge and cancelled the order, but she said the price is good
thru the end of the year.
If anyone else has a desire to order, it sounded as if the freight w ould be essentially the same even if the quantity w ere doubled, but as I was already mentally kicking myself
for dropping that much $$$ on an amount I'd never be able to use up, I was content to have an opportunity to exit gracefully. Guess I'd better get out the still and the
KNO3...:o
alancj July 17th, 2007, 06:57 AM

Well, for w hat it's worth, here is another place that fellow experimenters may find useful: http://www.hvchemical.com/
They have a lot of different chemicals including nitric for a pretty reasonable price, the hazmat is only $20. I haven t ordered from them myself but if I ever get tired of making my own
acid, then theyd be the first try.
One m ight also try ww w.kyantec.com; though som e here dont trust them (I dont really buy their arguments ). The quote I was given for nitric acid w as $24 per liter for 70% reagent
grade. You then have to add the $32 hazmat and regular shipping costs.
Its hard to find companies that w ill sell chem icals to individuals, especially hazardous chem icals , but these guys do.

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John456
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Posts: 105
From :
R e g i s t e r e d : M A R 2001
posted 05-27-2001 09:22 PM
--------------------------------------------------------------------------------
Before i comm e n c e t h e q u e s t i o n s , Y e s , i h a v e d o n e m u l t i p l e s e a r c h e s b u t t h e r e a r e s t i l l q u e s t i o n s t h a t h a v e g o n e u n a n s w e r e d ,
a n d i d o n t l i k e t h e i d e a o f a p ainful death . Anyway, i have been planning on producing some nitric acid for awhile, but still
h a v e s o m e questions i would like answered before i try.
First - W i l l a g o o d e x p e n s i v e g a s m ask protect me from n o x i o u s g a s e s a n d t h e l i k e ? ( I m not going to put m y h e a d u p t o t h e
receiving flask or anything crazy, but just in case)
Second - I dont have access to jointed glassware, so i a m using pyrex and boronsilicate labglass with rubber stoppe rs. W ill the
HNO 3 or resulting vapors eat at the rubber stoppers? If so, is there any way to acid-proof them ? (Possibly by wrapping them
tightly in teflon tape, or painting them with teflon if such a thing exists).
Third - The distillation setup is not com pletely sealed, i have it so it drips into an ehrlenmeyer flask from a b o u t a n i n c h a b o v e
the flask. W ill dripping through the air effect the purity at all?
A l s o , d o e s a n y o n e h a v e a n a p p r o x i m a te tem perature to heat the NaNO3 H2SO4 solution to? (I was thinking possibly 50 or
55*C or would this be too high and decom p o s e the acid before it forms?) Thanks for your time! -John
10fingers
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From : U SA
posted 05-28-2001 12:17 AM
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[ T h i s m e s s a g e h a s b e e n e d i t e d b y 1 0 f i n g e r s ( e d i t e d O c t o b e r 2 6 , 2001).]
PYRO 500
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From : s o m ewhere in florida
posted 05-28-2001 01:18 AM
--------------------------------------------------------------------------------
j u s t m a k e s u r e i f y o u n e e d a g a s m a s k t o w e a r a f u l l m oon suit but seriously if you notice alot of acid deco m p o s i n g m a k e s u r e
you are keeping it cool enough (I think) and for emerginceys make sure your cartrages are rated for NOx gasses
John456
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Posts: 105
From :
posted 05-28-2001 02:02 AM
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The procedure will be done ou t s i d e s o i g u e s s i d o n t n e e d a g a s m a s k a t a l l . H m m , i dont know what to do with the rubber
stop pers though. Any way i can get around that? It would be real expensive to buy new glassware. The rubber is very very
dense, so perhaps it wont get eaten very fast?
PYRO 500
Moderator
Posts: 1465
From : s o m ewhere in florida
posted 05-28-2001 02:36 AM
--------------------------------------------------------------------------------
just replace the stopperes, I beleve yo u can ge t teflon ones and there is a way to acid pro of corks
John456
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Posts: 105
From :
posted 05-28-2001 02:49 AM
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Hm m, dont know whe re i can get teflon stoppers, but i have m any corks laying around. Id be interested in hearing that
m ethod =)
John456
Freq uent Poster
Posts: 105
From :
posted 05-28-2001 03:01 AM
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Hit reply a bit too soon Anyway, i know where to get Teflon stoppers that dont have any holes for volum etric flasks and such,
b u t t h e s t o p p e r s i n e e d m u s t h a v e d i f f e r e n t s i z e d h o l e s . O n e g o e s a r o u n d a 6 m m or so tube that goes into the boiling flask,
a n d t h e o t h e r g o e s a r o u n d a 1 0 m m or so tube that goes into the condensor. C orks with drilled holes would probably work.
Here is a pic:
[This message has been edited by John456 (edited May 28, 2001).]
c0deblue
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From :
posted 05-28-2001 03:26 AM
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I f y o u c a n g e t h o l d o f s o m e *wide* teflon tape of the type used on very large threaded pipe (you m a y h a v e t o g o t o a n
indu strial supply for this) you can use the tape to cover the acid-exposed portions of the rubber stoppers. If you then push the
glass tubing right through the teflon in to the stopper holes, a "cuff" of th e m aterial will wind up squeezed b etween the glass
and the rubb er, form i n g a g o o d s e a l a t t h e t u b i n g p o r t s . D e p e n d i n g o n t h e t e m perature, it's even possible polyethylene film
m ight serve the purpose - some of it will stay im pervious (even though it gets softer) in boiling water.
As for acid-proofing corks, mo st chem istry handbooks p rovide recipes for acid-proofing substances.
10fingers
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From : U SA
posted 05-28-2001 11:42 AM
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*
John456
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Posts: 105
From :
posted 05-28-2001 02:32 PM
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I tried it today with 36m L H2SO 4 and 58g NaNO 3. I put a wide (2 1/2 cm approx) piece of teflon tape around both of the
stop pers with the glass tubes poked through it. It looke d like it was going fine till a sort of bubble of acid formed under the
teflon tape o n the rubber stopper. I stopped after about 10 m ins after that happened, and the sto pper didnt really look eaten
too bad, it ju st looked sort of bumpy. Guess ill just buy some jointed glassware, itll be worth it in the long run.
Dhzugasvili
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Posts: 64
From :
posted 06-05-2001 05:54 PM
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Late ly, I've been doing som e nitric acid distilling. I've got a whole distillation kit so I guess I'm lucky. Screw R u b b e r s t o p p e r s , I
have made my own stoppers out of tape and toilet paper, they last longer than you think and don't pollute your acid. I take
twice the amount of sulfuric acid and to it add nitric acid of 70% concentration. I then heat it up until I see droplets collecting. I
t a k e m y product once distillation has finished, and distill it another tim e, and again if necessary until you g et alm ost pure nitric
acid.
D e m olition
Freq uent Poster
Posts: 158
From : Austra lia
posted 06-06-2001 04:29 AM
--------------------------------------------------------------------------------
Dhzugasvili:W ith your distillation do you use a vacuum or not?
D e m olition
frostfire
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From :
posted 06-06-2001 01:06 PM
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http://www.im splus.com/im s.h tm l
g o t s o m e n i c e g a s m a s k s , c h e m ical bio hazard/warfare clothes, and even canon fuse
Gab
New Mem ber
Posts: 14
From : Q u b e c , C a n a d a
posted 06-07-2001 12:25 AM
--------------------------------------------------------------------------------
You may want to take a look at this MSDS page : http://www.jtbaker.com /m s d s / n 3 6 6 2 . h t m .
H e r e i s s o m e excerpts:
Ventilation System:
A system of local and /or gene ral exhaust is recomm e n d e d t o k e e p e m ployee exposures below the Airborne Exposure Limits.
Personal Respirators (NIOSH Approved ):

If th e e x p o s u r e l i m it is exceeded, wear a supplied air, full-facepiece respirator, airlined hood, or full-facepiece self-contained
breathing apparatus. [...]Canister-type respirators using sorbents are ineffective.
Dhzugasvili
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Posts: 64
From :
posted 06-14-2001 06:49 PM
--------------------------------------------------------------------------------
D e m olition: I have done the distillations without vacuum . Tried distilling acid twice and thrice but concentration did not rise to
acce ptable levels, will use NO 2 dissolving m ethod instead. From what I hear these vacuum pum p s a r e f u c k i n g e x p e n s i v e . Y o u
h a v e s o m e way of improvising one or creating lessened pressure?
I f a n y o n e i s f a m iliar with Sekur filters please reply. I ha ve just b ought the B2P2 filter. W ill this protect me against NO x f u m e s?
Or d o I n e e d the NO P3 filter?
John456
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Posts: 105
From :
posted 06-14-2001 09:28 PM
--------------------------------------------------------------------------------
D h z u g a , a s l o n g a s y o u h a v e a p a w n s h o p o r s o m ething near you you ca n pick up a refrigeration pump for $25-75. That might
not be the case in Kenya thou gh. I think you can im provise a va cuum pu mp out of a pool filter pum p a n d s o m e t u b i n g , b u t i
forget the URL. Also, today i distilled som e acid under vacuum (using 320m L H 2 S O 4 a n d 5 6 0 g N a N O 3 ) a n d i got a perfectly
clear, non fum ing acid product. It worked for RDX so i assum e it was pretty pure. I didnt see any NO x at all form ing in the
apparratus like all the other tim es. I didnt do anything different, so what could have happened?
frostfire
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From :
posted 06-15-2001 03:41 PM
--------------------------------------------------------------------------------
http://cgi.ebay.com /aw-cgi/eBayISAPI.dll?ViewItem & i t e m = 1 6 0 7 6 0 8 6 0 2
It's a pretty good deal for a retort...
has anyone had experience distilling HNO3 just using sim ple retort?
frostfire
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Posts: 266
From :
posted 06-15-2001 03:54 PM
--------------------------------------------------------------------------------
I got another confusion, the vacuum pum p act as a blower thoro ugh the aspirator, creating lower pressure as air travel faster,
hence, no acid fum e s i s p a s s e d t h r o u g h t h e p u mp...
s o a ny pum p c a n b e u s e d . . .
I m ight be wrong but do this really work?
John456
Freq uent Poster
Posts: 105
From :
posted 06-15-2001 05:14 PM
--------------------------------------------------------------------------------
I tried distilling some HNO3 with a reto rt a long tim e ago. it didn t work to o well, m ost of the vapors just escaped before they
had a chance to condensate. As for the vacuum aspirator blowing, i have no idea what you are saying, sorry.
10fingers
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From : U SA
posted 06-15-2001 05:45 PM
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*
John456
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Posts: 105
From :
posted 06-15-2001 10:13 PM
--------------------------------------------------------------------------------
Nope, the aspirator didnt work too well, but it was on a sink. to cool m y retort whe n i used one i cut a hole in the bottom o f a
plastic bottle and another hole in the lid, as well as two holes on the side. I put the end of the long stem of the retort into the
hole s in the back and front and tubing from a p u m p to circulate cool water in the side holes. Some thing you can m a k e t o u s e
with an aspirator that creates a relatively high vacuum (So ive heard, ive never tried it. Id rather use a store bought pum p
because this method is probably inconsistent) is here: http://rhodium .lycaeum.org/chem istry/equipm ent/aspirator.html . Id be
careful if you d o m a k e i t t h o u g h , o n e m inute your acid m ix could be fum ing nicely and the next it could boil and a bunch of
water and NO x vapor will condense over all at o nce.
[ T h i s m e s s a g e h a s b e e n e d i t e d b y J o h n 4 5 6 ( e d i t e d J u n e 1 5 , 2 0 01).]
Teck
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From :
posted 06-16-2001 04:20 AM
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John456: how much nitric acid did you use and what was your yeild on R DX?
[This message has been edited by Teck (edited June 16, 2001).]
John456
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Posts: 105
From :
posted 06-17-2001 12:39 AM
--------------------------------------------------------------------------------
The first m e t h o d o n M e g a ' s p a g e , e x c e p t i u s e d 4 0 0 m L n i t r i c a c i d a n d 7 5 g h e x a m ine. The yield was only about 7 grams but it
detonated.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Is my acid
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stanfield
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From: FRANCE
Registered: MAY 2001
posted 06-02-2001 02:18 AM
--------------------------------------------------------------------------------
I produce my own nitric acid by distilling NaNO3 and H2SO4 but I would like to know if the nitric acid I get is ready for RDX synthesis ?
thanx
-A-
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Posts: 100
From:
posted 06-02-2001 02:28 AM
--------------------------------------------------------------------------------
For RDX synthesis, you must use very pure nitric acid, it also has to be of high concentration. You can check it with an Hydrometer to see if it has the correct specific gravity.
-A-
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Posts: 100
From:
posted 06-02-2001 02:33 AM
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Oh, I forgot. If you haven't got experience in chemistry, specially nitrations, this can be a tricky one, with very poor yields, it looks simple, but you have to use good
techniques.
stanfield
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Posts: 166
From: FRANCE
posted 06-02-2001 04:20 AM
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thanx !
And you, what are the "good techniques" you are using ?
yt2095 June 21st, 2003, 08:37 AM

stanfeild,
i also use the same method, NaNO3 and conc H2SO4 (98%)
but after my 1`st distilation, i add half as much again of H2SO4 to my distilate and re-distil it. it may seem like a waste of good sulphuric but i re-use it with my next batch of
NaNO3 crystals and just keep this proccess going for 2 or 3 cycles.
even the "waste product" NaHSO4 is useful afterwards.
i end up with a Nitric acid that fumes when the bottle is opened. it`s percentage i don`t know as i have no hydrometer and only ever make small amounts enough to fill a
50ml brown glass bottle at a time.
as for it`s RDX worthyness, i have no idea, it`s not a synth i`ve tried. But it makes fantastic gun cotton, and metal nirates that i crystalise for use in color stars.
try the 2`nd distillation with added H2SO4, you may get a better product :)
all the best!

Anybody ever used magnesiumnitrate when distilling? This process is being used in the industry.
An advantage I see is that magnesiumnitrate is easier and safer to recycle than diluted sulfuric acid.
and metal nirates that i crystalise for use in color stars.
What a waste! 40% HNO3 with carbonates works like a charm for producing nitrates! No need to waste conc HNO3...:(

Improvised Manufacture of Nitric Acid > Generating Oxygen Gas for the Production of Nitric Acid - Archive File
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Dhzugasvili
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From:
posted 06-17-2001 04:59 PM
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I am using the process that I have read that works in the industrial method to produce Nitric Acid. I am bubbling NO2 through
70% nitric acid cooled to 5 degrees celcius. After a shitload of fumes were bubbled through, nitric acid became yellow, then
dark yellow, then fucking really dark green and vigorously fuming NO2. From another of my posts I learned that this could be
HNO2 instead of HNO3.
Well, down to the point. I also read in another post that by bubbling O2 through this weird nitric that I have now, I could obtain
very highly concentrated nitric acid, again, at five degrees. I was just wondering how the hell to produce oxygen, pure oxygen
other than by this method:
obtain 30% hydrogen peroxide and add chunks of manganese dioxide. Attach piping to erlhenmeyer flask and place tubing in
solution to be oxygenated.
Any methods of generating OXYGEN other than this? Or otherwise generating pure nitric acid other than by vacuum distillation?
kingspaz
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Posts: 347
From: UK
posted 06-17-2001 05:04 PM
--------------------------------------------------------------------------------
H2O2 and, liver, potato and yeast also work but a hell of alot better. also electrolysis of water producer oxygen (and hydrogen
another useful gas )
Dhzugasvili
Frequent Poster
Posts: 64
From:
posted 06-17-2001 05:25 PM
--------------------------------------------------------------------------------
Kingspaz, you mean H202 with yeast, potato, liver, etc? Sounds a little wierd, please clarify.
ALENGOSVIG1
Moderator
Posts: 766
posted 06-17-2001 05:43 PM
--------------------------------------------------------------------------------
you could always just purchase a oxygen tank from a harware store. if that is not pure enough, try getting your hands on some
medicinal oxygen. You'd most likely have to steal it out of the back of hospital supply truck. Tese are usually just pickup
trucks with the tanks in the back. Medicinal oxygen is usually a green tank. Mabe if you worked in a home for the elderly you
could steal one. Although i dont see whats wrong with the H2O2 + MnO2 method. just run the gas out of of the reaction vessel
through water to clean it.
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CragHack
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From:
posted 06-17-2001 06:23 PM
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i don't know about yeast or liver, but potatos contain the enzyme catalase, this is a very efficient liberator of O2 in H2O2. I
read online that it can produce 200,000 reactions per second. Human Blood also contains this enzyme.
------------------
"If you must, do it with intelligent people, at least they know how to talk to the cops."
DarkAngel
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Posts: 592
From: ?
posted 06-17-2001 06:44 PM
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Look at this site for some info about it:
http://www.chem.leeds.ac.uk/delights/texts/Demonstration_12.htm
I saw on a episode of David Letterman ones that someone blended some liver and than poured H2O2 to it,it started to foam
for a long time something like this:
http://www.chem.leeds.ac.uk/delights/photos/H2O2_cat/thumb_3.jpg
For explosives and stuff go to Section1 http://www.section1.f2s.com And http://run.to/section1

sendtosection1@hotmail.com
[This message has been edited by DarkAngel (edited June 17, 2001).]
Anthony
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Posts: 2306
From: England
posted 06-17-2001 07:03 PM
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I haven't used yeast for the catalase/H2O2 reaction but liver works about 10 times better than potato. Liver is really packed
with catalase.
Dhzugasvili
Frequent Poster
Posts: 64
From:
posted 06-18-2001 01:40 PM
--------------------------------------------------------------------------------
Ok, Far out! I got the oxygen, bubbled it through my green shit acid with apparently alot of HNO2 and NO2 dissolved in it.
After about 15 minutes or more of bubbling O2 in profuse quantities through it, it still remains the same fucking green color,
and I seriously doubt that this is >95% nitric acid.
Lemme get to the real actual point about my topic, the burning, frustrating question I have... HAS ANYONE MANAGED TO MAKE
CONCENTRATED RED FUCKING >95% NITRIC ACID WITHOUT A FUCKN' VACUUM PUMP?? IF SO, *PLEASE* TELL ME HOW THE
HELL YOU DID IT AND I WILL LOOK AT YOU AS A GOD... please understand I am *very* frustrated that I haven't got this shit
to work.

MnO2 as a solid is hard to administer at a constant rate without supervision. A separatory funnel or burette filled with a fairly
diluted KMnO4 solution dripping it's contents into H2O2.
BTW, the oxygen needs to be administered to the NO2 before reacting it with water, because the 2 gases have very different
solubilities in water.
Furthermore, simply bubbling NO2 into H2O will not yield much HNO2 as it is highly unstable in solution.
Ziqquratu June 21st, 2003, 05:51 AM

As a possible alternative to pure oxygen, all the oxidations I've ever done using oxygen as the oxidant (such as oxidation of
metal complexes) have simply involved bubbling compressed air through the solution to be oxidised. I mean, the only things
in air (in significant percentages) are nitrogen (inert), oxygen (what you're after) and carbon dioxide (not that much of it,
really, and probably reasonably inert under the conditions). The oxygen doesnt need to dissolve too much - just enough to act
as an oxidant, and you just keep bubbling so that as some oxygen is 'used up', some more is added.
It's certainly easier/cheaper than making or purchasing pure oxygen, and it should work in theory, so it's worth a try, wouldn't
you say?

BTW, the oxygen needs to be administered to the NO2 before reacting it with water, because the 2 gases have very different
solubilities in water.
Why do I need to requote myself?
Any HNO2 in solution will be fairly dissociated, so oxygen will not attack it to a noticeable extent.
Directly oxidizing the NO in solution isn't very useful either because you still need more oxygen to be added before you'll get
HNO3.
And then ofcourse you all have different kinds of gasses in solution with different solubility and different partial pressures on
the surface which makes it a mess equilibriumwise.
NO2 + H2O does not yield HNO3.

yt2095 June 21st, 2003, 08:09 AM
as another possible alternative, and it is ONLY an idea, the EXact chemistry of which will require a little research on your part to
get exact details.
I`ve had partial succes in making very dilute nitric acid, with the use of high voltage discharges.
a relatively simple peice of kit that can be made from things around your home, it`s called an Ozonator.
it consists of a jam jar with 2 pipes through the lid and 2 wires through the lid, the lid then being sealed with a glue gun so the
wires and pipes done come out or leak gas.
the solid core wires on the inside of the jar are placed half way down and seperated by about an inch. and electical arc is
passed between these two wire using the flyback transformer from an old portable TV.
a fish pump it attatched to one of the pipes so that air is passing through the arc and then out of the other tube as Ozone
(O3) and various other NOx gasses, these gasses are then bubbled through a glass of water over night, the water will be quite
acidic the next day.
it`s the same reason that large display Jacobs ladders are always enclosed in a polycarb or glass with the top left open, it`s
not just for safety, but to provide the veiwers from inhaling large quantities of Ozone and brown NOx gasses.
well considering that even Flourine comes second to O3 as an oxidiser, perhaps that MAY be an alternative method for
attatching your extra Oxygen?
if not, there`s nothing lost as it makes a great stain removing aparatus :)
i`m sure someone else may provide the correct chemistry for this writeup. but the theory seems sound enough, and it does
make nitric acid albeit dilute.
all the best :)
blindreeper June 21st, 2003, 09:12 AM

yt2095, the chemistry has been pointed out http://www.roguesci.org/theforum/showthread.php?s=&threadid=1919 - a thread
about making HNO3 from air using the electrical arc. It's funny how you just came up with the idea of using a flyback
transformer from a tv, and I guote from that thread by Alchemist:
and I really do think a good vacuum and better arc (maybe a computer or TV flyback tranformer) would work much better.
It seems ironic that you came up with that idea...any one else get my gist?
Thats OT
Now down to the O3, there are some things worth trying and some things that will never be tried. As I don't think anyone wants
to try distilling HF with a platinum rrtort in their home the same case with O3, it's not realistic. Although making NO2 with an
arc is feasable and is effective if it is running right, as mega has worked it out to be somthing like 94c for 1L of 68% HNO3
which I would pay for any day. But I am not going to get into anything on this thread thats what the other one is for!
yt2095 June 21st, 2003, 09:33 AM

blindreeper,
i REALLY don`t know what your issue is with me, but sort it out will you.
my email address is in my stats, as here is not the place to get arsey or debate personal issues.
if you`de have read my reply thouroughly you`de have seen that i mention that there are other places to obtain further
information. i never mentioned that i invented this method!
and the point of interest was the O3, the NOx was just a bonus.
this thread is Oxygen rellated, with regards to Nitric acid.

i considered my post quite apt.
Yes Ozone can be quite nasty in large doses, but be sure, it is quite safe with correct precautions, and is not a contact poison
that Flourine is! i fail to see your comparison.
i may add "does anyone get my gist" but that would be incitement :)
94c in a country where this readily obtainable is great, but for here and someone with the apropriate liscence, you may as well
ask for horse feathers.
and it wasn`t presented as a feasable way to generate HNO3 but as a way to get Oxygen to react with his NOx radical
mail me, we`ll chat :)

well considering that even Flourine comes second to O3 as an oxidiser, perhaps that MAY be an alternative method for
attatching your extra Oxygen?
Not true. Fluorine is a more powerful oxidizer than ozone, as reacting water with fluorine will yield ozone. Ozone does not react
as violently with most materials either, PVC tubing can be used to transport it, IIRC.
The formation of O3 in your apparatus is only a sidereaction and not really necessary, as NO reacts spontaneously with O2 to
give NO2.
BTW, reacting O3 with NH3 will directly yield HNO3, but this is a rather dangerous and impractical way. Should be a high
yielding reaction though...:D
yt2095 June 21st, 2003, 03:23 PM

Vulture,
yeah, i tried NH4OH 15% in the bottom of the jam jar as a test, the product stunk to high heaven of nitric!
the only change i noticed was the arc color was a little wider than with plain old air.
good stuff though :)
the copper electrodes became pitted as well and needed replacing after an over night session.
the water i bubbled this mix through crystalised on evaporation, i stongly suspect AN may have been a side product with a
heavy NA doping.
O3 is more reactive on the pauling scale than Flourine IIRC, i`m almost positive of this (no pun intended) :)
if i can find the URL`s on the Ozone sires i looked at, i`m sure there`s about 3 or 4 different refernces worded to this effect,
all different sites and beleive 2 of them were .gov sites (ok .gov is`nt alway beleivable to me either, with all the bullsh!t they
come out with over simple things) but indeed you maybe 100% correct. if this thread is still going, and i have the time, i`ll try
dig out these ref`s for you, and would welcome your opinion again.
and Vulture, never forget our new discovery... Cat Piss Chloride :)
all the best :)
Marvin June 23rd, 2003, 05:15 PM

I'm interested to know how long the chopper transistor lasts, and the multiplier from the TV, unless these have been replaced.
Sparks dont produce much ozone at all though. Ozonators use silent electric discharges, usually high frequency between
insulated plates.
I think absorbtion of oxygen by the solution will be very slow, and isnt being helped by the cooling. You want to speed the
equilibrium conditions, not attempt to retard decomposition. I dont think this will be useful without pressureised oxygen left for
long periods in sealed containers.
I dont like NO2 at all, and I think this method is impractical for high concentration nitric acid. Certainly for mid 90's without
pressurised acid proof containers.
Distilling az acid twice from equal volumes of conc sulpuric is supposed to produce something like 95+% vacuum optional. This
has been mentioned elsewhere.
As I understand it, adding MnO2 to the peroxide continually shouldnt be required as its action is supposed to be catalyctic.
Last time I tried this, the oxygen died away very quickly, but I assumed this was because I was using 3% peroxide and it was
simply exhausted.
vulture June 23rd, 2003, 05:29 PM

According to Pauling:
electronegativity of oxygen: 3,5
electronegativity of fluorine: 4,0
If you react an oxidizer with a reducer, the weaker oxidizer will always be liberated.
Therefore, if reacting water with fluorine yields ozone, fluorine is a stronger oxidizer.
Fluorine also reacts with noble gases, which oxygen doesn't. With oxygen I mean oxygen in all it's forms, as the oxidation
stage does not affect electronegativity.
Standard reduction potential for ozone: +2.076V

for fluorine: +2.87V
Convinced?
densest June 24th, 2003, 02:59 AM

a couple of comments:
the commercial synthesis of HNO3 is explained in some detail in the US EPA publications - google for them.
According to Merck, Cotton's "Inorganic Chemistry", etc.,

2 NO + O2 at STP -> NO2
NO2 + H2O -> HNO3 + NO (g)
According to something else that showed up on google, H2SO4 in (relatively) small proportions moves
the negative azeotrope equilibrium of HNO3 + H2O towards 100% HNO3
H2SO4 has a much higher affinity for H2O than HNO3
So, according to these authorities,

make NO by some means (say, electric discharge)
mix with air - NO2 should form (brown gas)
bubble through water
take gas remaining & mix with air again to form brown gas & recycle through water
take water mixture & distill to 70% HNO3
optionally, mix HN03 (70%) with H2SO4 (93+%) and redistill -> 95%+ HNO3
Details are available in the various references - please read them!

If you don't have the Merck Index and a few chemistry textbooks it would be a
very good thing to get them. A famous chemist once (reportedly) said:
A month in the laboratory can save as much as an hour in the library.
He's right ;-)
yt2095 June 24th, 2003, 06:06 AM

Vulture,
yes, your quite right, my mistake.

i re-read the links again (after taking an hour to find them again) and i obviously misread them the 1`st time round several
years ago.
sorry about that.
i supose to futher back your argument, it would be logical that if i was correct, then flourine in CFC`s wouldn`t break down our
Ozone layer, and it clearly does.
Marvin, i use the "dafodil" cap that connects directly to the tube through a 10MOhm resitor to chassis. i`ve never had a
problem with it so far. but your quite right, the yeilds for power used are quite low and not really worth bothering with except
for experiments sake.
also your idea about high frequency silent discgarge, am i correct in thinking that would similar apparatus to an Air Ioniser?
kingspaz June 24th, 2003, 12:19 PM

'then flourine in CFC`s wouldn`t break down our Ozone layer, and it clearly does.' actually the CF bond doesn't usually break.
its usually the catalytic effect of Cl* radicals produced by the homolytic fission of bonds due to light and UV hitting the CFC's in
the upper atmosphere that is responsible for destroying ozone.
yt2095 June 24th, 2003, 12:39 PM

i stand corrected again :)
it`s all good science tho, and hopefully of beneffit to others that MAY have thought as i did, thnx Kingspaz :)
Marvin June 25th, 2003, 10:36 PM

Silent electric discharge has been the accepted method for over a hundred years I think. Usually concentric glass tubes, with
the inner surface of the inner tube, and the outer surface of the outer tube being coated with foil, or immersed in sulphuric
acid. High frequency EHT at often around 20kv in modern systems but of old by an induction coil provides a silent discharge
over the whole volume at low ion density.
This does ionise the gas without a spark breakdown, but a home ioniser is typically very different. Here they are just a 20
stage cockroft walton ladder with a few (very large) resistors on the end. The live mains input being the isolated side of the
ladder. Produces a DC voltage of about 6kv below (I think for negative ions) ground and is sprayed into the air by sharp
terminals. I dont see any part of this being useful for ozone and the power is far too low anyway.
I'm not sure if this is what you meant by 'similar aperatus to an air ioniser' so take this post as you find it.
NO gets liberated very readily when water is treated with NO2 but as the acid concentration rises this stops.
Mendeleev October 22nd, 2003, 05:59 PM

The easiest way to get oxygen is to buy it at Home Depot or Lowes. They sell 40.1 gram, blow torch oxygen tanks for about
$8.00. The tanks are used in the oxygen-Mapp gas blow torch (which burns like 2,800 degrees Celsius!), which they sell for
$50 (it comes with both tanks). All of the gas blow torches sold at hardware stores are made by a company called bernzomatic,
and they are located in the tools section. To release oxygen you need a valve. I would get the "jumbo torch valve" because it
is the simplest one, it's just a short nozzle. Screw it on, turn the clamp and you've got about 6-8 minutes of oxygen at max
flow, which should be enough for your purposes.
:D
Mendeleev October 22nd, 2003, 06:35 PM

The oxygen-Mapp gas torch they sell has both oxygen and Mapp gas valves, so that is a good bet, plus you will have a very
hot torch, I use it to ignite thermite :D.
Dhzugasvili October 23rd, 2003, 04:55 AM

Well, evolution in this field has now taken me to higher places:cool:...long ago I managed the synthesis of density 1.52 nitric
acid using simple distillation of 75% Nitric with H2SO4 (98%). Also I succeeded with metal nitrates and H2SO4 simple
distillations. My product was sufficient and produced many HE's such as HMX and RDX, and others requiring high conc nitric.
The HE's were produced with decent yields. I stopped making anything for about a year, but now im back in business. Now I
want to set up a vacuum distillation (some of the diagrams in another Nitric Acid thread for building an aspirator are helpful)
and carry out distillation of H2SO4 and Nitric (75%) in order to get white nitic acid for fabrication of PETN and other explos.
BTW, how do you guys think that my red fuming nitric might have affected my HE prod in the past? What exactly does
presence of NOx fumes in nitric do to an rdx reaction? I did treat it with urea but it didn't seem to do much help of ridding the
acid of NOx. Im assuming white nitric acid as pure as you can get it can result in larger yields and a purer product, a safer
reaction, w/out too much risk of runaway.......any thoughts?
megalomania July 23rd, 2005, 10:19 PM

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia. I did an Internet
search and all I could find was mention of the reaction yielding ammonium nitrite. Does anyone happen to have any specifics
about this reaction like what are the conditions? Nitrite salts are pretty valuable in their own right, and if all it takes is an ozone
generator in an ammonia atmosphere this could be a useful reaction.
megalomania July 23rd, 2005, 10:19 PM

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia. I did an Internet
search and all I could find was mention of the reaction yielding ammonium nitrite. Does anyone happen to have any specifics
about this reaction like what are the conditions? Nitrite salts are pretty valuable in their own right, and if all it takes is an ozone
generator in an ammonia atmosphere this could be a useful reaction.
DONMAN December 11th, 2006, 09:42 PM

Would it work to bubble H2 through a solution of nitric salt to get nitric acid?
Alexires December 11th, 2006, 11:25 PM
No, it wouldn't work Donovan.
1. You would need to have a nitric salt that was less stable than Nitric Acid and
2. H2 is relatively stable. For it to even begin to work you would need a reaction vessel capable of many atmosphere and high
temperatures, as well as some kind of catalyst that is capable of storing the H2 as monatomic hydrogen.
Or thats how I think it works.
See, the only reason that H2SO4 and a metal nitrate works (with distillation) to make nitric is because sulphuric acid is a
stronger acid than nitric, hence the equilibrium favours the nitric acid side of the equation.
The only thing you will get from bubbling H2 through a solution of a nitric salt would be an explosion hazard.
DONMAN December 13th, 2006, 08:41 PM

Thanks for the help, I am just learning chemistry. All help is appreciated greatly. Does any one have any good
recommendations for chem that are intermediate references?
rayman December 14th, 2006, 08:21 AM

I am reviving this old thread because I caught a tidbit here about the reaction between ozone and ammonia.
I seen that as well, Did you find any more information on that mega ?
FUTI December 15th, 2006, 12:07 PM

Ammonium nitrite? Isn't that so labile under that condition that should decompose to N2 and H2O? Interesting anyway...
10fingers December 18th, 2006, 06:33 PM

Perhaps someone already mentioned it but why not make O2 by electrolysis of water? I would think that's the easiest and
cheapest method.
sbovisjb1 January 14th, 2007, 05:42 PM

Why dont you get one of those suba diving tanks? Or paintball tanks. Take it to a suba diving shop and you can get it filled
up. Say you are going deep sea diving. But tell them to fill it up with pure oxygen and to leave out all the other gasses
(nitrogen).
festergrump January 14th, 2007, 07:04 PM

You could get it filled at a scuba shop, but they'll probably not give you anything but the regular mix. They wouldn't want to be
responsible for you getting high deep beneath the surface of the water from the tank they filled for you. It's a liability issue
should something tragic happen.
Chances are they dispense it from a premixed bulk tank and couldn't help you out, anyway...
sbovisjb1 January 14th, 2007, 10:31 PM

Festergump if you go past (I think) 50feet, oxygen becomes poisionous, so they add a mixture of pure oxygen and other
gasses. It wont just be taken out of the air then.
Dawg February 21st, 2007, 05:07 PM

I haven't seen anyone mention the use of medical oxygen concentrators here. They are capable of producing ~ 90-95% pure
O2 at 1-5 LPM. On Lab-X they just offered a palletload of 'em [used] for a $295 opening bid [min of 6/pallet]-there were no
takers. I emailed the seller asking if they'd sell 2 of 'em and yesterday received them via UPS. I really only need one...
http://www.labx.com/v2/adsearch/detail3.cfm?adnumb=314398
http://www.portableoxygen.org/july.html
Al Sheik Yerbuti February 24th, 2007, 11:29 AM

Or paintball tanks. (nitrogen).
I'm pretty sure those are CO2, since CO2 can be kept liquid at ambient temperatures; thus significant volumes of safe
propellant can be stored in those little tanks. :)
I'm thinking that everyone's best bet if you can afford it is to get an oxy-acetylene setup from your local welding supply.
Besides, learning to use one of those torches is a great skill for us experimental types. Oh, and the acetylene can be used
instead of calcium carbide when making (silver) double salts.
nbk2000 February 25th, 2007, 12:13 AM

The gases used for pressurizing paintball guns are (in order of commonality) CO2, compressed air, and high-pressure
Nitrogen.
chembio March 20th, 2007, 06:22 AM

You could try heating potassium permanganate crystals. It usually provides a source of oxygen gas. Just use a delivery tube
to channel the O2 from the heated KMnO4 into whatever solution you need to.

The post above about obtaining fuming Nitric from the reaction between Ozone and Ammonia interested me. However is it
right? My google search only indicated that it formed Ammonium Nitrate? However like so many things these days the
information on the net is censored. Can anyone back this up from a textbook or the like?
hydra April 21st, 2007, 06:17 PM

Yes, that O3/NH3 route to nitric caught my eye too. Would very much like to see more info on this one.
By the way, the ozone-generators work by what's known as "Corona effect".
Any surface charged to a high enough voltage -gradient- will ionize the atoms surrounding it. Note the emphasis on
GRADIENT...which is the variation in field strength =per unit distance=. I.e., so many megavolts per meter....or kilovolts per
centimeter....or volts per micron.
Very high gradients are most often achieved via sharp points and surfaces. The point of a needle gets VERY small right at the
tip...so even with relatively low voltages (e.g. 2-3kv) the 'gradient' becomes enormous.
By using a 'field' of such points; and a nice high voltage like 10-25kv (bw monitor to color-TV flyback output levels), you can
get a pretty good production volume of ozone.
The same effect can also be gotten from bare wires of very small diameter. The very tight curvature of such a small radius
produces a large gradient.
If you scrap out any old copiers, you'll find 1-3 of these "corona wires", almost always in pull-out mountings (since they attract
dust/dirt, they need to be cleaned regularly).
This corona process is interesting for other ions too, for that matter. The technique has potential application in enhancing (or
allowing in the first place) various chem reactions...via making the reactants more 'energetic', and producing various radicals
via ionization.
Alexires April 22nd, 2007, 02:09 AM

For those talking about the Corona effect, is this (http://jnaudin.free.fr/html/s_gdp1.htm) it?
Mega, might I suggest amalgamating this thread along with the "Nitric Acid from Air and Water" as well as the "A new take on
HNO3 production"?
If hydra and the others are, in fact talking about glow discharge, then it shows that if these three threads were amalgamated,
it wouldn't have been missed.
hydra April 25th, 2007, 06:05 PM

Alexires; just to be clear, my own plans involve low voltage, high current, arc plasmas; rather than high voltage, low current
glow-discharge.
Either type of plasma can dissociate molecules and ionize atoms; but I believe there are a number of advantages (in this
application) to using the LV/HC arc plasma; so that's what I'm focusing on.
As far as merging threads goes....I'm just a greenhorn here, so my take doesn't carry any weight; but I'd much rather see
Oxygen Production as its own thread; not even related to HNO3 specifically. O2 is useful in many other processes as well.
The other hno3-via-plasma threads might be amalgamated into one....but the arc-method and glow-method are rather
distinct. The equipment -surrounding- either method (e.g. weak acid recirculation etc) is probably quite similar tho.

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megalomania June 21st, 2003, 11:38 AM

pete
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From: u.k
posted 07-01-2001 07:14 AM
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I have had a lot of time on my hands of resont, so i thought that i would do some of those interesting little reactions that you often think about, but never dream of. First of
all, aquiring white nitric acid, to get over about 98% pure nitric acid then you are going to need the dreaded vacumn, but white 98 % is possible, without urea from conc red
acid. Some time ago i prepared a small amount of red nitric acid, i but time in a beaker, and went to get other materials. When i got back i noted the acid was clear, what the
hell. I poured it into a container and checked its density, which indicated 98 % purity, which is what i tend to get with my red nitric acid. I took some more red acid and did the
same trick, a shallow layer of acid in a beaker, i put it outside and watch it. Nothing for 2 minutes, then the wind gave a gust or two, the acid had turned visabilly clear, after
just a minute of wind it had turned clear. I reply cated this trick with more acid with a manual wind, me fanning the beaker with a big plank of wood. By this method the acid
turned clear quite fast, i think the reduced pressure the air flow over the beaker is creating in the beaker, and the air flow carring any nox gases above the liquid away, thus
preventing equalibrum of the liquid with the air is waht has caused this effect.
pete
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Posts: 56
From: u.k
posted 07-01-2001 07:35 AM
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One time i was left with some nitration acids, post nitration. I had read that nitric acid reacts with sulphur thus
S + 6HNO3 ----> H2SO4 + 6NO2 + 2H2O
This gave me an idea, what if you bubble the resultant NO2 gas through water to make nitric acid, you will have in effect then generated H2SO4 from water and sulphur. So i
added a small amount of sulphur too my mixed acids, in a sealed flask with a pipe leading out of it to a boiling tube full of water. I heated the acids and soon a vigourious
reaction was taking place, the water at first absorvbed the gas well, and but soon it turned red and absorbed much less well. Once the reaction had ceased i let the acids cool, i
removed the sulphuric acid from the container, this was boiled till concentrated, and acted just like pure sulphuric acid. The nitric was of a lowish concentration, put was boiled
to 70 % and again acted like good nitric acid. By the end of the reaction i had more conc sulphuric than i started with, and some 70% nitric acid. This reaction is, i'm told a
modified version of the lead chamber process.
mongo blongo
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posted 07-01-2001 11:25 AM
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wow!! that is interesting!! im gona try these!!
nice one dude!!!
Anthony
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Posts: 2383
From: England
posted 07-01-2001 06:11 PM
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The second idea is interesting... If the reaction was 100% efficient (so you always got as much HNO3 made as you used to release the NO2) then you could produce H2SO4
very cheaply. I wonder if there's a cheaper way to produce NO2? Heating NH4NO3 maybe?
zaibatsu
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From: England
posted 07-01-2001 07:59 PM
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wouldn't you make N2O by heating AN?
Anthony
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From: England
posted 07-01-2001 09:21 PM
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I thought it decomposed into both if over heated?
zaibatsu
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From: England
posted 07-02-2001 01:03 AM
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I too thought it would, but asked mr Cool, and he gave this response:
Heating NH4NO3 ---> 2H2O + N2O (laughing gas)
Heating Pb(NO3)2 ---> PbO2 + 2NO2 (nitric oxide. Not as funny, but more
useful!)
So if you can find any lead nitrate you can use this, and so save on the cost of H2SO4, but I'm guessing it will cost more than it would to use H2SO4/KNO3
Mr Cool
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posted 07-02-2001 03:05 PM
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I think it can make both if overheated in the presence of oxygen.
KNO3 can also decompose to release NO2, it's more common than Pb(NO3)2.
Anthony
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Posts: 2383
From: England
posted 07-02-2001 04:24 PM
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Thanks for the clarification, possibly something worth experimenting with in the future
pete
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Posts: 56
From: u.k
posted 07-02-2001 04:24 PM
--------------------------------------------------------------------------------
After some more experimentation i have found that the reaction is an equalibrum, as all are, but pure nitric works best. I have come to the conclusion that the reaction is hard
to drive, after much experimentation. Maybe someone else will have more luck, the reaction definately works however.
Ollie Snowie August 11th, 2003, 07:12 PM

You Have probably already thought of this but how about:-
PbO2 + 2NO2 --> Pb(NO3)2 + Heat

Then
Pb(NO3)2 + Heat --> PbO2 + 2NO2
You could absorb NO2 from a low conc. mixture (say from an electric arc), heat the lead nitrate formed and release fairly pure NO2. Use this to make some conc. HNO3 and re-
use the PbO2. It has been said in "http://www.roguesci.org/theforum/showthread.php?s=&threadid=1919" that sillica gel will do the same thing. -Hope this is in the right
thread as it's my 1st post.
knowledgehungry August 11th, 2003, 11:43 PM

I dont know what you are gaining from this reaction, why not just bubble the low conc NO2 through some H2O in the first place, reacting NO2 with PbO2 then reacting
Pb(NO3)2 to make NO2 seems a little redundant, if you already have the NO2 i dont understand the point of making Lead nitrate just to make NO2 again. Maybe i am missing
something.

Yes, you are ;).
When making HNO3 with H2O and NO2, an equilibrium is reached between NO2 in the gas above the water, and NO2 in the water. We need as much as possible in the water.
With air containing a low conc of NO2, such as that from an arc, there isn't much NO2 available to dissolve in the water, and an equilibrium is reached where the conc of NO2 in
the water is very low.
However, with high conc NO2 in the air, or pure NO2, there is much more available, and so the high conc in the air will allow a much greater amount to dissolve in the water
before an equilibrium is reached.
And so by forming a nitrate, and then decomposing it to form pure NO2, we can get much stronger acid.
A similar plan was mentioned in the thread in this section, about using an arc...
I hope that's clear, my thoughts aren't very lucid today due to a big fucker of a hangover, so I may not have explained myself very well...
Ollie Snowie September 1st, 2003, 06:58 AM

Just another thought on this:-
If NO2 is not very soluble in water and you have cheap, easy H2SO4, Why not make a nitrate from an oxide or hydroxide and NO2, then distill HNO3 from that and H2SO4. I
have heard that some sulphates (such as CuSO4) decompose on heating to form an oxide and SO3, so that means that you could regenerate your H2SO4, make more nitrate
and redistill.-- A bit of a long way round but with vacuum distillation you could get some conc. nitric acid.
Just another thought:-
If all you are after is H2SO4, you could re-use the nitric acid instead, or if you want both, you can keep adding S, O, and N at the required stages and tap the excess H2SO4
and HNO3 off as required. Presto! A mini nitrating acid factory in your shed.
Ollie Snowie September 11th, 2003, 02:33 PM

I recently read about this reaction (Thermal decomp. of lead nitrate). It doesn't do what I thought it would. It forms oxygen aswell as NO2, and PbO, rather than PbO2. The
question is, could 3 NO2s oxidise it back to Pb(NO3)2, one of them being converted to NO?
What about something more reactive, for example, iron nitrate. Being more reactive, it might be better at holding its extra oxygen, and staying in its high state of oxidation.
Hey. I think I could have hit gold here. What about making iron nitrate from moist iron oxide/hydroxide and NOX (from an arc). Then React it with conc. H2SO4 and vacuum
distill it, to extract the HNO3. Then (I hope i'm right on this bit) regenerate the H2SO4 by thermal decomposition (make Ye Olde Oil Of Vitriol) and also get back the iron oxide.
I did try the last bit with some iron(II) sulphate from a chemistry set and it does need a very high temperature to completely decompose. But... As always... Electricity is cheap
:)
THe_rEaL_dEaL September 22nd, 2003, 10:10 PM

This copper sulfate --> Cu0 + S04
If this is right then this has much promise> A VERY cheap source of sulfur trioxide for H2SO4 production as where I live Copper sulfate is very
available at even some well stocked supermarkets :) its crazy.
Could this Ionic sulfate principal work with a group 2 metal ion like MgS04 instead of a transition metal sulfate, as MgS04 is even more accessible
in the form of epsom salts. Allthough it a crystalisation of water compound in packet form, from my short chem experience, an oven could fix that!
simply RED September 23rd, 2003, 01:11 PM

This is wrong...
zeocrash September 23rd, 2003, 02:19 PM

as far as i know, strongly heating copper sulphate does not form CuO or SO3, it instead forms a white powder known as anhydrous copper sulphate. the only use i've found for
this is novelty in that when you add water it turns blue again and gets increadibly hot.
Ollie Snowie September 23rd, 2003, 04:39 PM

simply RED-Which post are you referring to?
and
THe_rEaL_dEaL-We are not really bothered about making H2SO4 here. The H2SO4 is only used to displace the -NO3 from the iron nitrate. I was talking about how to recycle
the -SO4 and -Fe so you don't have to keep adding H2SO4 and Fe2O3.
and
zeocrash-Heating hydrated copper sulphate to a bit above 100 deg. C just makes is anhydrous. Heating it more strongly makes it form CuO and something else (choking gas).
I'm not sure about SO3 though. My instinct tells me it would be SO2 and O2 but I'm probably wrong. Anyway, it wouldn't matter if we were making HNO3 by the method
described in my last post, because we could use excess iron nitrate to sulphuric acid, and then the heat would make it give off NOX as well as SO3, SO2 and O2. Any SO3 would
react with the water in the reciever to make H2SO4 and then the NOX would catalyse the oxidation of remaining SO2. Then the waste gasses from this stage would be returned
to the absorbtion chamber where it forms iron nitrate again with the moist iron oxide.
zeocrash September 23rd, 2003, 06:05 PM

copper sulphate does not decompose to sulphur thrioxide upon heating.
when heated above 560C it turns to anhydrous copper sulphate.
Properties: Grayish-white to greenish-white rhombic crystals or amorphous powder. On heating dec above 560degrees. d 3.6 . Hygroscopic. Sol in water. Practically insol in
alcohol. Keep tightly closed. -the merck index
are you sure it's copper sulphate you're heating, i know copper carbonate breaks down to from CuO and CO2
edit: apoligogies, i stand corrected, i was just unable to find any reference to this anywhere i looked. merck index, reinhold chemical dictionary
simply RED September 23rd, 2003, 06:40 PM

The post about decomposition of CuSO4 i was refering to.
It will decompose to SO2, O2 and CuO after the chrystalization water is removed. The decomposition starts when anhydridous CuSO4 is heated to 600 C.
Jackotrades October 3rd, 2003, 01:41 AM

I'm a bit weak in the chemestry department. Couldn't strontium nitrate be decomposed to for NO2? If so, there's a big market for it...AKA road flairs.
blindreeper October 3rd, 2003, 03:18 AM

Most things in chemistry look like they would work. A common question that came up when my class were doing ions and bonding is why don't you get O2 + O2 -> O4? It's
the just the way electrons are. Some things look like they would work but don't, so in short, no

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > 95%
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megalomania June 21st, 2003, 01:37 PM

Dhzugasvili
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From:
posted 06-21-2001 04:41 PM
--------------------------------------------------------------------------------
I Was just wondering if there is any way to:
a) improvise a home made vacuum pump
b) MAKE NITRIC ACID OF 95% CONC. OR MORE WITHOUT A VACUUM PUMP OR SIMILAR DEVICE.
I would be *grateful* if any of you that have succeeded in making RED NITRIC acid without a vacuum pump share your knowledge with me, or any of you that have made an
improvised pump tell me about it.
I have no problem acquiring most chemicals... but this one has proven to be a bit of a problem...what is red nitric used for in the industry so if I find a place that sells it and
they ask me what I want it for I may provide them with explanation.
simply RED
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Posts: 242
From: HELL
posted 06-21-2001 06:46 PM
--------------------------------------------------------------------------------
I haven't made clear 95-100 HNO3 in good quantities and it seems difficult to do it in high quantities at home. The process with the 2 bottles and KNO3/ H2SO4 distilling seems
good.
Azotna kisilina - towa e mateql koito maika si ebal. hehehehhehe
(what a nasty work is to find conc HNO3)
Can someone translate bulgarian?
mongo blongo
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posted 06-21-2001 08:27 PM
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dude, u want to make RED nitric acid? as far as i know the reason you need a vacuum is because water and nitric oxides get in the acid from a normal atmosfear (the nitric
oxides turn the nitric acid the red colour!)
but i do have an idea ( i have never tried it and don't know if it will work)
if you can somehow carry out the experement in an air tight atmosfear and put a bowl of anhydrous copper sulphate (white not blue) in there the water from the surroundings
will be absorbed ( turning the copper sulphate blue) and then you will have less water in your nitric acid
you could also use something like sillica gel
instead of copper sulphate!
but i have no ideas to keep the nitric oxides out
Teck
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From:
posted 06-22-2001 02:23 AM
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All pure acids are clear in color, and if your acid is red or whatever other color then it isnt pure and isnt as good as the clear stuff. Anyone correct me if Im wrong.
Mr Cool
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posted 06-22-2001 01:50 PM
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I assume you're not including picric acid etc etc etc etc.
All mineral acids are clear when pure, maybe?
Nitrogen oxides are formed by decomposition of the HNO3 in the still, they don't come from the air.
I've made red, very strong nitric acid with a normal glass retort, no vaccuum. It gelatinised normal cellulose fibres into a sticky yellow blob! It also worked for RDX when urea
was added.
frostfire
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From:
posted 06-22-2001 02:36 PM
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wait a minute,
is the glass retort the one with only single glass bulb and glass pipe going down from the top at an angle......do you put anything else
beside HNO3 70% or xNO3 and H2SO4?
How'd the red fuming got produced?
I read from at.engr.exp (catfood site) that even the guy is struggling with a vacuum distillation to get that thing
I've tried also the two joined glass bottle but end up with not even fuming clear acid and a broken (not braking) bottle
John456
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From:
posted 06-22-2001 03:54 PM
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I beleive this has been discussed before but recently ive been experimenting with converting ammonia to NOx gas by catylyzing with platinum-rhodium pieces i got from old
catylitic converters found in cars. The device i have built consists of a flat-bottom 24/40 florence flask thats filled with 30% ammonium hydroxide solution and capped with a
thermometer adapter on a hotplate. In the adapter a length of glass tubing is extended and put into a small (3 inch) length of flexible tubing that fits over some steel tubing of
1 inch diameter. The steel tubing goes for a couple of feet so the rubber tubing doesnt get hot and melt. The steel tubing is then connected to a 3-way steel pipe with a 3-inch
diameter that is shaped like an upside down T and has a threaded hole on the top and two threaded holes on the sides, and runs through an old gas grill. The tubing is put in
one of the threaded holes about 6 inches in, leaving a good sized space for air. The other side has a threaded adapter that screws in to fit 1-inch pipe. A right angled pipe is put
into a hole in a 2 1/2 or so diameter rubber stopper that fits into a jar i made, and flexible tubing with lots of holes in it (to lessen the pull of vacuum significantly) goes into
another hole in that same stopper that is connected to a vacuum pump. When the ammonium hydroxide solution starts boiling and a good amount of ammonia gas is passing
through the pipe pieces of platinum-rhodium in a steel pan are then heated on a gas burner until they are red-hot (it takes a while), and funnelled into the top hole in the steel
pipe. The steel pipe (which has been heating on medium heat on the grill) is then capped and the vacuum pump is turned on. The ammonia gas touches the red-hot platinum-
rhodium pieces and turns into NOx and a couple other things will be produced and when it is bubbled through the water in the jar nitric acid is formed. The vacuum pulls air
from the hole in the pipe so the reaction can continue and to make sure the NOx gets bubbled through the water. Theoretically you can make 100% acid with free NOx
(fuming) with this setup! Ive just started experimenting with it and the max conc acid ive been able to make is about 23% (But thats pretty damn good starting off with
nothing but ammonium hydroxide), seems like some ammonia is still getting by unreacted. I know this requires a vacuum source but i thought you guys would be interested in
it since i saw old threads discussing it but nobody ever said they tried it and i didnt want to start a new thread. Heres a picture i drew in paint to illustrate it (i hope the mods
dont get pissed at me for posting a pic).
Edit: fixed the pic link
[This message has been edited by John456 (edited June 22, 2001).]
Anthony
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Posts: 2383
From: England
posted 06-22-2001 08:20 PM
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Nothing worng with posting a picture, especially when it's as original as this.
Dhzugasvili
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From:
posted 06-23-2001 05:33 AM
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Simply Red, that's some pretty good Bulgarian! If you say you made the Hno3 but not in good quantities how did you get it in small quantities in the first place? Mr. Cool, what
where your distilling reactants? Kno3 and H2So4 or Nh4No3 and H2so4?
Confuscious once said: "Mierda, puta! Has de creer que estoy enfermo!"
10fingers
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posted 06-23-2001 09:00 AM
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*
John456
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From:
posted 06-23-2001 10:48 AM
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Hmm, regulating the temp might be a problem since i dont think the grill gets that hot. Might have to buy some type of small furnace. As for oxygen entering the vacuum pulls
it through the steel pipe with the ammonia gas. What should i use for drying? I have some potassium polyacryate gel i use for dessicating all the time, ill fasten a drying tube
out of metal and put it at the end of the steel pipe. For cooling the gas im using NH4NO3 and water, with the exit tube passing through a bucket of it.
Dhzugasvili
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Posts: 64
From:
posted 06-23-2001 12:41 PM
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Drazvitzie All! I realize this is quite a long reply, but it would really be enlightening if you take some of your time read it. John456, do you have access to dilute nitric acid?
Because if you do I am sure you are aware that you can get NO2 out of it by adding formol, all you would need to do then is pass the glass tubing into another flask containing
water to make nitric acid and also bubble in some O2 to make the yield greater. You would need to put it in a salt ice water bath for better absorption. This method has gotten
for me two results: 1) when bubbled with the O2, the acid appeared dark yellow and it fumed NO2. 2) when bubbled with only NO2, without O2, I got a dark green solution of
heavily fuming acid.
So that sucks because it doesn't give me the desired product, 95% or more concentration of nitric acid. I have tried distillations without vacuums. I have tried the following: 1)
distilling 100ml 70% Nitric with 200ml 98% sulfuric. the product was an orange acid that fumed NO2.
2) distilling that product from the above a second time. the same product was obtained with no apparent raise in the concentration.
3) distilling KNo3 with 98% H2So4. The product was the same, orange acid that fumed NO2.
4) distilling the dark green acid produced from the bubbling NO2 process. INTERESTINGLY ENOUGH, this gave me some REALLY CONCENTRATED RED/GREEN ACID. But then I
had to stop procedure because I had to go. I wonder if it would have continued to give me the same product. now this is an interesting product, dark green/RED nitric acid, and
it DOES gelatinize cotton. My only problem with this is that it is a little green, I wonder why. Will keep on trying since this has proven to be the most productive process.
I doubt any of the ORange products are 95%+ Nitric Acid. I have not tried to see if they gelatinize cotton though. ANy imput will be appreciated.
Dhzugasvili
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From:
posted 06-23-2001 12:45 PM
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...I forgot one more thing. I will try to distill sulfuric (98%) with ammonium nitrate. Is this process recommended?
John456
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Posts: 105
From:
posted 06-23-2001 01:49 PM
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Yes, i have access to dilute HNO3 but distilling H2SO4/NaNO3 makes a better product with better yield too. Ive succeeded in making acid from that procedure so now im
interested in making it cheaply and efficiently.
PYRO500
Moderator
Posts: 1513
From: somewhere in florida
posted 06-23-2001 02:53 PM
--------------------------------------------------------------------------------
I am guessing you acid may be green due to copper in your distillation apparatus, or other impurities though could cause your wierd NA.
10fingers
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From: USA
posted 06-24-2001 12:40 AM
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Mr Cool
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posted 06-24-2001 12:13 PM
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Yes, I used a plain glass retort. One bulb, one long glass delivery tube. Reactants were c. 100% H2SO4 (heated until it boiled, and used as soon as it had cooled) and dry
KNO3. Product was deep orange/red, and strongly fumed brown mist (not just NO2 gas, it was cloudy HNO3 vapour as well).
A gas flame will reach well over 1000*C with enough air. Pure oxygen won't be needed. However, you may have trouble heating an object to this temperature, since as it gets
hotter it'll lose heat faster!
John456
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Posts: 105
From:
posted 06-24-2001 02:06 PM
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When i heat the plat-rhod pieces they should get hot enough for the reaction (about 800*C im guessing) and since its an exothermic reaction it should produce its own heat.
THe grill is just there to minimize heat loss during the reaction. I modified the apparatus so there are more holes in the tube going to the vacuum to lessen the pull more. It
seems there is more NOx coming through the water than before. With 800mL of boiling hydroxide solution (30%) i was able to make 200mL of 40% nitric acid, and i still have
some hydroxide left over because i had to turn the vacuum off for danger of overheating. I was able to heat this acid down to 70% and then vacuum distill it with sulfuric acid
to obtain conc. 92% or so acid! All from ammonium hydroxide . The problems now are that eventually the reaction would lose enough heat to stop converting the gas, which
would stop the reaction all together and ammonia would come in and neutralize my acid. Also, the vacuum pump seems to get quite hot quicker than normal so im worried it
could overheat.
Edit: Oh yeah, the steel tube now goes through an elevated bucket with a hole cut in the bottom that has a cold-pak style mixture of NH4NO3 and water.
frostfire
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Posts: 267
From:
posted 06-24-2001 06:07 PM
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thx Mr. Cool, now I'm ready to buy one with a expereience reference.
Dhzugasvili,
that's a very interesting documentation but that green color is very weird....i've never seen anything like it in nitric acid distillation
[This message has been edited by frostfire (edited June 25, 2001).]
Bitter
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posted 06-26-2001 03:06 PM
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There isn't any stainless steel in your apparatus is there ? Nickel salts are usually green in colour.
Dhzugasvili
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Posts: 64
From:
posted 07-03-2001 06:26 PM
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According to the info I have read so far, the best, and hopefully SURE SHIT way to make NA of high concentration would be to distill NaNo3, Nh4No3, or kno3, HNO3 with
sulfuric acid and with a vacuum. HOW CAN I IMPROVISE A VACUUM? I thought of a very long bike pump but not too sure about that...
to check the concentration of the acid, what do I need to do? I have tried this distillation without a vacuum and i do not get a red color, but a light orange color (like oranges!)
could this be highly concentrated acid? what is the viscosity of highly 95%+ concentrated NA? In comparison to water, 98% sulfuric acid, and 70% NA? NH4no3 + H2so4 yield
of acid is higher in concentration than kno3 sulfuric A. yield?
10fingers
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From: USA
posted 07-03-2001 07:14 PM
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PYRO500
Moderator
Posts: 1513
From: somewhere in florida
posted 07-03-2001 08:51 PM
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I designed a vaccume still, but I don't know if any of the components would react with your product, anyways, a picture of it is here. "http://www.geocities.com/pyro2000us/
hno3.jpg"
simply RED
Frequent Poster
Posts: 242
From: HELL
posted 07-04-2001 06:13 AM
--------------------------------------------------------------------------------
I've made conc. nitric acid with KNO3-H2SO4 distiling and Pb(NO3)2 H2SO4 heating and decanting. It is concentrated and works for nitrating alcohols but not for RDX .
Sorry for the late reply. I had work with the urea fertilizer .
Dzugasvili otde znae6 bylgarskiq. Pi6i edno pismo ako iska6.(Where do you know the bulgarian from, Dzugasvili) .
Dhzugasvili
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Posts: 64
From:
posted 07-04-2001 07:42 PM
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Impressive...I'm a Rusky, but not living in Mother Rossia, living in Kenya, but anyways, know a bit of Bulgarian too. Ah! SLAvIA...Vissarionovic was aLmIghTy leader...
KatYa Gordeeva is my name...NIET!
Dhzugasvili
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Posts: 64
From:
posted 07-04-2001 08:14 PM
--------------------------------------------------------------------------------
Thank you for the link, Pyro500.
Dhzugasvili
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Posts: 64
From:
posted 07-05-2001 06:15 PM
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IM SUCH A STUPID FUCK!!!!!!! Guess what people, fuck the vacuum, I did the stupidest thing, and all this time I have been trying to produce 95% Nitric Acid when I had it all
along!!!! I hadn't tried to check the density and I checked the density of my ORANGE nitric acid that was distilled from sulfuric twice, and guess what, 1.53 density with
percentage error accounted for. 30ml of nitric weighed exactly 46g, so that divided by 30 is the density. NEXT with this very same acid I tried pouring a tiny amount on some
cotton...it gelatinized the fuck out of it!! Yellow sticky blob just like your product Mr. Cool. The acid fumes white and red fumes rather heavily. hooray! on to synthesis...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > From AN to
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megalomania June 21st, 2003, 05:04 PM

PYRO500
Moderator
Posts: 1513
From: somew here in florida
posted 07-01-2001 03:40 AM
--------------------------------------------------------------------------------
I recently visited an agricultural supplier and I found out that they sell 24-0-0 fertilizer, he also said it wass AN. I want to know about experiences w ith making high
concentrations of nitric acid with AN and H2SO4 w ithout a vaccume. I know I will have to purify the AN first and boil the H2SO4 dow n before mixing them, what would be the
optimum mix for the two andw hat temp w ould I have to do this at? I dont have any money for glasw are currently, but I plan on getting a cheap retort when I get some cash
and then w hen I get alot more money (don't ask me how it will be a couple of months) I will try to order some jointed glassware from UGT. so I w ant to know what I could use
as a distillation/receving flask. I was thinking like kurt saxon's mayo jar flask, as the boiling flask and I guess the receving flask dosent need to be sealed. does anyone know
what tubing types I could use for this all I have read is surgical tubing but isn't that rubber witch gets dissolved my NA? please help me if you have experience in this field.
Tony Montana
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Posts: 145
From: Australia
posted 07-01-2001 04:34 AM
--------------------------------------------------------------------------------
An aspirator can be acquired reasonably cheaply(or made), and provides a half decent vacuum.
The improvised munitions black book states, 2 parts by volume Potassium nitrate.
1 part by volume Concentrated sulfuric acid.
It also states: If sulfuric acid is obtained from a motor vehicle battery, concentrate it by boiling it until white fumes appear.
The amount of nitric acid produced is the same as the amount potassium nitate you start with. Thus, for 2 tablespoonsful of nitric acid, use 2 tablespoons of potassium nitrate
and 1 tablespoonful of concentrated sulfuric acid."
Dry potassium nitrate is added first,
followed by sulfuric acid and stirred into a paste. The heating of this paste produces red fumes(un-condensed nitric acid).
The black book uses a somew hat questionable method for condensing, using 2 coke bottles taped together at their openings. The bottle with the paste(distilling bottle) is put
over a small flame, w hile pouring cool water over the other bottle(collecting bottle). While the obvious safety concerns ring out with this method, like bottles w ith acid breaking
mid sythesis, I wouldnt do it, but hope it helps as it shows the most basic sythesis,I think you could get away w ith.
[This message has been edited by Tony Montana (edited July 01, 2001).]
wantsomfet
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Posts: 239
From: EU
posted 07-01-2001 05:57 AM
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Nitric acid from AN & H2SO4: At least one mole H2SO4 for every mole AN!
Jointed glassw are should be used!
------------------
kangaroooo.cjb.net
Donutty
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Posts: 228
From: UK
posted 07-01-2001 10:36 AM
--------------------------------------------------------------------------------
My glassw are should be coming some time next w eek. I ordered everything needed for HNO3 productionm, so when I make some, I'll let you know how it goes.
John456
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Posts: 105
From:
posted 07-01-2001 12:22 PM
--------------------------------------------------------------------------------
AN is not the best for making nitric acid, NaNO3 and KNO3 are far superior, but it can be done. Everytime ive made nitric with AN though, some impurity has been in it which i
cant figure out, but i cant make nitroglycerine with it even when its of high concentration.
Also, tony, if you get red/brow n fumes w hen you produce nitric acid they are not uncondense nitric acid. They are nitrogen dioxide fumes and w ill not condense unless cooled to
a very low temperature. What you want is for the nitric acid to become gaseous, when its gaseous it looks clear. Without a vacuum, though, some decomposition is inevitable
which is w hy the nitric acid fumes and is red. It is possible to make clear white nitric under a vacuum.
The book is also w rong, measuring things by volume is fine with liquids but it doesnt provide accurate measurements with solids. KNO3 can be a fluffy pow der or dense prills
and the volume can differ alot with its density. In my experience 34mL (about 62.4g of 98%) sulfuric acid for every 58 grams of NaNO3 or 68g of KNO3 is the best ratio. In
order to find how much AN to use youd have to figure out how many NO3- ions are in it and compare it with NaNO3 or KNO3 and adjust the amount. A normal aluminum coke
can would certainly react with both nitric and sulfuric acid and that method w ould be foolish to try.
Edit: Pyro, when you buy from UGT look on Ebay and they are selling a full set of jointed glassware for distillation for $125. Thats 30 or 40 under their regular price and also
buying through a money order is more anonymous than a credit card.
[This message has been edited by John456 (edited July 01, 2001).]
frostfire
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Posts: 267
From:
posted 07-01-2001 04:40 PM
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darn Donutty, you beat me at ebay....
it's not really wise to use the same name though (if it's really you)
Anthony
Moderator
Posts: 2383
From: England
posted 07-01-2001 07:45 PM
--------------------------------------------------------------------------------
Now you mention it, I seem to have more success using KNO3 than NH4NO3 or NaNO3 in simple nitrations with H2SO4 although maybe since these are all fertilizer grade, the
KNO3 is just purer (maybe easier to purify than the other salts?).
Anyway, when I get round to it I'll be in the same boat as you PYRO500 - HNO3 production on the cheap, I plan to use a glass bottle as the distilling vessel make a bung from
fibreglass resin (I tested this at room temp and it was HNO3 proof) and use PVC aquarium tubing (H2SO4 proof, haven't tested w ith HNO3 yet) although I'll most likey use a
glass elbow through the bung as I have a small amount of glass tubing.
BTW 1.27gm NH4NO3 and 0.77gm H2SO4 make 1gm HNO3

Good luck and if at first you don't succeed, try again, then again, then cry and smash it up
[This message has been edited by Anthony (edited July 01, 2001).]
PYRO500
Moderator
Posts: 1513
posted 07-02-2001 12:39 AM
--------------------------------------------------------------------------------
will aquarium tubing hold the heat? I think that it may melt, what is the optimum tempature to distill the paste at? I also can get calcium nitrate fertilizer 18-0-0 and I may get
potassium nitrate fertilizer if I can find out where to get it from. does anyone that lives in the U.S. know what kinds of fertilizer has KNO3 in them, and what are the numbers on
it. if I know the numbers I can mass dial the fertilizer company's and their stores to find suppliers. I think I really take advantage of free local calling (w ith a wardialer and a
third phone line ) anyw ays, any one in the US please tell me where you get your KNO3 from.
c0deblue
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Posts: 229
From:
posted 07-02-2001 01:27 AM
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Fertilizer grade "pure" KNO3 is normally sold as 14-0-45 (the numbers can vary a little depending on the manufacturer). Our local agricultural supplier had none in stock, but
could get it in one day from their supplier. The quoted price was $23.00 for 25 lb. I've heard of lower prices, but this is probably a typical range for retail outlets. Don't know if
this was prills, granular or powder.
BTW, AN fertilizer is usually 34-0-0, so if the stuff your local supplier had was really 24-0-0 as you said (not a typo), it probably means its got a lot of inert material like chalk
mixed with it. You'd first have to get rid of that.
Anthony
Moderator
Posts: 2383
From: England
posted 07-02-2001 05:07 PM
--------------------------------------------------------------------------------
I've used aqaurium tubing for distillation at temps over 100*C, it goes a bit soft (so you can squash it w ith your fingers) but does hold up.
Donutty
Frequent Poster
Posts: 228
From: UK
posted 07-02-2001 05:40 PM
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Thats strange, I thought I was the only Donutty about!!
Anthony
Moderator
Posts: 2383
From: England
posted 07-02-2001 06:38 PM
--------------------------------------------------------------------------------
If you're talking about this post:
"My glassw are should be coming some time next week. I ordered everything needed for HNO3 productionm, so when I make some, I'll let you know how it goes."
Then it's you, you daft git same number of posts and the first 5 digits of the IP's are the same.
Tony Montana
Frequent Poster
Posts: 145
From: Australia
posted 07-03-2001 03:09 AM
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JOHN456: I may need to clarify my last post!
1. In my first post, the book (or I) did not say anything about applying a vacuum with the afore mentioned procedure. Therefore the fumes will be red.
2. Prilled KNO3 would be crushed into powder, if it was aquired that way. Making volume measurements more accurate.
3. A BOTTLE is glass
A CAN is aluminium
I say nothing about a CAN, I do refer to a bottle though.
PYRO500
Moderator
Posts: 1513
posted 07-03-2001 03:53 AM
--------------------------------------------------------------------------------
I think I designed a vaccume still that might w ork, I just need to convert it to gif to upload and host the image of it
ALENGOSVIG1
Moderator
Posts: 782
From: Canada
posted 07-03-2001 03:58 AM
--------------------------------------------------------------------------------
I have purchased a complete 24/40 distilling apparatus from united glass technologies and should arrive soon. should be great! i jut gotta rip the compressor outa that old fridge
in the test field and make a vaccum.
Donutty
Frequent Poster
Posts: 228
From: UK
posted 07-03-2001 04:35 PM
--------------------------------------------------------------------------------
Mmm.. Must be a coincedence! It's a small world, afterall...
Oh and nice one using your power as an Admin to view my IP and tell everybody!!
Anthony
Moderator
Posts: 2383
From: England
posted 07-03-2001 05:07 PM
--------------------------------------------------------------------------------
Notice how yours and "his" post count is going up sychronously? Maybe someone used your computer and posted a message, but it's a very strange thing to post...
I think you should lay off w hatever it is that's killing yout short term memory...
I didn't tell anyone your IP Besides it's a dynamic one, I presume your ISP alw ays uses the same first 3 digits.
No more acetone fumes!
PYRO500
Moderator
Posts: 1513
posted 07-03-2001 08:30 PM
--------------------------------------------------------------------------------
oops!
[This message has been edited by PYRO500 (edited July 03, 2001).]
PYRO500
Moderator
Posts: 1513
posted 07-03-2001 08:31 PM
--------------------------------------------------------------------------------
here is my idea for A nitric acid still, I am assuming hardened fiberglass putty is acid proof does anyone think it looks workable? here is the location sorry I cant post it directly
geocities wont let me.
to view it just cut and paste into the location bar.
"http://ww w.geocities.com/pyro2000us/hno3.jpg"
[This message has been edited by PYRO500 (edited July 03, 2001).]
John456
Frequent Poster
Posts: 105
From:
posted 07-04-2001 12:03 AM
--------------------------------------------------------------------------------
Tony-
I know you didnt say anything about a vacuum, but the red fumes arent nitric acid vapors, there are some vapors among them that condense and thats why a vacuum is
preferred for better yields. it w ould probably be accurate enough measuring by volume if it was pow dered but id still rather measure it by weight =) Sorry about the bottle,
English is not my first language and i sometimes confuse bottles with cans especially when i see aluminum cans of coke in the stores everyday.
simply RED
Frequent Poster
Posts: 242
From: HELL
posted 07-04-2001 06:20 AM
--------------------------------------------------------------------------------
Someone said that making HNO3 from NH4NO3 and H2SO4 can be dangerous because some nitramines form....
PYRO500
Moderator
Posts: 1513
posted 07-04-2001 02:23 PM
--------------------------------------------------------------------------------
any comments on my still?
Donutty
Frequent Poster
Posts: 228
From: UK
posted 07-04-2001 04:39 PM
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Would probably work if the tubes were uniform ( unlike the drawing ). I prefer to use professional stuff though because (I hope) you can trust it! (and it looks good)
PYRO500
Moderator
Posts: 1513
posted 07-04-2001 05:53 PM
--------------------------------------------------------------------------------
in the draw ing I w as trying to imply that the tubing is in coils betw een the jars. it was hard to duplicate the drawing and I w as tired so it looked kinda funky I do not have the
money for expensive glassware so I decided to desingn a vaccume still that could work for many purposes. I am assuming that the fumes of the solution that are the least
volitle will condense in the first jar and then the fumes that need to be cooled more w ill go to the second jar and so on till the fumes are condensed, the aquarium air manifold
lets the vacume suck in air to keep from getting such a high vaccume that all liquids evaporate.
Anthony
Moderator
Posts: 2383
From: England
posted 07-04-2001 06:27 PM
--------------------------------------------------------------------------------
Looks good. The onlt thing I can think of is that, depending on the strangth of the vacuum, the liquid HNO3 might not go up the tubing and into the jar (it'd collect at the bottom
of the U's between the jars). Also, no provision to stop HNO3 vapours getting into the vacuum pump (unless it's expendable?)
PYRO500
Moderator
Posts: 1513
posted 07-04-2001 08:06 PM
--------------------------------------------------------------------------------
I was thinking of sunig small tubing, 1.5 or 2 mm inner diamater tubing that would have the liquid pressed out of it easily, if there is still liquid in the tube I will release the
vaccume by opening all the valves in the air manifold and unstoppering the distillation flask then I w ill slowly close the valves and let the vaccume pull the HNO3 into the jars. I
plan on having awater aspirator powered by a pool pump if I can find one cheap and I w ont have to worry about the vapors ruining the pump. the air manifold allows me to
slowly open pathw ays for the air till the vaccume is just enough to lower the boiling point of the liquid so it w ill only boil when above room tempature.
neo_philosopher June 27th, 2006, 02:32 PM

My way of translating AN into Nitric acid is like this-
1) dissolve alot of AN into a bucket of water

2) Perform electrolysis with copper electrodes.
3) Boil till all the w ater is gone. usually turns from green
to blue
4) decompose at ~180C and dissolve the gases in water
electrolysis makes ammonia and copper nitrate. I like to buy a

big chunk of copper from a scrap yard, use that on the positive
end and just a wire close to the surface on the neg. end.
See, weird compounds come alive with impurities, I think its like:
[Cu(NH3)4]SO4
this kind makes the solution green, once the temp is over 140 it releases
the final ammonia making blue copper nitrate liquid. Decomp is like this-
Cu(NO3)2 -> CuO + NO2 + O2
so perfect gas solution is made for water dissolving.
All it needs is to cool it down a bit. its better than any other metal decomp. b/c its the coldest. Cheap, simple. Although the pow er supply needs to be high amps, I found out
that computer power sources can dish out 10amps for 12v+. so I use two sources in parallel and the neg in ground. 20 amps at 12v is good enough to make alot of copper
nitrate. Just a warning, sometimes I had the result that the CuNO3 decomposed very rapidly... very rapidly indeed- BOOM
The_D uke June 29th, 2006, 04:19 AM

Why bother... :rolleyes:
neo_philosopher March 10th, 2007, 09:17 PM

I would bother because not only electrolysis is good for making copper nitrate, but also you can just heat ammonium nitrate and copper or copper oxide and that releases
ammonia. Then you have a cyclic process which only uses AN and outputs in one phase NH3 and in the next NO2 + O2. AN in, HNO3 out
Squizzy April 1st, 2007, 12:25 AM

Why not convert the AN into Sodium nitrate using Sodium Hydroxide. Much safer making nitric acid from that than AN.
I ve used a cast iron camp oven (dutch oven) as a reaction vessel instead of glass vessel. Drilled a hole and used a conventional distillation head , condensor and receiving
flask. To seal the camp oven use clay lute around the rim and the distilation receiver hole. Heat the oven to burn off any organics and oils.
Afterwards theres only a bit of surface rust on the oven after it dries mainly.
I used gas burner to gently heat the oven

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megalomania June 22nd, 2003, 03:47 PM

Tony Montana
Frequent Poster
Posts: 145
From: Australia
posted 07-13-2001 09:58 PM
--------------------------------------------------------------------------------
I know this topic is covered a fair bit, because I have just been reading olpd posts. But I dreamed of having 70% HNO3 and wanted to concentrate it. The way I am pretty much
going to go about it is:
Pouring 100ml HNO3 70% into a flask, then pouring 200ml H2SO4 98% into the same flask. Then Basically condensing the HNO3/H2SO4 with no vacuum, at a temperature of
80*-90*C hopefully collecting HNO3 90%-100% in the collecting flask? And dilute H2SO4 in the distilling chamber?
Does anyone know how successful this method w ill be?
mongo blongo
Frequent Poster
Posts: 175
posted 07-13-2001 10:48 PM
--------------------------------------------------------------------------------
Im with u until the "diluting the h2so4" ?
As far as i know to concentrate your HNO3,
well yes that's how evrybody does it as far as i know !
I would try to use a vacum pump to avoid nitric dioxides, Usally it is prefered that your HNO3 is white for most stuff (EG.RDX)
Watch those temps!
too much heat will decompose your HNO3!
John456
Frequent Poster
Posts: 105
From:
posted 07-13-2001 11:50 PM
--------------------------------------------------------------------------------
HNO3 ive distilled from 1 part H2SO4 and one part 70% or so HNO3 has only been around 85% or so. Ive found that adding about 3g of NaNO3 per 5ml HNO3 ensures the
concentration of your acid and increases your yield. Ive been able to distill HNO3 with that method (w ithout a vacuum) with densities up to 1.522 after being freed of NOx. I
should also mention that afterwards the sulfuric acid removed can be cooled and the sodium sulfate removed, and then reboiled to concentrate it, for 200mL of 98% sulfuric i
usually get about 120mL back.
froot July 23rd, 2003, 11:46 AM

I dreamt the follow ing:
After setting up a basic distilling appauratus I added 1 part 55% NA to 2 parts 99% H2SO4 into the distilling flask. I used a basic straight condenser. The receiver was immersed
in ice w ater. So I fired this baby up and here's what happened.
Nothing happened until about 90 degrees C. The solution then became slightly yellow and feint traces of brown NOx gas appeared in the distilling flask. The bubbling only
started at about 120 degrees C, w hich then slowed to almost nothing and the brown gas cleared up. Droplets of a pale yellow liquid was runnung into the receiver. At about 130
deg. the bubbling started again and soon slowed again. This pattern continued until about 170 degrees C. The liquid runnung into the receiver cleared up and the yellowed again
towards the end of the burn. The volume of liquit that left the distilling flask and is now sitting in the receiver is equivalent to 55% of the volume of dilute NA i started with. I'm
not too worried about the H2O in the acid because H2SO4 maintains it's boiling point even if diluted to a certain point.
It seems that the yellow liquid I've ended up with is a very high concentration of NA with a bit of NOx. There is brow n NOx gas present in the bottle above the 'acid' and the
'acid' fumes profusely in open air w ith that typical choking smell.
I speculate that during distillation tha NA is formed not only from NA vapours but also from a loop type reaction involving NOx, H2O, and O2.
Check this link: URL= http://www .cheresources.com/azeotrop.pdf (section 3).
Tonight I'll dream about adding a little AN and hexamine.
Off the topic; There is this chemical 'tris-hydroxymethyl aminomethane' C4H11NO3

Is there a use for this stuff in the spirit of this forum? Can it be used to make something that can be useful?
grandyOse October 6th, 2003, 12:48 PM

In another thread on this topic, someone suggested anhydrous epson salts as a drying agent for HNO3. I distilled some red/yellow fuming nitric acid that I estimate to be 75%. I
carefully w eighed and dried some epson salts and figured that the dry salt would absorb 55% it's weight in w ater. I added 7.38 grams of acid and 6.57 grams of salt. Now I
have a wet yellow salt. It is not sepparating, probably due to the similar densities of pure nitric and wet salt. I could filter it, but the loss of evaporation and filter absorption will
probably be too great. On a larger scale this may work OK. Any suggestions on how to separate the mixture?
Also, during the distilation, I had to keep the w ater bath to a boil to maintain distillation temp. inside the retort. Having to keep adding w ater, plus alerting the neighbors w ith
clouds of steam is a pain. Next time, I think I will use dilute sulfuric acid for the bath and kill two birds. Any ideas about this?
Anthony October 6th, 2003, 02:10 PM

Use cooking oil instead!
H2SO4 would be:
1) more expensive
2) less obtainable
3) A hazard, especially when hot
4) would still steam (possibly boil) as you mentioned using dilute stuff.

Originally posted by Anthony
Use cooking oil instead!
H2SO4 would be:
1) more expensive
2) less obtainable
3) A hazard, especially when hot
4) would still steam (possibly boil) as you mentioned using dilute stuff.
Since I am concentrating my sulfuric acid anyw ay, many of your points are moot. BUT I think the cooking oil is a supurb idea! Without having to add to the bath, I can maintain
a steady temp of 85C or so in the retort and have a more uniform and reliable process. This stuff will probably only splatter when a bug flies into it and I w on't have water
condensation on the ouside of all my glass. Wesson, it is. Thanks.
me234 October 20th, 2003, 12:27 PM

What about using anhydrous sadium sulphate to absorb the water from dilute HNO3?, This has been used to dehydrate esters after their formation, any opinions on how well this
would work?
knowledgehungry October 20th, 2003, 04:26 PM

You w ould end up with a mixture of Na2SO4 H2O and HNO3, unless you are suggesting using it as a dessicant. In that case i would doubt the Na2SO4 would w ork very well
either.
Mendeleev October 21st, 2003, 07:07 PM
I have read in numerous threads that a very good process for getting 100% HNO3 is by adding to potassium nitrate to 98% sulfuric acid. The reaction w ould be:
2KNO3 + 1H2SO4 ---> 2HNO3 + 1K2SO4
This is great and everything except that sulfates are soluble unless they are either lead, mercury, calcium, or barium sulfates. However the other product of the reaction K2SO4
contains an alkali metal, and alkali metal compounds are alw ays soluble. This is where the problem arises. How can one have 100% HNO3 (I am trying to make RDX) if you
have large quantities of soluble K2S04 in it? I have read the potassium nitrate method in so many threads and other sources that it greatly puzzles me. Any reply or clarification
would be helpful. Furthermore if you added calcium nitrate, wouldn't the product, CaSO4 be insoluble and thus precipitate out of the solution, creating pure nitric acid???
Thanks :D
knowledgehungry October 21st, 2003, 11:21 PM

:rolleyes: It's called distillation, also CaNO3+H2SO4--> sludge. More like a syrup than a precipitate and liquid.
Dhzugasvili October 22nd, 2003, 03:41 AM

I have found throughout my experience w ith Nitric Acid that the best way of concentrating is by simple distillation of 2 parts 98% sulfuric to 1 part 60-75% nitric acid.
Temperature was always regulated to keep the still going at anyw here from 1-2 drops per second, depending on the phase of the reaction (towards the end it slow s down). The
acid collected from this was found, using a density meter/hydrometer, to be of density 1.52. How ever, it was always impure from NOx fumes. Urea removes some of them but
not all. I am looking to build a vacuum pump for vacuum distillation. This would give me white nitric. This red fuming nitric i have used to make rdx, hmx, and a w hole bunch of
other shyt. It has w orked fine, but i w ould like to perfect the method.
I have also tried simple distillation with CaNO3 and H2SO4. Product w as of equal density but slightly more NOx fumes.
I have also tried w ith KNO3 + H2SO4 , all these reactions giving red fuming nitric acid of 1.52 density...which is suitable for many reactions i have found. but it seems there is
only one way to get white nitric acid that is completely pure, being a density of >1.5 and free of NOx fumes....vacuum distillation w ith any of the above processes - making an
aspirator for vacuum distillation is not too hard it seems. Comments, reactions, suggestions, pretty much appreciated. Do you guys agree vacuum distillation is the way to go for
white nitric acid?? I don't think there are any shortcuts.
rooster October 22nd, 2003, 04:03 PM

Hey there dhzuga;) , mail me about new s!
You are right about the 1-2drops per second thing. I have done several distillations of nitric acid, including too fast ones. I got about 5-8 drops per second at most, and was
happy seeing that my product was yellow . I thought is w as 95%+ . When measuring afterwards, the density was 1,45:( . And after all that work. This was with a 2-L distillation
bottle, 2:1 sulfuric:nitric. Of course I had too high temperature, so most of the nitric decomposed.
With 2-3 drops per second, you can't make many liters at a time, but hey, its 95%+ !
This acid is suitable for almost all reactions where high percentage HNO3 is needed.
Dhzugasvili October 23rd, 2003, 05:03 AM

ROOSTER ;)
Will mail you about news!! Good to see you posting! You're right your temps were too high and acid must have decomposed. You should take a look at the thread on vacuum
distillation and what they say about an aspirator and simple construction of one... i think this would be strong enough for vacuum distillation. Then you can start cranking out the
white nitric acid, w hich is under my impression as pure as you can get it w/out NOx fumes. Will keep ya posted :D
SantasL.Helper October 23rd, 2003, 12:58 PM

What are you guys measuring the temperatures of? The evolving gas or the fluid in the starter flask?
grandyOse October 23rd, 2003, 02:42 PM

Santa;
good question. I am using a retort with a condesner, and put the thermoter bulb at the same level as the retort output port (sorry about the nomenclature, if w rong). If possible,
I think it w ould be helpful to also measure the temp inside the reacting fluids (to keep down the NOx) and also the vapor out of the condenser to make sure you are cooling it
enough. It seems to me, if you can only measure at one point, it should be the excaping vapor.
SantasL.Helper October 24th, 2003, 09:24 AM

So you only need to make sure the Gas temperature is around the boiling point of nitric acid and don't need to mind the other temperatures? I got 2 thermometers, one for the
gas and one for the fluid. Can anyone tell me what to monitor?
+
I'm using a spiral condensor that is hanging vertical, instead of the normal classic cooler. Last time w hen i tried distilling nitric i only got a verrrrrrry small amount of acid (+ -5
drops total). Now i'm wondring, will my condensor cool enough to condensate all the nitric acid gasses? The water is about 8 degrees i gues and is constantly being refreshed
(connected it to our garden hose, let my parents pay all the water ;) ).
And w hat w ill give me better yields? Distilling concentrated sulfuric acid w ith 60% Nitric acid or ammonium nitrate?

Santa, define yeild. Both synths use up different chemicals. If the 60% nitric is cheep, this could w ell be the best for you.
According to orgsyn a good way to produce 95%+ acid is to distill 70% tw ice from an equal quantity of conc sulphuric, I'm not sure how doing it once from twice the amount of
sulphuric would change things.
Its unlikley to matter much which you measure, the gas or the liquid unless you have something to compair against. The liquid w ill probably be a lot hotter than the boiling point
of nitric acid w hen it comes off, ideally you should do fractions as the temperature of the liquid rises and compair that temperature with the strength of nitric acid being
produced. The results will only be valid for the specific process you use, method, concentration of reagents, but it would give you a reliable indication of how strong the acid was
in future attempts simply from the temperature of the liquid. I would not have thought under the circs that the temperature of the gas would be a reliable indicator. This is
completely the oppasite as to how organic distillations are done.

marvin; I am not one to doubt you, but I have seen many diagrams showing the thermometer bulb at the outlet of the reaction vessel. I have in front of me a college organic
chem textbook that show s the thermometer at this position in every distillation diagram. In fact it states that the bulb should be slightly below the outlet tube. Perhaps the
theory states that the boiling liquid, the vapor, and the condensing vapor are all at the same temperature. Perhaps my old textbook is so far out of date that their methods are
wrong, now . It seems sensible to me, though.
SantasL.Helper October 24th, 2003, 10:47 PM

But in order to get as pure nitric acid as possible from my 60% nitric and somewhere round 95% sulfuric acid: at what temperature should i keep the mixture or the gasses that
evolve?? Bp of nitric? Remember, i'm NOT using a vacuum (don't have a pump, nor an adapter).
PS, i got one of those thermometers in my setup :rolleyes:

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Cleaning
up after nitric distillation - Archive File
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megalomania June 22nd, 2003, 03:56 PM

stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-16-2001 04:53 AM
--------------------------------------------------------------------------------
By distilling H2SO4 and NaNO3, i produce my own nitric acid but after the distillation, the stuff who remains in the boiling flask is hard like rock and is very difficult to
eliminate...
anyone has a tip for cleaning this shit ?
thanx
John456
Frequent Poster
Posts: 105
From:
posted 07-16-2001 12:36 PM
--------------------------------------------------------------------------------
Put some hot vinegar (5% acetic acid) in and let it sit over night. In the morning if its not all dissolved youll be able to break it up and pour it out.
stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-16-2001 01:30 PM
--------------------------------------------------------------------------------
Is more concentrated vinegar will increase the speed of the "cleaning" ?
if yes, could it possible to distill vinegar to concentrate it ?
sorry for my bad englsih ...
and thanx !
John456
Frequent Poster
Posts: 105
From:
posted 07-16-2001 02:47 PM
--------------------------------------------------------------------------------
It may but i wouldnt bother, as concentrating it may take longer than using the 5% stuff to clean it =). To concentrate acetic acid you must first convert it to sodium acetate
and distill it with sulfuric acid. More info is on mega's page.
stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-17-2001 04:25 AM
--------------------------------------------------------------------------------
could you give me the exact page plz ?
thanx !
John456
Frequent Poster
Posts: 105
From:
posted 07-17-2001 12:52 PM
--------------------------------------------------------------------------------
http://roguesci.org/megalomania/synth/synthesis1.html#acetic you lazy bum
Trinitrotoluene June 22nd, 2003, 08:42 PM

Another way you can get that NaHSO4 or whatever waste out is to add 2 times the volume of water ratio of waste,then put it on some heatsource and bring it to a boil.After a
good 10 minutes of boil over half of it will dissolve into the soloution and the other can be broken into smaller pieces without any hastle. It works pretty well for me as I use
500ml erlinmyers flasks.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > short
question about hno3 - Archive File
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jam007
A new voice
Posts: 36
From:
--------------------------------------------------------------------------------
ok in the nitration proces of rdx it sais that it needs nitric acid free of nitrogen oxides so how do i eliminate this oxides after making it from ammonia bubbled into water????
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Could you be more concise I don't see the point: RDX or HNO3 made from ammonia bubbled trough water?????? Maybe some more readings couldn't hut you!
------------------
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
But if you really mean what I guess:
urea is the key to your problem.
NH2-C=O-NH2 gives urea nitrate what react whit the NxOy leading to HNO3, H2O, CO2 and N2!!!!!
------------------
SafetyLast
Frequent Poster
Posts: 233
From: the cretaceous period
--------------------------------------------------------------------------------
hey jam007 don't you mean heating ammonium nitrate and bubbling N2O gas into water?
you should just do a search on nitric acid there are a few topics about it already.
I think red and white HNO3 can be used (concentration must be above 80%) also which process will you be using? I suggest either the K process or the W process.
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Philou: you've confused me! In the little formula you wrote, the carbon only makes 3 bonds, and the oxygen also makes 3! What's going on?! I'm not saying you're wrong, I
just can't see how it works. Is it like in the ammonium ion, where the N is bonded to 4 H's?
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Yeah NH2-CO-NH2 is actually H2N-C(O)-NH2 or (H2N)2C=O; it is a formalism of organic chemistry to write things like NH3 HN3 HNO3 CO2 and not like O2C H3N N3H or
O3NH....you just have to live with that!I have written it NH2-C=O-NH2 so that everybody can see it is a cetolike form....
------------------
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Ahh, I see now. That makes a lot more sense!
nbk2000
Moderator
Posts: 1135
From: Guess
--------------------------------------------------------------------------------
OH __// / \ = C H OH = C7H6O \__/ 6 5

Which one is easier to write and still get across the structure?
Pop quiz hot shot, what's AcH and MeOH stand for?
As far as nitric from ammonia through water, I thinks he's referring to the catalyzed breakdown of ammonia into nitric oxides, which are then bubbled through the water to
form nitric acid.
------------------
"The knowledge that they fear is a weapon to be used against them"
Go here to download the NBK2000 website PDF.
[This message has been edited by nbk2000 (edited February 17, 2001).]
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Well, C6H5OH (yes, I know the numbers should be subscript but it doesn't seem to be working on my comp. for some reason) is the easiest to write while still getting the
formula accross because it makes it clear that there's a hydroxyl group, although it could be some kind of unsaturated alcohol I guess, because you can't tell that it contains the
benzene ring from just the formula. C6H6O could be loads of things, and the structural formula is just too time consuming to write.
As for the AcH and MeOH, I have no idea (or were you talking to Philou?). I suppose the MeOH could be methylamine hydroxide or something, and the AcH could be acetyl
hydride. But I've never used those abbreviations before so I don't know.
He would need to react the ammonia with oxygen with a catalyst to form water and nitrogen monoxide, and then dissolve the nitrogen monoxide with oxygen into water to
form nitric acid
4NH3 + 5O2 ->(??iron catalyst??)-> 6H2O + 4NO
4NO + 3O2 + 2H2O -> 4HNO3
PHILOU Zrealone
Frequent Poster
Posts: 479
posted March 14, 2001 11:29 AM
--------------------------------------------------------------------------------
MeOH is methyl-hydroxyde or methyl-ol and thus it is methanol CH3-OH an hybrid form often used in org. chem. between chemical formula and written name.
So does AcH; it is acetic protonated thus acetic acid (or more conveniently ethanoic acid CH3-CO2-H (Ac= CH3-CO2(-)))
Marvin June 25th, 2003, 10:45 PM

This topic has allready been rezzed and replied to. It should be deleted before anyone adds information better added to the older clone.

Improvised Manufacture of Nitric Acid > distilling inside
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piro July 13th, 20 03, 01:4 6 AM

Hey guys. I have a vacum distillation apparatus, but im wondering, since i dont have a vacum , can i attach a hose to the
v a c u m a d a p t o r o n m y glassware and b ubble the gasses through water so i can more safely distill inside? Or should i just
connect a hose to the vacum adapter and mabe run it out a window?
Arthis July 13th, 20 03, 05:5 2 AM

Y o u h a v e a v a c u u m distillation setup, and you want to use it as a standa rd non-vacuum system. That's your choice, I can't see
the interest (or do you lack the pum p m a y b e ? ) .
This depend on what you're distilling. Obviously, for nitric acid th e gas released by the setup are what you want to keep.
I n t h e c a s e o f s o m e t h i n g e l s e you want to purify, like sulfuric acid, the exhaust gas can be dangerous or not depending on
what you're distilling.
Y o u n e e d t o t a k e t h e d e c i s i o n case by case. No need to waste water as when distilling sulfuric acid you'll get mostly water, fo r
e x a m ple.
knowledgehungry July 13th, 20 03, 02:4 7 PM

He lacks a "vacuum " m ost likely he wa s referring to the pump.
Arthis July 13th, 20 03, 04:0 8 PM

Y e s , a n d t h e t i t l e o f t h e t h r e a d m a k e s m e think the problem is inside distillation. You should form ulate your post in such a
m anner they are m ore easily understood.
T h e v a c u u m p u m p d o e s n o t m ake the distillation safier. In fact a small part of th e gas released is dissolved in the water flush,
b u t d e p e n d i n g o n t h e c o m pound distilled, it will still be nocious.
Do your distillation near a window, because if you have to use a big lenght of tube to release nasty gases outside, you m a y
e x p e r i e n c e p roblem with rising internal pressure. The pressure p roblem is always im portant, that's why vacuum setu p s a r e
used.
If you don't have the pump, you should certain ly not bubble the gas thru water, because that will cause a e ven high er
pressure, and is not very good for the effectiveness of the distillation.
Trinitrotoluene July 13th, 20 03, 09:0 0 PM

I don't think distilling inside is a very good idea. I rem ember a few tim e s I d i s t i l l e d a c e t o n e , e t h a n o l , a n d m a t h a n o l i n d o o r s .
But when I tried to distill HNO3 indoors in m y kitchen, I was upstairs on I computer I can smell NO2. I guess the reason is the
teflon wraped around the stop pers are perm isable so NO2 can can diffuse through. I never tried to distill HNO3 indoors again.
Arthis July 14th, 20 03, 06:3 6 AM

I would say that you can do it with proper equipment. If I had a com p l e t e l a b , a n d a d e d i c a t e d r o o m, with good ven tilation,
etc., then why not ? But with hom e m a d e e q u i p m e n t y o u would take risks. I have a distillation setup, stolen from the school,
without PTFE rubber, so if I ha d a fum e hood I would try inside.
And while distilling nitric acid, supervising the process is useful, instead o f surfin' around o n your com puter ! ;)

Improvised Manufacture of Nitric Acid > Best condenser for NA vacuum distillation
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BLASTER July 16th, 20 03, 10:1 4 AM

W hile browsing old topics, I've not found any specific on type of condenser good or best for vacuum distillation of nitric acid.
I'm b u i l d i n g n e w a p p a r a t u s , s o l o o k i n g a l s o f o r a d e q u a t e t y p e a nd size of condenser, for boiling flask volum e o f 1 0 0 0 m l . A l s o
I want to know, if som eone have experience with various types of condensers.
Arthis July 16th, 20 03, 01:3 6 PM

The first principle of a condenser is to have the largest area possible in contact with a cold source, to allow the fum e s c o m i n g
out of the column to cool down and condensate.
There are several sorts of condensers, about any works well with NA, but som e a r e m o r e e fficient than others.
First Liebig condenser, consisting of 2 imbricated tubes, the fumes go through the sm allest one, and water is going between
the two. This is the base.
T h e n c o m e s s e v e r a l m odifications, to allow a larger cooling area. Bulb condensers are the same, e x c e p t e d t h e s m a l l e s t t u b e i s
replaced by a succession of bulbs, you get the point.
You can m ake about any design, I'm thinking about the one Blindreeper m ade.
T h e l o n g e s t y o u r c o n d e n s e r , t h e m ore efficient it will be (if we silence the problem of overpressure, which can be considered as
m inor in the case of happy am ateur's first time distilling NA). Standard condenser are about 30-40 cm, available at school, I
m e a n ; ) . W h en m aking yours make it as long as possible with neon tubes since they have a pretty high diam eter.
W ater cooling is recom mended, as if you don't do it you're m ost likely to experience problems with fum e s n o t c o n d e n s i n g
(also Blindreeper).
BLASTER July 16th, 20 03, 03:1 2 PM

So, as I understand vacuum s h o u l d n o t b e a p r o b l e m for any type of condenser. Then I m ay om it spiral types, where
condesation occurs just in spiral and liquid can collect in condenser, while not installed in alm ost vertical position. Also bulbs
had probably similar problem . W hile looking in lab glassware catalogue, Dim roth spiral type com es in m y m ind, where coolin g
m edia flow inside in spiral and is also cooled from outside. Look s like efficient condenser, I think about length of 300m m .
ALENGOSVIG1 July 16th, 20 03, 04:5 9 PM

I don't believe you can use a alihn condensor for distilling. Just get a 300 or 400 mm liebig or west condensor. They are pretty
cheap and they work well. You can get away with using a 200 m m condensor for d istilling nitric acid but it's not great for
distilling things that are harde r to condense or for refluxing.

Improvised Manufacture of Nitric Acid > Vacuum Distilator Schemes
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I spent hours searching and could not find all schem e s o f a v a i l a b l e v a c u u m distilators.
So this thread is dedicated to all available and known ways to distil under vacuum and the s c e m e s ( p i c s a n d l i n k s ) o f t h e
devices.
mongo blongo August 30th, 2003, 12:06 PM

Here is a cool idea from Rhodium using an water aspirator which would be a piece of piss to m a k e .
http://www.rhodium .ws/chemistry/equipm ent/aspirator.htm l
simply RED August 31st, 2003, 03:42 PM

C a n s o m e o n e d r a w m e the schem e of this aparature:
http://www.roguesci.org/theforum/attachment.php?s=&postid=38401
IPN August 31st, 2003, 04:59 PM

I l o o k s q u i t e s i m ilar to this:
http://www.rhodium .ws/chemistry/equipm ent/pictures/distillation_big.jpg
simply RED S e p t e m b e r 2 nd, 2003, 06:56 AM

beautiful!
0EZ0 September 2 nd, 2003, 08:21 PM

Shhh...
This (http://orgchem .colorado . e d u / h n d b k s u p p o r t / d i s t / d ist.html) should provide som e u s e ful information for you simply red. Be
sure to check out the rest of the lab te chniques on the site. Very informa tive.
Regards
simply RED S e p t e m b e r 4 th, 2003, 10:10 AM

really informative!
Today i was testing the resistance of PVC against nitric acid.
And noted th at PVC is not coroded from nitric acid in any concentrations, PVC was also resistant to concentrated sulphuric acid
a n d m i x e d a c i d s ( i n t e m perature interval from 25 to 100 degree s C).
Chemical_burn S e p t e m b e r 2 4th, 2003, 02:38 AM

W hat about useing PVC Al tub eing it would be resistant to the nitric so it should work for a nitric still.
Idiot April 10th, 2005, 04:19 AM

I have just m a d e i n m y o p i n i o m v e r y g o o d h o m e m ade aspirator. I didn't have any m onometer so I can't m e a s u r e v a c u u m
,but there is som e inform ation about it and photos. I have tested with 2 different nozzles Suction and water consum ption tests.
fi 3.5m m C o n s u m ption 280m l/s(A lot of ...) , Suction 175m l/s(Not bad ...)
fi 2.5m m C o n s u m ption 100m l/s(better ... not so m uch water will be wasted) , Suction 205m l/s. The last test with 2.5m m
showed very good results. And here is photos ... Btw all tests were perform ed at 3.3-4Bar pressure and with cold water.
http://img.photobuck et.com / a l b u m s/v281/form yfaFire2/sonas.jpg

http://img.photobuck et.com / a l b u m s/v281/form yfaFire2/Vacuum source.jpg
http://img.photobuck et.com / a l b u m s/v281/form yfaFire2/Purkstuvai.jpg
http://img.photobuck et.com / a l b u m s/v281/form yfaFire2/isrinktas2.jpg



tom haggen April 18th, 2005, 09:29 PM

I'm not quite sure what your asking for. It sounds like you want a schematic drawing of a vacuum distillation aparatus. Heres a
good pic m aybe this will give you som e i d e a s .



Improvised Manufacture of Nitric Acid > Q uantitative report on HNO3 distillation
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Microtek S e p t e m b e r 2 nd, 2003, 08:50 AM

Thus far, I have been content to view nitric acid of sufficient concentration to prod uce RDX as "high ly concentrated". However,
now that I am m oving on to HMX, the need has arisen to acertain that th e acid is more than 85 % concentrated ( th e m inimum
required to g et a m easurable yield of RDX ).
An NaOH soln of known concentration was prepared by dissolving solid NaOH in deionized water and titrating a carefully
weig h e d a m ount of pure benzoic acid in neutral ethanol.
- A batch of ca. 50 % H2SO4 was heated to 170 C to drive off most of the water. Titration showed a concentration of 90 %.
- 100 m L of this 90 % H2SO4 was m ixed with 1 00 m L 62 % HNO 3 in a retort of 250 mL capacity,
and distilled at atm ospheric pressure on a sandbath on an electric hotplate ( the hotplate is for cooking, and was set at 50 %
). No cooling was applied to the condenser.
- After 3 hours, no more distillate was com ing over, and the collected acid was seen to be distinctly yellow with NOx.
- About 50 m L distilla te is recovered from this batch size, which is a quite good yield.
- A s a m p l e o f the distillate was titrated and fou nd to be 88.00 ( +/- 0.04 ) % concentrated ( but note that NOx was not
removed prior to titration, so actual value is slightly lower ).
- The rest of the distillate was m ixed with 50 m L 96 % H2SO4 from a lab supply and redistilled under the sam e conditions as
before.
- Almost the same amount of distillate was recovered and was purged of NOx by bubbling dry air through it and adding about
0.25 g urea with heating ( the bubbling had to be continued for m o r e t h a n 1 0 m i n u t e s , a n d w a s m u c h m o r e e f f e c t i v e a t
e l e v a t e d t e m ps ( 50 C )).
- O nce the acid was com pletely clear, a sam ple was titrated and found to be 95.88 (+/- 0.08) %
I believe that the acid was diluted som ewhat by the purging process, and that som e o f t h i s d i l u t i o n c o u l d h a v e b e e n a v o i d e d
by n ot using urea and bubblin g at elevated tem p s f r o m t h e b e g i n n i n g .

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Hands on
experience with DCM method
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vulture September 28th, 2003, 05:50 PM

Recently I've been trying to extract HNO3 using DCM, as mentioned in US patent 3,981,975.
Materials used:
96% H2SO4 technical grade
70% HNO3 technical grade
DCM, technical grade, no information about contaminants
(all OTC material)
I added about 50ml DCM and 30ml HNO3 to my separatory funnel. After that 20ml of H2SO4 were added SLOWLY, as the hydratation energy caused a significant amount of
DCM to evaporate, leading to potentially dangerous overpressure.
After vigirous shaking and frequent venting I let the 2 layers separate for a few hours.
The first interesting fact was that the NOx which were present in my yellow HNO3 did not dissolve in the DCM phase, which was now totally clear and colorless.
I drained some 5ml of extract for testing.
The extract started fuming copiously after some time, presumably because most of the DCM had evaporated. Spills which were cleaned up with paper immediatly nitrated the
paper, again releasing large amounts of HNO3 vapor.
Also, after prolonged exposure to air, it seemed to attract fair amounts of water.
When I tried using the DCM/HNO3 mixture "as is" in a nitrating mix, I observed that sulfuric acid was mixable with the extract. However, as soon as trace amounts of water are
present, the H2SO4 will only dissolve in the aquous phase, possibly because of it's hygroscopic behaviour.
On a side note, I'd like to point out that H2SO4 is still needed for most nitrations, since it does not only dehydratate, but also makes the formation of the necessary NO2+ ion
possible:
2H2SO4 + HNO3 ---> H3O+ + NO2+ + 2HSO4-
Nitration of cellulose was only partially succesful, but the cellulose was of unknown quality.
A larger batch experienced a horrible runaway.
I left the separatory funnel and it's contents standing for 2 days and when I returned to try an RDX synth (no H2SO4 needed here) a bad surprise was awaiting me.
For some mysterious reason, the DCM/HNO3 and H2SO4/H2O layers mixed! :confused:
Upon careful examination I found out that my PTFE grease (used to lubricate the valve) had become a distinct yellow, but I don't know if it's the one to take the blame here.
Further testing is to be conducted in the future....
I'd like to hear comments/ideas/personal experiences, as this method does seem to be able to produce highly concentrated HNO3 without dissolved NOx.
EDIT: hexamine seems to be slightly soluble in DCM. This should be a good thing for RDX synthesis, because if the 2 reagents are dissolved in DCM, they can't come into
contact with H2O. Furthermore, the DCM will separate any formed H2O, shifting equilibrium to the right. Atleast that's my theory...
zeocrash September 28th, 2003, 06:39 PM

where do you get your DCM from, in the UK the only source i've seen is as paint stripper, and the main impurity in this is methanol, this could explain the mixing of the layers.
correct me if i'm talking out my ass but i bleive methanol is miscable with both water and DCM, which could explain some of the mixture mixing

The one time I tried it, I used a dry ice/acetone slush to freeze out the NA as crystals. They immediately liquified once I removed the container from the cooling bath, so I
wasn't able to filter them out, though I suppose you could use a fine metal mesh like that used for tea filtering and had it cooled in the the acid mixed, you could scoop them
out and dump them into something else before they melted.
Or you could distill off the DCM which would leave the NA behind.
Where'd you get your DCM from? Is it a paint stripper or an industrial solvent?
FYI, water is slightly soluble in DCM, though something less than 1%, and DCM is soluble in water at (IIRC) 4%.
I posted about this method elsewhere on here.
vulture October 3rd, 2003, 12:27 PM

I'm not exactly sure about the purity, it comes in an unmarked container. My guess is it comes from bulk industrial stock, I buy it OTC at a shop where I can get all kinds of
technical grade chems.
I doubt it was methanol contamination that caused the layers to mix. They only became miscible after 3 days or so.
zeocrash October 6th, 2003, 03:47 PM

Hmm wouldn't distilation produce some decomposition to NOx.
would it be possible to remove the DCM by bubbling dry air through the acid DCM mix. causing the DCM to evaporate off.
mongo blongo October 6th, 2003, 04:19 PM

The boiling point of DCM is well below the decomposition temp of HNO3, that's the advantage. :)

Electrolysis of Ammonia
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This has been a burning question of mine for a while, and I don't have the balls to ask it on the other forums (still a noob), so the water cooler seems like the best place. For
production of NOx, I was thinking you could run a high voltage electrical arc through hydrated ammonia, with sufficient oxygen. I have not seen any other posts talking about
this (I've read just about everything in the Nitric section), and numerous searches have brought up nothing. This leads me to the conclusion that 1) it forms diatomic hydrogen
+ electrical spark :eek: 2) it doesn't do crap, which would make sense because nitrogen compounds are not that stable, then again running an arc through air can produce
NOx. I've been trying to make a device that I could test this with made out of snapple bottles but it keeps breaking the glass when I try to drill the electrode holes! But has
anyone tried this, and how well has it worked?
xyz October 25th, 2003, 11:17 PM

You can make NOx by simply passing a high voltage/current arc through air.
So long as your equipment is kept dry then you can use plastic up until the point where the NOx is bubbled throguh water to make nitric.
EDIT: Oops, looks like you already knew that air could be used, yes this method has been tried by a couple of members but I can't remember who it was (10fingers?), and he
was able to produce 500mL of nitric in a few days.
IIRC I think he used a microwave oven transformer to get the voltage/current required.

Yea I guess I was thinking along the lines of electrical arc-driven Ostwald process, minus the platinum (still can't find a cat converter grrr), but then I realized air has 70% N
(smacks self), once I get a TV transformer I will try a Jacob's ladder setup, though there was a microwave on the side of the road with some other "For Free" stuff, my mom
wouldn't pull over though (realizes the need for own car once again).
On a side note, I have about 100-200 grams of Ammonium Chloride, used for moisture absorbers I presume. I read about Silica gel being able to absorb and catalyze NOx and
later release it, would NH4Cl have a similar effect, perhaps form NH4NO3 and Cl2 gas (yummy, jk).
Wait, wouldn't it form NH4NO3 if you bubbled NOx into Ammonia? The water would absorb and form some HNO3 and that would probably react with the NH4OH. If it works, it
would result in less loss of NOx I think which is good becomes it comes at a price (not really I don't pay utilities yay).
xyz October 26th, 2003, 07:04 PM

Yes it would form NH4NO3 if you bubbled it through ammonia, but HNO3 is much more useful and can be turned into NH4NO3 at a later date.

Woulddn't just burning ammonia yeild NO2? as in 4NH3+7O2-->4NO2+6H2O? maby I'm just an idiot.

I don't think hydrous ammonia burns, it has too high of a water content, and the rest is a stable salt (NH4OH). Maybe if you added a chemical you might be able to get it to
burn, meaning Period 1 elements...That would just give off ammonia gas though -
NH4OH + Na ---> NaOH + H+ + NH3

I believe the hydrogen ion would be absorbed by the water or precipitate as hydrogen gas. Well it still doesn't solve the problem that I've been facing all along - Nitric Acid.
Grrr...Right now it still seems like an air spark is the best way to produce NOx (goes and thinks on the crapper for a while)
BTW this is a problem for me because I have pretty much no way to get my hands on any kind of oxidizing chemicals. Fireworks are illegal in NY, I don't have a car to drive
around looking for fertilizer and then there is still no guarntee that I will find any. If only it were 50 years ago....yea thats what we all wish.

YayYouGoBoom if you try to tell me what I can and can't burn. If something has "too high a water content" what will happen if I heat it up? Will the water evaporate? I
think so. Will it dehydrate? I think it will. Anything will burn if you get it hot enough, more so if it is entirely composed of hydrogen and nitrogen. And if you cant find
"oxidizing chemicals" in NY I pity you.
nitric63 October 27th, 2003, 10:19 PM

If you heat aqueous ammonia the ammonia gas will be released along with water vapors so it
will still have high water content unless the NH4OH was very concentrated to start with. You'll
need an ammonia generator that uses an ammonium salt and a hydroxide like NaOH along with
a dessicating chamber to get anhydrous NH3 easily. Then you could oxidize it. Also, everything
most certainly will not burn if you get it hot enough, ever hear of the noble gases?
Zeitgeist October 28th, 2003, 02:12 AM

Actually didn't they use anhydrous NH3 as a fuel for the X-51? With liquid Oxygen as a rocket propellant in other things too IIRC.
Maybe you get N2 if it burns with insufficent oxygen
YayItGoBoom! November 4th, 2003, 10:40 PM

Yes I know you can burn just about everything, its called fluorine (XeOF6, used in microchip etching I believe). We're talking some kid's basement here. And it wouldn't be so
hard to get nitrogenous compounds if I had a car, which I don't, so I'm stuck here pondering up the possibilies of nitrogen oxidation. Though I think I have come up with
something that could produce a decent amount of nitric acid and other useful nitrates. A high power electrical arc (thinking carbon arc lamp) is used to produce Ozone, as well
as NOx. This air mix is supplied with auxillary oxygen and bubbled through the ammonia. The ozone oxidizes the nitrogen of ammonia, leaving water and hydrogen gas, while
the NOx readily converts NH4NO3. It seems a lot more efficent than using a spark to produce NOx and bubbling it through water, making very little use of the extra ozone.
Sonny Jim November 5th, 2003, 04:29 PM

I tried to generate a high voltage arc today by using a step down transformer backwards. I don't know if it would work at all since it blew out the power every time I tried to
turn it on. Is there a good way to prevent this from happening?
xyz November 6th, 2003, 04:06 AM

Hook something into the circuit to provide resistance (such as a resistor, a heater, some lightbulbs, etc.) this will lower the amount of current passing through the circuit and it
won't cause problems any more.
I advise that you get a multimeter, and learn about Ohm's law. If you do these two things you will be able to work out exactly how much resistance you need for the best
balance between arc power and not causing problems.
T_Pyro November 6th, 2003, 12:13 PM

A step-down transformer generally uses thicker guage copper wire for the primary, and the secondary has narrower guage wire. If you try to use it in the reverse order, you'll
be connecting the narrow guage coil (with lesser windings) to the power supply. With such a setup, you'll end up either blowing the mains fuse due to excessive current flowing
through the primary coil (which was originally the secondary), or just end up vapourising your primary. If you try to limit the current in the primary coil by using a current
limiting resistor, you'll end up reducing the power output of the secondary. Also, there'll be quite some wastage of power due to the resistor.
Why don't you just get a step-up transformer from an old TV or microwave?

I think I will do. I've gotten through so many DC converters though, by frying the diodes, I have a good few of said transformers lying about for experimentation. If they end
up cooking, it serves them right for being part of an already broken devive :p
Ive been thinking as to whether there's actually any point in going into the high voltage region though. I reckon a good few spark plugs fixed along a PVC pipe could do a
similar job, without having to go into dangerous levels of power, relatively speaking.
By the way, if you havn't guessed already, Im doing this to try and form NO2.

What about a microwave oven transformer? Plentiful, high power handling, and relatively high current output, if ~2Kv is enough for you.
Surely on a step-down transformer, the secondary will have the thickest windings? As there's more current on the low voltage side, and due to the lower number of turns,
there's more room for thicker wire.

I just have to get one of them. I've heard them mentioned as a good source of high voltages so often here!
A quick question though. How far will, say, from a microwave transformer, the electrical arcs jump? Ive had a long and interesting read on the thread in the HNO3 project
section, but it doesnt say much about the arks themselves. Sorry if this is irritating but I've always been brought up to be scared of electricity, and it seems to have affected
me more than I thought!
Ollie Snowie November 6th, 2003, 04:42 PM

I have seen pictures of the arcs from MOTs getting to 10cm in length. I have personally acheived ~5cm arcs, but that was with my heavy resistive load in series for current
limitation. This is sure to decrease the voltage a bit and definitely the current (Well, that's what it's there for!).
Also, I've tried putting a H.V. arc through ammonia ages ago and definitely didn't get any NOx. Maybe it wasn't conc. enough or maybe it just won't happen.
From my experiments with electric arcs goung through air to make NOx I have found that it is best to have a power supply capable of very long arcs but keep the electrodes
close together, play around with magnets to make the arc unstable in the position that it would normally be most stable in, and then suck air quickly through the arc and into a
tube. The arc is stretched out by the air frow and the magnets and the residence time of the air is short, creating lots of air containing a smellable conc. of NOx in it. Also, if the
arc does break, the electrodes are close enough together to form it again with no gap adjustment.
[EDIT - IMPORTANT - If you are getting one of these be careful to discharge the capacitor first with two electrodes on the ends of poles connected with a wire. The capacitors
usually contain a bleed resistor to serve the same purpose, only slower, but just be on the safe side with capacitors that could cause a limb to explode.]
T_Pyro November 6th, 2003, 10:02 PM

Anthony:
The secondary windings should, and do use a thinner copper wire. Even if the current in the secondary is greater, the power dissipation in the primary will still turn out to be
greater, unless the step-down ratio isn't too high. Both the secondary, and primary coils are wound over the same core in most real-world transformers, so the question of
"more room" does not arise.
Like Ollie Snowie said, be sure to discharge the capacitor before touching any contacts. While discharging the capacitor, do NOT, I repeat, do NOT just short the terminals with a
simple wire, or you'll get a major fireworks display. Use some current limiting resistor in series with a thick copper wire to discharge the capacitor gradually.
The distance that the spark can travel depends on the dielectric constant of the medium, and the dielectric strength of the medium. Reducing the pressure of the gases reduces
the dielectric strength, thus increasing the probability of sparking. Also, if the air is ionised before entering the electric arc chamber, the arc can be made longer. For best results,
try low pressure, pre-ionised air in the arc chamber.
Tuatara November 7th, 2003, 01:15 AM

T_Pyro: there are no hard and fast rules as to which side of a transformer has the thicker wire. In general the higher the current in a winding, the thicker the wire is. Usually
the manufacturer designs the transformer to have equal loss in the primary and secondary to give best efficiency and use of materials. The big problems with just reversing an
ordinary step-down transformer are
a) the insulation inside the transformer will not withstand the higher voltages
b) the magnetising current will be huge, as you are now driving way too much voltage into a small inductance. Most likely the transformer core will saturate and the inductance
will drop to 1/100th, so the current skyrockets and the breakers trip.
For gas breakdown voltage under low pressure search the web for "Paschen's Law". The breakdown voltage of a gas is largely related to the mean free path length of the gas
molecules. The breakdown voltage of dry air at sea level is about 3kV/mm, damp air seems to be around 1kV/mm.
In air you may notice that you can strike an arc at a certain distance , then draw it out further by spreading the terminals. Strike distance depends on voltage, how far you can
stretch the arc depends largely on the current. The construction of the arc terminals also affects strike distance (pointy => further)
Useful hint: ordinary light bulbs make great resistors for discharging capacitors - when the light goes out the cap is discharged!
T_Pyro November 7th, 2003, 01:52 AM

Tuatara: You are right in stating that there are no hard and fast rules as to which side of a transformer has the thicker wire. However, for a 230V AC I/P, 12V DC O/P (the most
common type I've come across) power adapter, the secondary is either designed for 1000mA, 12V O/P, or 35V, 2A O/P, which is then connected to a regulator (like the
LM317). In such a transformer, the secondary coil, I've noticed, almost always has a thinner copper wire. Like you said, such a coil would have a very low inductance, causing
the rms current value to exceed the rated value, and thus melting the leads/frame/insulation etc. I'd once tried to use a transformer in this way in our elecs lab, and ended up
blowing the fuse, as well as melting the plastic frame of the transformer... Not a pretty sight!:eek:
I'm curious: How good are the yields in terms of purity/ quantity of products in this small-scale method of preparing nitric? I really don't have much of a problem getting hold of
nitric acid, but if anybody recommends this process as a fair alternative to buying the acid, I might set up my own plant...
Ollie Snowie November 7th, 2003, 04:48 PM

I have to say that ordinary light bulbs will be a very bad choice for discharging this type of capacitor. Most likely the thin wire will explode from the intense heat and send bits
of glass flying. You are alright with discharging one of these capacitors with a fairly thick (~1mm) copper wire connected between two insulating rods for handling. Microwave
oven capacitors are not that huge (They will discharge through 1mm coper wire without a fireworks display apart from at the terminals, but you can be ready for that. The
bleed resistor will probably have already discharged the capacitor - this is just for extra safety.).
Also, I see no point in using step-down transformers backwards. They will saturate, as Tutara said, and MOTs are readily available and just right for this purpose (Perhaps the
current could do with being a bit lower and the voltage a bit higher.).
Also, before disaharging a capacitor with a short circuit, check that the capactior does not contain PCB oils - it normally says so if the capacitor is PCB free. PCBs are poisonous.
I think that a series resistor would definitely be a good idea as the capacitors sometimes explode from the intense magnetic repulsion between the plates in rolled capacitors
when discharging them without a series resistor. The only problem is that normal resistors explode with high voltage capacitors as well.
You should be fine with rubber gloves for insulation and DRY, THICK woolen gloves for an air gap while holding the outside of the capacitor, but don't go prodding the terminals
all the same.
Tuatara November 8th, 2003, 04:41 AM

You just have to pick your lightbulb ;)
Bleed resistors are an extremely good idea - a permanently affixed discharge device can avoid nasty accidents. For this application a 5W 1 MegOhm would do just fine. You can
even put a little neon bulb in series with another 1 meg resistor, in parallel with the bleeder - if its glowing then theres at least 90V on the cap, and it will bite!
I did just this to the electric fence energiser that gave me the nasty 25 joule 900V shock. Never got bitten after that.
I've never personally had a cap explode through heavy discharge, but I have seen them go open circuit. It seems the high current gradually burns the connection between the
foil and the lead wires. I opened about 10 of them that failed in my fence energiser, thats how I know. They only failed because the fuckwits who made them didn't
understand I^2T ratings, and gave their caps too high a rating, which I used of course.

Improvised Manufacture of Nitric Acid > ammonium nitrate--> nitric acid
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roux February 2nd, 2004, 10:07 PM

tho this may not be the most efficient or cost friendly way of obtaining nitric acid, i think its a method worth exploring. it uses
ammonium nitrate and hydrocloric acid.
ammonium nitrate is made of a possitive ammonium ion(NH4+) and a negetive nitrate ion(NO3-)
hydrocloric acid is made up of a hydrogen ion just like the one in ammonium nitrate and a cloride(Cl-) ion that is more
negetive than the nitrate ion.
i figure that if one were to mix the two compounds, the cloride ion would combine with the ammonium ion making ammonium
cloride. this would result in a left over hydrogen and nitrate ion that would be forced to combine to make nitric acid.
HCl+NH4NO3--->NH4Cl+NHO3
i have not attempted this reaction, but i would be thankful if anyone were to tell me how it goes.
Mendeleev February 2nd, 2004, 10:59 PM

Nice method, I have considered it, but it has a problem, unless you're using HCl gas your HCl will be at least 62% water, and it
doesn't have the hygroscopic properties of sulfuric acid, so the acid you distill over will be low concentration, at most you'll get
to the azeotropic point. Why do you say it is more costly? HCl= $2.50/gallon, H2SO4= $8.00/liter, NH4NO3=$6/25kg
KNO3=$15/25kg. And now that I think of it, not so bad considering you could get azeotropic acid for cheap and then distill with
H2SO4, which can be recycled. Eureka, that should save me a ton of money! One thing I am not sure HCl, NH4Cl, and HNO3
completely dissociate in solution (although NH4 doesn't NH4Cl does), so won't all the ions just be floating around in aqeous
solution causing HCl to distill first since it has a lower boiling point than all the others?
Marvin February 3rd, 2004, 09:24 AM

"i figure that if one were to mix the two compounds"
Nice try, but such speculation is almost always useless at your level of understanding (I cant think of a more tactful menthod
of saying this). As you progress in chemistry you'll have a much better grasp of what can work and how.
Mendeleev is a little uncertain in his terms, but his basic idea is correct. What you get is a nasty mixture of ions and oxidised
compounds, Aqua Regia, and a method for obtaining nitric acid would have to involve extracting just this from it. It would be
uneconomical for any method suggested before, or that I can think of. I'm sure this topic has come up before though perhaps
not in this section.
vulture February 3rd, 2004, 10:08 AM

NH4Cl <-----> NH3 + HCl is an equilibrium and will greatly interfere.
gliper February 6th, 2004, 02:01 PM

If it leaves NO3 or HNO3 in any resonable concentration you should be able to make uria nitate (mix with uria) and from there
nito-uria (7000 m/s). Both more powerful and sensitiv than AN.
As for HCl being cheaper when you can get ether one its not that simple. $2.50 is for 30% where as sulferic Is 30% for $3 a
gallon (at auto shops I've read) or 90ish% $17 a gallon, also remember 1 SO4 is worth 2 HCl s. I calculated that the cost of
HNO3 is the same for my drain cleaner and HCl but SO4 is more consentrated and easyer to use.
THEBOARDER February 12th, 2004, 08:49 AM

ok.
i have fertilizer 10-0-30 , 30% k2o and 10% N , name ( N-NH4 ) , can i have nitric acid from this
Rhadon February 12th, 2004, 02:49 PM

THEBOARDER, you're having three posts, and every single of them is nothing but crap. HED.
tom haggen February 26th, 2004, 04:43 PM

Since this is the official NH4NO3--> HNO3 thread, I have a couple quick questions relating to this topic. For starters, how much
more efficient is KNO3 and H2SO4 in the manufacture of HNO3, versus using NH4NO3 and H2SO4. Also If you did NH4NO3 and
H2SO4 would the ratios be about the same as they are when using KNO3 and H2SO4.
Boomer February 27th, 2004, 10:11 AM

My compi crashed during 'reply', and my reply did no come up after logging in again. Sorry if it comes twice for some reason
later:
Why should KNO3 be better? AN contains 20% more nitric and is much cheaper! And for the ratios: SEARCH or (even better)
calculate. 1 mol H2SO4 converts 2 mol AN to 2 mol HNO3, leaving 1 mol (NH4)2SO4 over. H2SO4 is 98g, AN is 80g, KNO3 is
101g per mol. Now it's your turn....
P.S. If you use more (max. twice as much) SA, the process is cooler/safer and the NA decomposes less, making it more
concentrated (less water and less NOx/nitrous acid).
markgollum March 15th, 2004, 01:17 AM

About reacting hydrochloric acid with ammonium nitrate.
In my experience, I have found that when ammonium nitrate is dissolved in 31% hydrochloric acid, crystals of what should be
ammonium chloride precipitate (I say "should" because the crystals were not tested).
The precipitate quickly dissolved when more water was added, being completely dissolved when approx 75%IIRC of the
original acids volume of water was added.
With this knowledge in mind, this is how I think nitric acid could be produced from HCl(aq) and AN (with terrible yields).
(1) Dissolve AN in conc hydrochloric acid.

(2) Filter out ammonium chloride.
(3) Boil soln until either more chloride ppts, (unlikely because of increased solubility of chloride due to high temp, and
NH4CL(aq) > NH3(g) + HCL(g))
or you reach azotrope, (if ammonium chloride ppts then refilter.
(4) Cool solution to try to ppt more chloride. (saves on H2SO4 by reducing this from happening H2SO4 + NH4Cl > HCl +
NH4HSO4)
(5) Extract nitric acid from solution with either sulfuric acid and distillation, or by using a dichloromethane extraction.
I am sure that the yields would be abysmal, but considering the value of nitric acid, and the availability and cost of reactants,
it might just be worth it.
simply RED March 16th, 2004, 12:28 PM

How do you thinik (NH4)2SO4 can be reached?
The reaction stops when you have (NH4)HSO4 or KHSO4 it does not matter.

You can almost certainly make an aq mixture of HCl and HNO3 where the HNO3 is the larger componant. But if remotly
concentrated, it will be highly reactive (destructivly oxidising, etc) and removing the HCl will be either tricky or expensive.
Standard method is to distill from silver nitrate, producing also silver chloride which is difficult to recycle, and needs surprise
surprise, nitric acid free from chloride. Overall it will certainly make dilute nitric acid, but its a hell of a lot of work and you then
have to concentrate it.
Steps 3 and 5 in the suggested process look unworkable to me and you cant distill nitric from nitric+AgNO3+H2SO4 in order to
concentrate and remove chloride at the same time - just in case that is what you were thinking of suggesting next :)
tom haggen March 17th, 2004, 01:55 AM

I would just like to follow up on my previous post. I did further reasearch on this topic and found that it is extremely
dangerous and unefficient to manufacture HNO3 with NH4NO3 and H2SO4. As for manufacturing HNO3 with hydrochloric acid
and ammonium nitrate, it might be safer I don't really know. It seems pointless unless you want to manufacture some HNO3
with low concentrations.
grendel23 March 17th, 2004, 05:34 AM

Tom,
On what do you base your statement that using NH4NO3 to make HNO3 is "extremely
dangerous and unefficient".
I have read posts from members who had poor yields, but I had not heard that the procedure was more dangerous than using
other nitrates.
In this thread, http://www.roguesci.org/theforum/showthread.php?t=2333, Rosco Bodine states;
"For making azeotropic nitric acid 68 per cent which

distills at about 120 Centigrade, Ammonium Nitrate
is actually preferred . There is added to the mixture
sufficient water to account for the water to be contained
in the azeotropic nitric which will result , plus a few
more per cent of theory because the dehydrating action
of the sulfuric tends to disrupt the azeotrope in favor
of more concentrated nitric being produced . A nearly
100 per cent yield of azeotropic nitric acid 68 per cent
is the result from a very smooth and rapid distillation
where the residual mixture remains a liquid
having no precipitated acid sulfate salts at the
120 degree C temperature of distillation."
I have not tried this yet myself, but I have a lot of respect for the knowledge and experience that Rosco has shown.
I am going to give this a try soon, I like the idea of no fudge in the flask afterwards.
tom haggen March 17th, 2004, 10:05 AM

"Ammonium nitrate, unlike alkali metal nitrates, breaks down at a relatively low temperature. The reaction may be self-
perpetuating once started."
I'm quoting polverone from a different forum. However, it was uncertain if this was 100% accurate. Also it was stated later on
in the same thread that your final product would be heavily contaminated with ammonium nitrate.
Another quote from the same thread was "Heating this a little too hot is a serious problem since over a cetain T HNO3 will
evolve NOx that will destroy your NH4NO3 quite fast (maybe explosively) and your HNO3 also!" by PHILOU Zrealone
markgollum March 17th, 2004, 07:48 PM
Marvin suggested that nitric acid with HCl in it would not be useful to preform nitrations with.
You can almost certainly make an aq mixture of HCl and HNO3 where the HNO3 is the larger componant. But if remotly
concentrated, it will be highly reactive (destructivly oxidising, etc) and removing the HCl will be either tricky or expensive
While I was thinking about this, I noticed that the only reason that the this equilibrium is on the right, is because the chloride
is being removed from the system.
HCl(aq) + NH4NO3(aq) > HNO3(aq) + NH4Cl(s)
HOWEVER, (this is the interesting part) once the amount of chloride that precipitated is removed, the equilibrium should shift
again, (way to the left) because of the excess nitric acid, and the fact that nitric acid is a stronger acid than HCl(aq).
excess HNO3(aq) + remaining NH4Cl(aq) > HCl(aq) + NH4NO3(aq)

(pretty much completely on the right)
Then in step 3, (boiling) the hydrogen chloride would evaporate pushing the equilibrium even further towards NH4NO3.
Because of this, I think that the remaining solution would contain only AN, nitric acid, and water with only an insignificant
amount of HCl(aq).
Guerilla March 18th, 2004, 04:19 PM

Take into account that raising the temperature will change the whole equilibrium constant, and most likely so that it will go
more towards HCl + NH4NO3 due to it being an endothermic direction. Let alone how it will also favour the decomposition of
NH4Cl and oxidation of HCl as has been stated earlier. While this may not be an issue in a small scale its good to note that
Cl2 that forms (aqua regia) can react with NH4Cl forming nasty NCl3.. This method seems to be of no practical use for making
HNO3, mostly because of the equilibrium reactions that interfere with each other.
Boomer March 19th, 2004, 11:48 AM

Maybe you are right. But I remember reading somewhere that if heated stronger, the sulphuric is completely used up till the
X2SO4 is formed.
You should avoid this by using a little over 1 mol acid (not 1/2 mole) per mol of nitrate as the NA decomposes faster at the
temp needed for full conversion.
I am no chemist but I could imagine that, even though the hydrogen sulphate is the weaker acid, it converts more AN to NA.
Perhaps because NA is more volatile? Even though HCl is stronger than SA, it is driven of if SA is heated with NaCl.
To tom haggen: Using NH4NO3 IS efficient! 1 mol AN give 41ml HNO3 in theory, and that is what you get. I usually stop at
37ml as then the dropping gets slower at the same heat, and I want to avoid decomposition.
The resulting NA is nearly white (only very faint yellow), and works well even for RDX. :)
And it is NOT that dangerous. Pure AN can decompose explosively if heated above 200C. But it is mixed with 2.5 times it's
weight of SA, and most is converted to the non-explosive sulphate anyway. The rest cannot heat the whole mass enough, and
you work slowly at low temp anyway to avoid diluting your nitric with water from its own decomposition.
I have done it lots of times, and it stops boiling if you turn the heat of, even in litre batches. :D
tom haggen March 19th, 2004, 02:23 PM

I'm not a chemist either, and I'm somewhat skeptical of how dangerous this process is. However, something I don't like to do
is waste my time on projects that aren't going to give me any results. This method of manufacturing HNO3 is completely
unefficient. As madscientist said "It technically will work, but not well at all. The ammonium hydrogen sulfate formed will be
decomposed into sulfuric acid and ammonia from the heat; the ammonia gas will then react with your nitric acid to form
ammonium nitrate. You will get some nitric acid, but I doubt that your yields will be worthwhile, for much of the nitric acid will
have been converted back into ammonium nitrate, as well as the fact that what nitric acid you do have will be heavily
contaminated with ammonium nitrate." With this happening I find it hard to believe that you manufactured HNO3 capable of
synthesizing RDX.
Rosco Bodine March 19th, 2004, 05:50 PM

There is a German patent DE280967 which should provide
some accurate information about making nitric acid from
ammonium nitrate and sulfuric acid . Maybe Rhadon
or someone else here can translate the German to English .
I know that what I reported concerning azeotropic nitric

is accurate .
And yes ammonium nitrate does decompose at lower

temperatures than metal nitrates . However , unless
that decomposition was highly catalyzed by certain
impurities , ( chloride comes to mind ) , nitric acid
is formed and distills at a fairly low temperature ,
which is well below the temperature at which there
would usually occur significant decomposition of
ammonium nitrate .
In COPAE pg 370 , Davis mentioned that ammonium nitrate in

a large excess of concentrated sulfuric acid produces a mixture
which contains free nitroamide , but that the nitroamide
is hydrolyzed to nitric acid if the mixture is "digested"
for a time with gradual and gentle heating at 90 to 120 C
which is precisely the way a nitric acid distillation proceeds .
"Failed experiments" are not a waste of time , for you

are then equipped with good information about what doesn't
work in reality as it would seem it should work in theory .
Experimental results beat the hell out of anyone's guesses
and speculations based upon theory .
Rhadon March 19th, 2004, 06:31 PM

Rosco, I was unable to find this patent on the net. Can you supply me with a link or otherwise give me access to the file? Then
I could take a look at it.

Attached is the zipped pdf for DE280967 .
For some reason the file size upload limit
was exceeded for the uncompressed pdf file .
Go to the following page and enter the de280967 in the

second search box , then hit the Go button and follow the links .
http://ie.espacenet.com/espacenet/ie/en/e_net.htm
or a couple of direct links which may or may not work ,
http://l2.espacenet.com/espacenet/bnsviewer?CY=ie&LG=en&DB=EPD&PN=DE280967&ID=DE++++280967A++I+
or try clicking the highlighted patent number on this page
http://l2.espacenet.com/espacenet/viewer?PN=DE280967&CY=ie&LG=en&DB=EPD
Rhadon March 20th, 2004, 07:54 AM

Thanks for the patent, Rosco. I've been to the German version of the page you linked me to, but for some reason I wasn't
able to get this patent and I was told that it wasn't available on the server. Probably I did something wrong.
Anyway, here's the translation. I begin with page 1, line 25 as we don't need the preamble. Just remember that the patent is
from the beginning of the 20th century.
There's no doubt that ammonium nitrate can be reacted with sulfuric acid just like sodium nitrate. But applying the same
process would result in considerable losses in the nitric acid yield because of the height of the temperature required. According
to Berthelot, ammonium nitrate does already melt at 152 C, but decomposition starts at the same temperature if the reaction
is carried out in an iron vessel. At 185 C the salt will decompose completely under the evolution of N2O.
Now the invention is to measure the amount of sulfuric acid so that the production of nitric acid is already completed below the
temperature reaches 152 C or 185 C respectively. This can easily be achieved by using so much sulfuric acid that for each
molecule of ammonium nitrate there is at least one molecule of sulfuric acid. Hereby the reaction product does already melt
completely and the resulting nitric acid has already completely distilled over without any ammonium nitrate being
decomposed, at temperatures that don't exceed 120 C significantly.
Important advantages of this process are:

A higher, almost theoretic yield of nitric acid.
Significantly lower content of nitrous acid in the nitric acid produced.
The distillate is free from sulfuric acid.
Calm way of working, since the reaction mass doesn't show the tendency to rise in the reaction vessel during any time of the
process.
The possibility to use this process for concentrating less concentrated and impure nitric acid, such as that gained with the "air-
nitrogen process" [probably reacting NH3 with air at elevated temperatures].
The possibility to neutralize the remaining excess of sulfuric acid with ammonia and thereby gaining commercial grade
ammonium sulfate what cannot be done to the same extent with sodium sulfate when sodium nitrate is used respectively.

Rhadon ,
Thank you for the translation .
That's good information . Generally I have found that reports

from German chemists are highly reliable .
Prills and Drain Cleaner , yeah ....it doesn't get any easier :)
Just bring up the heat slowly and use a slight excess of sulfuric
for satisfying the equation
H2SO4 + NH4NO3 -----> NH4HSO4 + HNO3
The water in the 92.5 per cent sulfuric acid drain cleaner
actually helps the reaction in that it helps hydrate any nitroamide
formed to convert it to nitric acid . Also , the highly soluble
ammonium acid sulfate by product remains a liquid , not
complicating the distillation with any bubbling curd of solids ,
and probably also contributes an affinity for water to keep
it from distilling over at lower temperatures . Ammonium salts
also have the property of reacting with nitric oxides to decompose
them to nitrogen and water , similarly as does urea .
Boomer March 23rd, 2004, 08:04 AM

Well, obviously Madscientist was wrong and those of us that get 90% yields of RDX-grade nitric acid from AN (like me) were
right. The patent gives a scientific explanation why it works! :)
In another book I found the statement that at SA : NA : H2O = 1:1:1 (mol), the formation of N2O5 is just prevented. With
less water it starts to form, decomposing to N2O4/NO2 and O2. This ideal ratio is 55% SA, 35% NA and 10% H2O (weight).
This means drain cleaner (92%) is more than strong enough, even if the AN is a little moist.
Another thing I found: If you use a little more SA, you first destil RDX-grade NA off, then add more AN to fully use up the SA
(if it is your most expensive precursor). The second crop is less concentrated and contains more NOx (deeper yellow instead of
nearly colourless), but can still be used for MNT/DNT etc. where NOx and a little water do not matter much.
NTAN May 12th, 2004, 10:50 AM

Some thing here disturb me,
I know that HCl and strong oxidizers react and emit Cl2
so why you got HN4Cl and not free Cl2?
Boomer May 12th, 2004, 11:36 AM

We don't get Cl2 because there is no Chlorine in the reaction! The problem is rather that some of the nitric acid is
decomposed and forms dihydrogen monoxide ..... :p
OK, you might have missed that the conversation moved towards SULPHURIC acid plus ammonium nitrate.
P.S. What is HN4Cl ?
0EZ0 May 13th, 2004, 01:36 AM

He most likely meant NH4Cl or Ammonium Chloride.
I don't understand all this who-ha about the credibility of producing Nitric Acid from H2SO4 and NH4NO3. It should be well
noted that most Ammonium salts tend to decompose at relatively low (go figure) temperatures as compared to other more
traditional ionic salts. An easy way to avoid substantial decomposition and thus contamination of your final acid is to as noted
distill at low temperatures with an excess of H2SO4. It makes quite alot of sense does it not?
I suspect what madscientist was getting at was the trend of low temperature decomposition of Ammonium salts. Distilling at
such high temperatures as 120 degrees Celsius will also result in alot of NOx contamination of the final acid and so is a less
suitable temperature for distilling. People who do distill at higher temps are probably more impatient and think that a little
contamination is worth the shortened distilling time. There is nothing wrong with doing that with methods using KNO3, NaNO3
and Ca(NO3)2. You really only have to be wary of the Sulfate salt produced and it's decomposition when using methods
incorporating NH4NO3.
Note that most Ammonium salts (and alot of other compounds) don't just "go poof" at their written temperature of
decomposition. Decomposition starts at much lower temperatures and is increased as the temperature rises. This should
already be known but I thought for the sake of clarity I would add it.
nbk2000 May 13th, 2004, 06:51 PM

Fortunately for us all, madfag and his delusions of "kHemIcL" knowledge, have long since been purged. :)
Chemistry is not simple 1+1=2, try as you might, because there's many variables involved that are not linear progressions
from point A to point B. He couldn't grasp that concept. :rolleyes:
Thus, people who've empirically determined that the process works, by actually trying it, have knowledge on the subject that
cook-book theorists will never have. :p
tmp May 16th, 2004, 02:45 AM

I've always made NA with KNO3 and SA. I can see how AN would work with
SA, but even the most concentrated HCl(liquid) is still mostly water. Even
though it's cheaper, HCl looks like too much work for too little acid. I'll try SA
with AN method to satisfy my own curiosity.
ikbendirk May 16th, 2004, 10:29 AM

How about the NH4NO3 -> HNO3 + NH3 rxn?
It is a self-sustaining reaction I believe*, but there are only two problems:
- The reaction should not be mistaken with the rxn which produces nitrous and water, I believe the HNO3 rxn can be catalysed
by Cl- ions.. am I correct?
- As a product, you will most likely get two gases, namely NH3 and HNO3 as a gas (because of the heat) one must try to
condensate the HNO3 gas as quick as possible to get it as liquid. The concentration should be very high, as no water is
included with the reaction...
[HNO3 = Boiling point: 121 C (69% boils at ca. 86C)]

[NH3 = Boiling point: -33.3 C]
What do you say.. could this be practical?
[Edit:]
* according to "Basic Inorganic Chemistry" the H of the HNO3 rxn is 171 kJ/mol, meaning the rxn is endothermic and cannot
possibly be self sustaining. I quote:
Many ammonium salts volatilize with dissociation around 300, for example:
NH4Cl (s) = NH3 (g) + HCl (g) H = 177 kJ/mol

NH4NO3 (s) = NH3 (g) + HNO3 (g) H = 171 kJ/mol
Salts that contain oxidizing anions may decompose when heated, with oxidation of the ammonia to N2O or N2 or both, for
example:
(NH4)2Cr2O7 (s) = N2 (g) + 4 H2O (g) + Cr2O3 (s) H = -315 kJ/mol

NH4NO3 (s) = N2O (g) + 2 H2O (g) H = -23 kJ/mol
<...>
Nitrous oxide, N2O, is obtained by thermal decomposion of molten ammonium nitrate:
NH4NO3 (s) --250--> N2O (g) + 2 H2O (g)
I don't know quite how to seperate the N2O and HNO3 reactions, but i guess it should have something to do with the
temperature which should be kept above 300.
I am still a bit puzzeled about the '=' in the equitation, but I guess it is meant as an '-->'.
Well I guess it would work as follows:

1) Heat the NH4NO3 (300+)
2) Collect the gases
3) Cool the gases down to any temperature between 80 and -30 this could be done with ice, or just plain water.
4) let the NH3 gas escape and you should have some nice pure nitric acid.
http://www.redrival.com/blackstorm/HNO3.txt
I have not tested it yet, but I guess it should work...
nbk2000 May 17th, 2004, 12:28 PM

Heating ammonium nitrate gets you nitrous oxide (laughing gas) and water, not ammonia and nitric acid.
Chemistry is not 1+1=2.
Just because AN is made from ammonia and nitric acid doesn't mean you'll get the same two chemicals out of it when you
break it down. :rolleyes:
Boomer May 18th, 2004, 11:19 AM

If you want to learn about NA decomposition, read the Escales book on AN explosives. He gives 7 (IIRC) ways of reaction, one
of them being into HNO3 + NH3, others give N2O + H2O; NO + N2 + H2O; N2 + H2O + O2; NO + NO2 + H2, ... I forgot some.
You can get every possible gas mix, but in the end he says that it comes down to either laughing gas and water, like NBK said,
or nitrogen, oxygen and water (if fully detonated).
I would not try to get high on the N2O though, because you might have traces of NH3, HNO3, HNO2, NO and NO2 in it ... :p
K9 May 18th, 2004, 11:36 AM

Although there are going to be a variety of gases produced during the decomposition of NH4NO3 (as stated by the above
poster), the main gases formed are N2O and H2O thus making that quite an ineffective method of production.
As far the N2O goes, it's not too hard to purify it by bubbling through cold water which will remove the nastier of the products.
Then again, I wouldn't try inhaling it.
nbk2000 May 18th, 2004, 05:43 PM

I would not try to get high on the N2O though, because you might have traces of NH3, HNO3, HNO2, NO and NO2 in it ...
TRACES being the operative word in the above.
You might get nitric from AN, but it wouldn't be under conditions you could duplicate with standard glassware, likely requiring
high pressures and temperatures, same as those required to create it from air in the first place.
And there's 9 forms of ice crystallization possible, but only 1 happens in your fridge, so what's your point?
K9 May 18th, 2004, 08:29 PM

Not really on topic, but I'm fairly certain that there are even more than 9 forms of ice. Something like more than 12 even.
Which again reinforces the point you're not going to have an effective production method this way.
TOX August 8th, 2006, 05:54 AM

Hell ya I got the video at last ammonium nitrate --> nitric acid .English Subtitles for at least the concentrations and
temperature would be great.
http://rapidshare.de/files/28607245/_________________.wmv.html
Enjoy,guys
nbk2000 August 9th, 2006, 04:31 AM

I love how the raghead chemist is wearing latex gloves and wearing sandals while handling open beakers of Sulphuric acid and
fuming NA. :rolleyes:
The still they used in the video would be easy to duplicate. An improvement would be to put a U bend in the acid outlet tube
to keep uncondensed acid fumes from venting out. Not only is that wasteful, but also hazardous to the operator.
As for ratios, concentrations, and yields, UTFSE here and you'll find plenty of discussion on these details in other threads. :)
NoltaiR August 18th, 2006, 08:16 AM

I also really like that they use some proper glassware.. but they also don't forget the necessary cooking pot :-P oh there's
nothing like watching the middle-easterners play with chemicals..

Improvised Manufacture of Nitric Acid > C oncentra ting HNO 3 W ithout Apparatus?
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c0deblue May 8th, 2004, 04:11 PM

A ve ry early patent m ay provide clues to a possible m ethod of obtaining high strength HNO3 without distillation,
heat, vacuum , or lab equipm ent of any kind apart from a suitable glass container. The use of phosphoric a cid as a dehydrating
agent for HNO 3 has bee n touche d on in a few past posts, but the possibilities don't seem to have been really
explored.
Ba c k g r o u nd:
Patent # 1,008,690, awarded to Eberhard Brauer Novem ber 14, 1911, discloses m ethods for concentrating HNO 3
using phosphoric acid or arsenic acid as substitutes for H<SU B>2SO4 in a simple (non-reflux) distillation
process. But it is what the patent states about the properties of phosphoric acid - not the described m ethod itself - that
suggests avenues for further investigation.
Quoting from the patent:
"Sulphuric acid as a d ehydrating agent in conce ntrating dilute nitric acid by distillation possesses this disadvantage, that in
addition to the water with which it chem ically com bines to a considerable extent it also unites with the nitric acid itself, with th e
resu lt that th e boiling point of the m ixture is re markably increased whereby a con siderable decom position of the nitric acid
takes place in additio n to an increased expenditure of heat, as compared with the simple distillation. ...
The use of acids of the phosphoric acid group, especially phosphoric and arsenic acid, as compared with the above, possesses
the following advantages: They do not enter into any chemical com bination with the nitric acid, but merely combine with the
water. The production of a nitric acid that contains but little water, from a mixture of diluted nitric acid and phosphoric or arsenic
acid, therefore does not require any kind of decom position of any chem ical compound, as is the case when em ploying
sulphuric acid as a concentrating agent. ... It is, therefore, neither necessary to em ploy more heat than required for m ere
distillation, which m eans a savings in fuel, nor is there any fear of a decomposition of the nitric acid taking place. Hence it is
possible to o btain as a product a nitric acid of a high pe rcentage and free from nitric oxid."
T h e p a t e n t g oes on to describ e the progression of a sim ple distillation em ploying 1.7 S.G. (about 85%) phosphoric acid in a
2:1 ratio with 65% nitric acid. HNO 3 yield and concentrations are given as follows:
"On heating, nitric acid of nearly 100% strength is distilled off, the concentration decreasing as the distillation is continued. On
stop ping the distillation when 80% of the absolute nitric acid in the dilute d nitric a cid used have passed over, a nitric acid of
92% strength is obtained."
T h e p a t e n t a lso gives HNO 3 yields and concentrations for distillation using arsenic acid (of undisclosed
concentration). These data are shown here for reference, but arsenic acid should probably be avoided due to the difficulties of
obtaining it and dang ers associated with its use:
"... During th e distillation, the first fraction which passes at 97 percent strength is 30% of the pure nitric acid contain ed in the
original diluted nitric acid. The first 86 percent of the quantity of pure nitric acid in the original dilute nitric acid used, when
collected together, will result in an acid of 94 percent strength. The next 14 percent of the quantity will still contain 47 percent.
Ultimately, pure water will pass. W hen so conducting the process that the distillation is stopped only when nothing but pure
water passes, the entire quantity of nitric acid employed will be recovered in the form of nitric acid of 86.9 percent strength."
The idea:
The patent states that phosphoric acid "chem ically com bines" with water but not with nitric acid. I take this to m e a n t h a t t h e
phosphoric acid form s a true solution with water, but only a mechanical m ixture with HNO<SU B>3. Even though the
m ethod disclosed in the patent exploits this characteristic in connection with a distillation process, it seems logical that there
s h o u l d b e a n e q u a l i f n o t g r e a t e r a d v a ntage if gravity separation rather than distillation is used as the concentrating method.
In a batch distillation process the pot solution strength continually declines as the product distills o ver, resulting in an ever-
dim inishing distillate concentration. If the reasoning above is valid, this should not be true of the proposed gravity separation -
after thorough m ixing, the phosphoric acid (at a suitable ratio) should sim ply take up all the water in the dilute HNO 3 and then slowly separate into a distinct layer, leaving high-concentration HNO3</SU B> to be drawn off.
A r o u g h a p p r o x i m ation:
Initial estim ates show that at the 2:1 ratio called for in the patent, the density of the resulting pho sphoric acid solution (afte r
taking up the water contained in the in itial charge of dilute HNO 3) is too close to the 1.51 SG density of pure
HNO 3 to facilitate much separation. Howe ver, the differential increa ses to m ore work able levels as the ratio of
phosphoric acid to nitric acid is increased.
At a 3:1 H3PO4 to HNO 3 ratio, for example, th e density of the phosphoric acid after
taking up all the water is (very roughly) 1.6 SG, corresponding to a solution strength of ab out 76%. This 1.6/1.51 differential
ought to be sufficient to effect distinct separation if allowed to stand (pro tected from light) for a few days. Naturally, waiting
tim e could be shortened considerably if a centrifuge or acid-proof mechanical separator were available, but the object here is to
come up with a method that d oesn't require fancy equipment.
N o t e : T h e a b o v e a p p r o x i m a t i o n i s b a s e d o n t h e u s e o f t h e c o m m only available o rtho-pho sphoric acid H3PO 4, 85% strength. Results would d iffer for other acid forms and concentrations.
Obtaining the product:
If initial concentrations are known, it is a sim ple matter to work out the e nd product volum e s a n d m a r k t h e s e p a r a t i o n
container to facilitate drawing off. If concentrations are not known exactly, the dem arcation line should be somewhat visible at
the right viewing angle due to a slight difference in refractive ind ex of the respective layers. The upper laye r will be the
concentrated HNO3 end product, which can be carefully siphoned off. Alternatively, the bottom component could
be drained off if the vessel is fitted with a bottom outlet, although in this case som e adulteration of the HNO 3
will occur due to its contact with the phosphoric-acid-wetted-vessel-walls. O bviously, using a tall narrow vessel will m a k e t h e
process easier. The recovered phosphoric acid (which is valuable at about twice the cost of sulphuric acid) is reconcentrated to
its o riginal 1.7 S.G. by heating in the usual way (a hydrom eter is helpful).
W hile adm ittedly not a very efficient or speedy process, a method such as this would have the advantage not only of being a
c o m p l e t e l y n o n - d e c o m posing process (provided initial m ixing is done with care to m inim ize dehydration heating), but of
o p e n i n g n e w a v e n u e s o f e x p e rimentation for those with limited equipment budge ts.
C o m m e n t s p lease, but be gentle if I'm com pletely off base! :)

W ell this is interesting... as you say, phosphoric acid is certainly not cheap (relative to H2SO4) though especially the OTC stuff,
a n d e v e n t h e n , I ' m not sure how pure or concentrated it is.
I'm not sure if separation will occur though, as this depends m ore on the m iscibility of one liquid with another, after which the
densities control which layer will be on top. My fear is that the nitric and phosphoric acids will be m iscible and therefore will not
separate.
I f I c a n g e t h o l d o f s o m e phosphoric a cid som e t i m e I m ay try this, and if it fails then at least the distillation should be
s o m ewhat easier than with H2SO 4.
nbk2000 May 8th, 2004, 06:38 PM

Sim p l y R e d a l r e a d y p o s t e d a b out this topic, though not this detailed.
Roy Paci May 16th, 2004, 11:52 AM

I will try this m e t h o d a s s o o n a s p o s s i b l e . I a m already lookig for th ortho.phosphoric acid .
I was wondering if I could concentrate HNO 3 65/70% cooled to 1-2C by bubbling NO2 in it. what do you think about this?
palpy May 16th, 2004, 05:49 PM

W ell, this is exactly the way the 68% HNO3 is m ade. If it was possible, why do you think they would stop at 68% ? ;) You can
get m ore concentrated nitric just by distillation, dehydration, extraction with DCM (or some other ways I may not know).
meselfs August 28th, 2004, 10:05 PM

IIR C you can get m a x i m u m concentration if you mix NO 2, O2, a nd your 68% acid in the p roper am ounts only if the pressure is
around 50 atm, which is a pretty big load of pressure. A m achinist could probably make a device to contain this, but how to get
the O 2 in there I don't know.

Improvised Manufacture of Nitric Acid > Nitric Acid from Air and Water
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bongincarnate August 27th, 2004, 03:57 AM

http://species8472.dyndns.org/no2/no2.html
Something called a Birkeland-Eyde reactor, anyone know if something like this would work? Several folks over at
sciencemadness.org were discussing this, and it was too damn cool looking to not share.
FUTI August 27th, 2004, 09:29 AM

I'm trying to reply second time and as newbie I don't know if it is first one pass trough (by what I think it didn't; my computer
just freezes itself and that was it). Original old proces of that kind was named by Lavoisier...it is abandoned because it cost
too much and only Holland could make it easy that way because they had hydroelectric plants on their dams. After Haber-
Bosch process invention it became obsolete...but the name of the reactor you stated is unknown to me (I will google it, and do
some research...). Mine first assumption is that it is some new-wave project of the continuous-constant-flow-small-scale-
reactor type. Can be interesting but I doubt you guys can have some practical use of it. As for this electrolysis thing I think
only ozone producer kind of reactor have some future. What you found is very educative simple mind trilling exercise:)
I did google it and its the same stuff I described.
Marvin August 27th, 2004, 05:57 PM

bong, SEARCH THE FORUM FIRST!
I suspect neither this thread nor your questionable self will last long enough for my reply to be even read, but there is a
massive thread on this subject allready.
http://www.roguesci.org/theforum/showthread.php?t=1919
Birkland-Eyde was the process norway used, it is extremely well known.
FUTI,
I dont know why you brought the headless chemist into this, but the process was discovered by Cavandish, not Lavoisier.
FUTI August 30th, 2004, 01:28 PM

I will try to find and quote a source of the info about inventor but it can also be a common rivalistic nationalistic idea that no
nation is immune at...as example we can quote a diferent Russian and American naming of some chemical elements
(because each of them claim priority of discovery). Cavendish or Lavoisier really makes no difference since they are
counterparts by the way I see it (both of them are phlogistonic chemist). I stated this only to state a time frame as old
process (Layden , but I agree I mised to state this with a necesary reserve about matter. I did in the first post that never saw
a light of day...second post was writen in a more hasty manner. And here goes mine browser goes that thing again:(
(If this was the post that vanished into 'electronic fog' then you'd be wrong. It just needs to be approved by a moderator -
kingspaz)
10fingers October 22nd, 2004, 03:50 AM

Awhile back I tried the electric spark method of making nitric and it did work. It takes a long time and a lot of electricity. If
your system is well designed though it requires little attention and no raw materials except electricity, air and water. My system
had numerous flaws though. I have since been rethinking how to do it better and I am going to start working on it. The first
system used a neon sign transformer which was rated at only 300 watts. I ran two pieces of copper tubing into a sealed pyrex
vessel and pumped air in and out of the vessel with an aquarium pump. The tubing was also the electrodes and the ends of
which were held about 1 inch apart. When the air was pumped in it had to pass directly through the arc to go in and out of the
vessel.
The flaws in this system I think were that the power output was too low and that the arc should really be as large and wide as
possible. Also, the air needs to pass quickly through the arc so that it cools before the NO can decompose.
This time I'm going to use an MOT for the power supply, rated at 1.5 kilowatt. One of the electrodes is going to be attached to
a small motor. This electrode will rotate in the center of a piece of steel pipe. The pipe will be the other electrode. As the
electrode spins it will make a disc of plasma inside the pipe which the air will pass through.
One problem though is cooling the electrodes. The pipe will be self cooling but the center electrode that spins will be a
problem. I might try using a heavy piece of copper with a piece of tungsten brazed to the end.
Another problem is that of starting the arc. I have found that an MOT will only arc a couple of mm's. Once the arc is started
you can pull a much larger arc but this is of no help when the electrodes are inaccessible. I might try using a auto ignition coil
to start the arc.
Marvin October 22nd, 2004, 04:15 PM

If you use an ignition coil you risk damaging the insulation on the MOT windings.
The electronic solution isnt much good either, you could have a diode on the MOT that protects it, but it would need to be
rated for the peak reverse voltage of the ignition coil and the peak current of the MOT.
You could try playing with starter electrodes that take the full MOT voltage over 1mm or so and try to arange is so it gets
pulled into a larger arc but with only 2kv or so this might not be possible.
Another possible solution if your arc chamber is strong enough, would be to suck most of the air out and start the arc that way.
Tricky to design for particually if you have a spinning electrode.
10fingers October 23rd, 2004, 12:58 AM

Yea, that's what I was going to try is putting a diode in the circuit to keep the ignition coil voltage from going through the MOT.
I have some high current, high PIV diodes that I salvaged.
The ignition coil is going to be continously pulsed because when you start blowing air through the arc I think it will want to keep
blowing itself out.
Another thing I might try is to get hold of a large toroid and make a high frequency step up transformer. I could make a spark
gap oscillator on the secondary of the MOT and put a high frequency, high voltage into the primary of the toroid, then take the
output of the toroid and use it for my arc. The spark gap may also provide a means of controlling the current through the MOT
so it doesn't overheat. I like the high frequency but I don't really like a spark gap because it makes a lot of noise and will
probably require continual fiddling with.
Zeitgeist October 23rd, 2004, 12:17 PM

Another solution could be a Cockroft-Walton multiplier network with capacitors and diodes
ProdigyChild October 25th, 2004, 06:49 PM

Using a Cockroft-Walton multiplier is difficult, because the burning arc shorts the caps (not a problem) and some diodes
(REALLY a problem). Won't last long, I believe.
Using a series resistors isn't an alternative, because it wastes most energy.
I remember times, when I increased power further and further using high voltage switching transistors and rectified primary
voltage (230V). Was never really good.
The best results I ever had where a low frequency high energy pulse system made of a car ignition coil and a darlington high
voltage transistor. The idea behind it is: Heat up the air very fast by a spark, the shut off the spark and let the plasma cool
down by expansion and diffusion quickly. Then next pulse. I had better yields from this less than 30W (!) system than my
best 800W high freq. switching design (melting electrodes all the time).
The frequency I use is about 20Hz, about 10A peak current (primary side of course) through the ignition coil. Power supply 15-
30V (doesn't really matter, if you adjust peak current to 10A). Make sure to limit flyback voltage to the maximum the
transistor can take. I use a diode that tries to charge a capacitor to flyback voltage. The capacitor is held below 400V by a OP
+ switching transistor + power resistors thus forcing flyback voltage below 400V, too.
Unfortunately, the pulses seem to confuse a NE555 timer and I had a really bad time until I managed to create a reliable
pulse generator using a uA2240 (XR2240). That's a timer + digital divider (:256). The divider reduces the effect of unwanted
toggling of the oscillator.
You don't need any moving parts for this, physics does all for you: plasma cooling by explosion/expansion, removing product
between the electrodes by hot air moving upwards :)
The only drawback is the annoying sound. It's NOT a silent burning arc at all!
Chris The Great October 27th, 2004, 05:17 PM

I've got a 4 MOT pack and some bottle caps from my tesla coil, I'll try using these with my sparkgap and see how this works.
At least it will be a way to get some nitric acid, I still haven't found a source :(
I'll try to figure out the watts/nitric acid produced ratio, at least to estimate what kind of efficiency you can expect from a
similar setup. It will be more than using a smooth arc, as when testing my sparkgaps, a straight arc produces very little NO2,
while a arc from putting the cap in parallel makes the smell get strong pretty fast.
I'll hopefully do a test within the next few days.
Marvin November 7th, 2004, 08:00 AM

I think using caps may turn out to be a massive step backwards.
The accepted method is to ignite the arc and then stretch it to the point it only just stays alight. This should provide a good
yeild of NO, though better if you can make it move with magnets. If you use a cap you dump all the power into the arc at its
shortest point just as it starts. This may look to be generating more power than transformer alone leaving the arc short, but
with a long arc more NO should be produced.
ProdigyChild November 15th, 2004, 05:53 PM

@Chris: have you tried already?
I've made the following experiment: A mains voltage doubler creates 640V (European 230V) with two 10uF caps in series. This
voltage is applied across 2-3mm spark gap. No firing of course from this low voltage. Now a spark gap trigger of 10kV is
applied between the electrodes, causing an enormous discharge.
My circuit is buildt in a way, that it automatically triggers every 1/50s or every 1/25s.
The result is is a powerful arc (about 50-100W) more or less directly from the socket :D
2-3mm is quite long for 640V, isn't it?
It fills a 100ml glass with brown gas within 3-5minutes. Not that bad!
To be correct, I should note, that:

a) it is not a normal voltage doubler of 2 caps and 2 diodes, but has two 1.3mH inductances between caps and diodes.
Otherwise the diodes are fried from RF oscillation and escpecially capacitor voltage reversal (inevitable L-C-system!).
b) a 150uH inductance was put in series with the spark gap to reduce stress on the caps.
Unfortunately, my triggering circuit has random behaviour (sometimes) concerning firing rate. A bit like a Geiger-counter
sometimes....
My conclusion is:
Caps don't spoil NO formation. High current pulses from caps DO produce NOx. After a few seconds, the smell becomes
noticable.
On the other way, I observed Marvin's accepted method of using the longest possible arc. But rather than stretching it after
ignition, I ignite it by HV-ionisation 50 times a second, dump all energy into about 3mm x 3mm x3mm withing microseconds
and then have about 20ms of no current flow.
Pulse current is around 50A I estimate.
So my system is a compromise between 'soft arcs from HV' and capacitor discharge.
If someone wants to judge efficiency from color, I can post a series of photos.

I have to admit that is a very cunning solution.
I still dont think it will do well though in terms of yeilds. The goal involves heating up air to around 3000C and then freezing in
the NO. Going to higher temperatures fails to yeild much more NO because of the rate of cooling problem. I would expect a
capacitor discharge to get a tiny volume to a massively high temperature and thus waste a lot of power.
Pietruszkin November 20th, 2004, 05:16 AM

o jezus..
hno3 from air and water, total non-sense..

this method was good for biig institutions..
greetz..

Everyone is entitled to an opinion - if they can justify it.
Would you care to elaborate on why you think this method is "non-sense", and totally impractical?
j_dmillar November 21st, 2004, 05:07 PM

This is going back up the thread a bit to 10fingers' rotating electrode plan. If you want to maintain an arc and then maintain it
at a longer length, then why not have the rotor off center?
I assume you are planning to have an offset electrode which rotates about the center of the tube. Thuse the electrode is
closest to different parts of the tube at different times, yet the distance from the electrode to the closest part of the tube is
constant. Instead of this, place the axis of the rotation offcenter. Then at different points in the rotation the distance to the
closest point will be different. Set it so the arc just barely strikes at the closest point, and at the other extreme the arc will be
moderately drawn out for a portion of its travel. Not a perfect solution, but better than nothing.
Hmm, was just thinking more about it. Instead of placing it off-center, have a protrusion from the side of the tube at one
point. As the electrode passes close to that spot, the arc will ignite and will be "carried", I think, around the pipe as the
electrode spins.
You could even set up a T-joint or similar in the pipe, and screw another pipe or a rod in and out as the protusion -- once the
arc is struck and stable, move it back so it doesn't tend to 'trap' the arc too much
Honestly I don't know if the idea of the spinning electrode in the pipe is a good idea or not, these are just suggestions about
how to make it work well. Good luck.
10fingers November 21st, 2004, 05:07 PM

This process does work, I had a small system set up awhile back. However it does take a long time and uses a lot of
electricity. But H2SO4 and a nitrate cost money too.
I don't think you can get much out of this method with just high voltage, you need to have power into the arc. The Birkland-
Eyde reactors used industrially used 10's of Kw's. More power, more heat, more NO.
The best setup I think would be with one or more MOT's powering the arc. The arc should be as wide as possible on an axis
perpendicular to the flow of air. You want the air to pass rapidly through the arc so that it is rapidly heated and then cooled.
ProdigyChild November 23rd, 2004, 05:02 PM

Any ideas how to measure concentration of NO2 ?
We need some quantitative data. I observed, that white paper gets light brown from NO2 in a few hours - I use this as a
qualitative test to 'measure' performance of the arcs.

Intensity of the brown gas depends too much on the temperature, as would direct reactions. Making nitric acid and then
neutralising would be my first choice. Or even leading the gas into sodium hydroxide until the pH changes. Could be fairly
sensitive and repeatable if CO2 is scrubbed out of the gas pre arc. Needs an indicatior NO2 isnt going to affect.
FUTI November 24th, 2004, 09:59 AM

I guess that we could pass the gas stream which contain nitrogen oxides through a sulfite solution and after that determine
amount of sulfite and nitrite in solution through titration or spectrofotometry, and also the amount of sulfate and nitrate
combined after subtracting the above mentioned value from whole acid measured through neutralisation as Marvin said. There
are number of possible solution for this problem...what are the requirements for a detection you want?
ProdigyChild November 24th, 2004, 01:39 PM

Requirements?
It should work at low concentration and low total amount: 1mg NO2 in 100ml air or similar.
And: everyone should be able to do it.
Expensive chemicals - no problem, if this improves/eases the test.
Dissolving NOx in water is nasty. I have the impression it does not like to dissolve. So the amount of dissolved gas is a
function of my patience rather than NOx concentration ;)
Pb1 November 24th, 2004, 07:53 PM

To measure the amount of NOx formed, put a known mass of copper oxide into the water. This reacts with NOx to form copper
(II) nitrate, which is very soluble and can be washed away from the insoluble oxide. If you want your NOx back, simply heat
the nitrate.
FUTI November 25th, 2004, 11:20 AM

hm...I'll work on that. You seem to look a solution that do not involve instruments. I'm curious how you colect gas from
generator. Do you have a posibility to measure the volume of gas passed through a generator and after that through a water
detection solution (that could help a lot!)?
I thought that simple color of gas is good enough for NO2, but it seems that is not good enough for you (anyway it doesn't
measure NO2 corect since NO concentration and pressure/composition change make a mess in system). Then I turned to heat
capacity of gas, that could work for NO2, but wont work for NO. IR is to complicated for "home-device". I don't know why you
find it difficult to dissolve. Make a split in gas line and pass a small stream through a sintered glass into basic solution of
known concentration. Measure the volume of gass passed through it. Titration of a sample for base remained give you a total
acid oxides produced. Second sample you add KI and acetic acid, little starch and titrate with tiosulfate (or make some other
combination like sulfite and "something else") and after oxidoreduction reaction and titration you can obtain second value.
Solve as system of two equation with two variables and you will have NO and NO2 conversion. Maybe even ammonium nitrate
in acidified solution can generate enough N2 to measure NO from sample directly. If you look for some "lithmus paper" kind
of test that could take some time to develop and verify its detection limit (and range).
Don't take this personaly boys, but I agree with Pietruszkin, this is not a good way to nitric acid from my point of view, but I
still look close your work because where is the good chemistry there I'm;) So I understand your work and value your effort, but
it is not cost effective, but boy you will be pride to make it:)
I can think several more solution involving electrical measurement in water solution etc., but it needs specific equipment and if
you are not sure that gas can be dissolved what is the point of making such device even if it could work continously? BTW I
know that there is some kind of strategy to purify exhaust gasses from electric coal plant removing sulfur and nitrogen oxides
by some catalytic process and ammonium sulfate is one product (I guess then the N2 is the second)...anyone have an idea
how and could this be used here? It would be nice if you could just measure the weight of produced salt.
Pietruszkin November 26th, 2004, 12:34 PM

Everyone is entitled to an opinion - if they can justify it.
Would you care to elaborate on why you think this method is "non-sense", and totally impractical?
hah
maybe i think so becuse in my country hno3 is as expensive as mineral water? :rolleyes: i don't knowww :D

Good for you!
So, your suggested alternative method for making HNO3 is to buy it? What about those who cannot buy it easily, or cheaply?
What about if one day its sale is restricted by government? What about makiing HNO3 simply as an academic exercise?
Basically, I'm question the worth of your input into this thread. Your first post was an affront to the contributions of other
members, and described a real industrial process as "non-sense". Your second post simply boasted about your supply of
HNO3.
How has any of this contributed at all to this thread?

Braggerts and morons are about as welcome here as a leaky asshole in a crowded subway car after a Texas chile cookoff.
:rolleyes:
ProdigyChild November 27th, 2004, 10:03 AM

@FUTI: I do like electronic sensors, but possibly other members don't. If I want to compare my yield with others, I can't insist
on special equipment.
Any known electric effects of O2, N2, NO, NO2 are welcome. O2 does slightly increase magnetic fields (paramagnetic; ur=1 +
1.4E-7), while N2 is diamagnetic (ur=1 - 3E-10).
What about IR properties of NO2? IR diodes and detectors are easily obtainable (wavelength a bit above 800nm I believe).
When experimenting, it's convenient to us a closed glass.
By the way, I had the following idea today: I put the electrodes into an (insulating) oil bath, electrodes sticking out of the
surface a few cm. Now I put a glass on top of it and let the arc burn for a few minutes inside. The oil prevents gases from
flowing in or out. After cooling I should be able to measure a reduction of gas volume as:
N2 + 2O2 ==> 2NO2 (3 parts ==> 2 parts)

Of course this works only, if there's enough O2 to form NO2 (in favour of NO)
Pietruszkin November 27th, 2004, 11:39 AM

Good for you!
So, your suggested alternative method for making HNO3 is to buy it? What about those who cannot buy it easily, or cheaply?
What about if one day its sale is restricted by government? What about makiing HNO3 simply as an academic exercise?
Basically, I'm question the worth of your input into this thread. Your first post was an affront to the contributions of other
members, and described a real industrial process as "non-sense". Your second post simply boasted about your supply of
HNO3.
How has any of this contributed at all to this thread?
ok, sorry for my non-sense post (as this method of obtaining hno3 :D :p [joke])
havent you got any connections with chemists or other people who can obtain hno3 very easy? oh people, think sth, ask
people..
old chemists could understand your sitiuation..
if u havent got any connections, you can go to the gas station and buy some electrolyte (rare to obtain, but can try) - heat this
(this is 30% h2so4), -water is pairing-> and you have ~90% h2so4, add some kno3 and ya can nitrate sth (or destylate this
mixture to obtain fume hno3)...
havent got destilation aparature (? [poor english]) - do it!

instead of distilling flask - shampane bottle, some glass pipes etc)...
thats all!
and once more sorry for my previous post, but i cant imagine that i cant receive basic (chemicals) like acids (hno3, h2so4)
etc..
greets
ps, i have request - if i write sth bad (grammar) - tell me - i am learning english, but it isnt my speciality) ;)

I posted this method a few days ago but it never appeared for some reason.
Put a known mass of cupric oxide (CuO) in your vessel with some water. The NOx should react with this to form copper (II)
nitrate and leave insoluble cupric oxide, which can be filtered out and weighed. If you want your NOx back, just heat the
nitrate.
@Pietruszkin: That method and its variants have already been discussed on this forum ad nauseum. Please search before
posting.

ProdigyChild,
Most oils will react with the NO2. For IR to work you would need specific magic values of IR LED. You could use the brown colour
of the NO2 radical but you would need very accuratly controlled temperature at measurement. Sodium hydroxide will remove
all the NO2/NO from the gas but at only a few percent NO2 I think experimental error would outweigh the results for most
people.
Pb1,
The copper oxide idea is insteresting, but I dont know how fast or well it would react. Also it forms a hydrate that cannot be
fully dehydrated by heating (decomposes first). A decent potential method if you can ensure what you have is the pure oxide.
I would expect some nitrite to be formed as well from NO2 and NO, but this should not affect the math based on remaining
copper oxide. Dehydrating reliably to the same point and weighing accuratly might be more tricky.

@Pb1 I have to measure the amount of dissolved copper nitrate or is there a way to dissolve CuO or Cu2O only from the
insoluable part?
I guess I'll try a pH-based test first.
Measuring NO2 yield seems to be double as difficult as producing it!?
Another question:
When I ran a 25W arc for about 1/2hour, I got a white (!) dust on the walls of the 100ml glass. When dissolved in water, a
faint blue colour can be seen.
The electrodes are copper (really pure one - from electric conductors). The heat evaporates some copper.
The only white copper salts I know are CuSO4 and CuCl.
What could that white dust be? A copper nitride? anhydrous copper nitrate?? :confused:

Yes, I was thinking that you could weigh the oxide left behind. You would first filter out the insoluble part left behind and
wash it free of the nitrate. Then you d heat it to above 160C to drive o ff water and decom pose the hydroxide back to the
oxide. The only problem with this is that you might get different oxidation states of the oxide and have to dissolve it in
sulfuric acid to get CuSO4 which could be dried out and weighed.
I don t think nitrites would really be a problem. Nitrous acid would decom pose at the surface of the water, leaving only nitric to
react. Any nitrite ions lying around would be removed as HNO2.
This idea could also be applied to other elements and their oxides.

I agree copper oxide idea is interesting, I believe that old Egypt used some copper based procedure for nitric acid so I guess
this can actually work maybe even as analytical procedure. Don't take this as certain the info is from history of chemistry book
I read once. Now where is that...I need to clean up my room more often:)
Chris The Great December 15th, 2004, 11:24 PM

[LEFT]
@Chris: have you tried already?
Unfortunatly, technical difficulties have prevented a test. The 4 pack decided to self destruct my 240V circuit breaker, and so I
have no high voltage ability right now. The breaker replacement was also low on my priority list, so I haven't had a chance to
buy a new one.
I have a two week break coming up, so I'll probably have time to get my parents to pay up :mad: and get a new breaker as
well as something to limit the input power to about 7000 watts. I can then build the actual generator after I get some washers
and nuts to heatsink the electrodes inside the pipe, where the airflow is. I kinda got pissed after I blew the breaker and didn't
do any more work.....
Would one of those black 'misting' hoses used for watering a garden work well for a bubbler, or would the NOx/nitric destroy
the material to quickly?
xyz December 18th, 2004, 12:34 AM

The hose will be eaten away much too quickly, leaving you with no hose and nitric that's contaminated with the reaction
products.
Mr.ANFO December 31st, 2004, 03:10 AM

In Canada HNO3 is unable to be purchased in 50% vol or above unless you are licenced.
ProdigyChild January 6th, 2005, 10:59 AM

I'm still dreaming of making NO2 that way.
In contrast to most of you, I focused on low power systems, that can run without interruption.
Yesterday I finished a relative simple, reliable HV-system. I uses a car ignition coil and a small circuit, that allows to plug that
into the 230V socket. The coild produces an arc of 20-25mm, total power consumption is 9W and nothing gets even warm. It
takes 20min to form visible NO2, with the vessel (0.5l) still beeing only slightly warm.
The good thing about this circuit is, that the arc is switched of nearly all the time, only 50times/second it creates a intense
pulse of 200us / 650V / 18A primary. This pulse is one full sine wave (5kHz). Three quarters of the energy (1uF cap charged
to 650V) seem to be gone afterwards (used by the arc + device losses).
If watched with an oscilloscope, you can see a flat line with a 18A spike every 1/50s.
I've described a powerfull three electrode setup (triggered spark gap) design in this thread before, but I have problems
harnessing one problem: the trigger electrode must be thin to be a good trigger electrode. Also it must be close to the main
electrodes, to trigger the main current. But then the powerfull main arc eats it away eventually. And the main electrodes need
to be MASSIVE otherwise they are aeten away slowly, too. The more massive, the electrodes, the harde to trigger!
Problems, problems, problems.....
...some of which we all share :(
Now comes the good news:

The triggering problem can be solved easily!
Below I attached a schematic. The electrodes doing the real arcing work are gap G1. In the shown configuration, C3 is charged
negative, while line P in negative (negative half sine of mains). Likewise C1 is charged at the same time.
A half wave later, P is maximum positive. At that time, switch Q is closed, discharging C1 (mains+charge = 2x 320V) into the
ingition coil. Secondary side of the ignition coil charges C2 (290pF / 30kV) to about 10kV until G2 (9mm) breaks down. This in
turn switches L2 (1.3mH) to 10kV and the inductance L2 is really willing to allow that, because the spark gap switches so fast.
At that moment, you have the 10kV also across the main gap G1. G1 is driven into conduction and C3 will be discharged over
gap G1, too, although it was by far not charged to G1's breakdown voltage. C3 can be a huge cap or a MOT capable of driving
POWER through G1.
The point is, that the voltage of C3 (or MOT) needs to be in sync with mains voltage. A transformes is in sync, unless you've
done some magic. The schematic shows, how a simple capacitor can be used as power supply. Be careful with the polarity of
D1 and D2, otherwise, the whole thing will turn into smoke :eek:
I've modified the design described and used a transformer in place of L2. This transformer increases the overvoltage further
(2:1) resulting in an even longer arcing across G1. This transformer uses 15 / 37 turns of wire on a 8cm diameter, 15cm long
cardboard tube. Limiting factor seems to be the capacitance of the windings. I've not exceeded 1inch spark length so far :(
But come on, this method ignites an arc, that can have 1000Amps, low voltage (<1KV) and massive power. And it re-ignites it
every 1/50s if necessary, so you can't blow it out!
The only downside is the need for good timing of the switch. I've done with a SCR + 1 trigger diode (DIAC), 2 resistors, 3 Z-
diodes and a 0.1uF cap. Can't be that difficult, does it?
[devoted to 10finger's suggestion about ignition coil triggering, page1 of this thread]
EDIT:
Using a transformator-version and not grounding the circuit properly seems to be a bad idea. 5minutes ago, my setup found
its own way to earth ( ;) ) by the help of the pre-ionizing HV and wiped out electricity in my lab. No fuse seems to be gone but
still dark!?
But I could test it before. Quite powerful! Nice brown NO2 within minutes!
ETCS (Ret) August 29th, 2006, 10:47 PM

V. S. Komelkov and V. I. Modzolevskii developed a small apparatus for the purpose of Nitrogen fixation (Nitrogen Oxides)
which is described in the Russian Journal of Physical Chemistry 52(6), 1978 "Formation of Nitrogen Oxides in High Current
Pulsed Discharges in Air"
The process can be made quite efficient, even on a small scale, and the Nitric Oxides produced can be used for the gaseous
phase nitration of dry cellulose directly.
One of the primary applications of the device was intended to be the production of slow release fertilizer (cellulose nitrate) by
the use of dried vegetable waste.
http://www.gobrainstorm.net/~ohare/
ETCS (Ret) August 31st, 2006, 08:42 PM

Prodigy Child,
Your Post above (#37) presents some interesting possiblities.
Your Ignition Coil portion of the circuit is Capacitive Discharge in the style of the automotive ignition systems many electronics
experimenters constructed in the 1970s and 1980s for their cars. It is easy to control the timing of the discharge into the
primary of the ignition coil with an SCR or HV MosFet and associated timing/trigger circuitry which would operate on about 12
volts DC.
To simplify the concept, I'd recommend pulsing the ignition coil capacitive discharge input at several hundred hertz and
applying the ignition coil output to a high voltage capacitor (which can be home made) across the spark gap in order for the
arc to pulse operate at 30 KV or more.
Several pulses of ignition coil output would charge the high voltage capacitor, through a suitable high voltage diode, and build
its potential stepwise up to the point of spontaneoous arcing across the gap when the energy would be disruptively discharged
in an intense "bang" similar to what Tesla did with his infamous Tesla Coils.
By adjusting the width of the spark gap you could adjust the discharge pulse rate to some suitable range in the vicinity of 20
to 50 or more discharges per second.
By the way, what did you use to create your schematic diagram? It is very clear and easy to follow.
fractional distiller February 7th, 2007, 10:02 PM

It seems to me that even though both of the two threads that are focused around the birkeland-eyde reactor no one has gone
through a balanced chemical equation.
I myself am in the process of prep work for construction on my own reactor but I can not do any of the really important
calculations without the proper equation for the reaction.
From what I can determine the equation goes such as this.

The 78% diatomic nitrogen in air and the 21% oxygen are pumped into my reaction vessel with a certain surplus of O2 to help
the yield of the reaction which saves me some efficiency due to the heat conversion.
N2,O2==> 2N + 2O: plasma breaks air apart and when it cools forms 2N + 2O
2N + 2O==> 2NO2: after cooling it reassembles as 2NO2
2NO + O2==> 2NO2: after exposing the nitric oxide to air yields 2NO2
2NO2 + 2(H2O) ==> 2(HNO3) + H2
Comments, suggestions, corrections, are all welcome. Especially corrections it would suck to figure out all the math for my
dream set up and have it catastrophically fail on me.
Alexires February 8th, 2007, 04:47 AM

Actually, I think that the reaction would look something like this:
N2+O2 ---(heat)--> 2NO

NO+1/2O2 ---(heat)--> NO2
NO2+H2O --> HNO3
I'm assuming it would be something like this because of the Ostwald Process (making nitric from ammonia gas).
I don't think you need to worry much about the ratios, depending on what reactor you make. If you just passed air into a
jacobs ladder, then passed the air straight into water, you should have 68% fuming nitric acid, if you wait long enough.
Also have a little look at this (http://www.efma.org/Publications/BAT%202000/Bat02/index.asp). It may help a little.
NGfan February 10th, 2007, 11:01 AM

Ok, what would be the preferred voltage for this experiment, between 4 and 10 kv, and what would be the rate of air flow
throught the arc? I'm going to -attempt- this project but will be pissed if I buy 100 worth of transformer that does nothing...

I will be trying this experiment too as soon as I can locate a suitable HV transformer.
I think you guys may be reading a bit too much into this project at this time. If you want theoretical kinetic mechanisms and
thermodynamic equilibriums perhaps another website, or rather just about every other website, would be more suitable.
What you should be concerned with at this point is if the damn things works, and HOW to actually do it. I will be plinking down
some hard coin as well, and I will be disappointed if it does not work, but I am willing to take the risk. That's why it's an
EXPERIMENT, not a recipe.
To my knowledge there is no system like this you can buy, no website demonstrating it, and no book with the procedure
written down. The Ohare patent is very compelling, and it is what I will be trying to accomplish, but if that guy actually got this
thing to work, then how come he can't put a picture of the working apparatus on his website?
NGfan, if you want your question answered, a question I want to know as well, you are just going to have to do the experiment
and find out. That's what I intend to do. We are blazing a new path here.

I agree with Mega here definitely this is a new path. There is one website on one of the two threads related to this topic,
species I believe is the site, he has pictures and claims to actually have done this with success but right when you get to what
really counts the end results and final data there is nothing. So its sketchy at best.
Although Mega I am sorry I do not agree with you with the idea of just pure experimentation. Now let me explain why, now if it
turns out that I am wrong I am sorry for opening my ignorant mouth. The purposed way I believe to go through this is going
to require two fields of knowledge the first chemistry which I believe we all have a little knack for, and the second which I have
no idea about electricity. This is going to be a little something like electrochemistry except we do not have an electrolyte and
our substance is gases not liquids.
We need to investigate the bond energies required to break down each molecule through its steps in the reaction process; this
is why I wanted to see a balanced equation. From here we need to go about doing the dredge work of calculating how much
energy it translates to in raw power from electricity. Then the devil is in the details here we have to find that special equilibrium
point where we balance volts and amps so that we have enough power to break our bonds and have them reconnect but keep
the amps down just enough not to cause problems with thermal decomposition. This is where the experimentation is going to
come in.
I purpose someone run a bench test, I myself will try to perform one but in all honesty it probably will not happen. But if it
does of course I will share my results.
Its my hope we can pull together and collaborate what the energy to break down the bonds will be and then convert that to a
certain ratio so we can just multiply that ratio to an amount to get a rough estimate. Then we need someone who has the
experience and knowledge to help us find the sweet spot for our power input needs.
This is too big of a project for us to handle by ourselves, it would be better as a combined effort. I will try to step up and lead
it if I can.
What our first priority is for someone to post a balanced equation and I mean completely balanced even though its may
seem trivial.
Explain or all of us collaborate how much energy will be needed for the reaction. Again the more superfluities and trivial the
better so we can see every aspect.
Finally try some bench test for what power we need and what amps/volts combination works best. Then extrapolate are
design from there.

I agree that the calculations and equations are important, after all chemistry would not be chemistry without those things. First
things first we have to try this and see if the theory bears some semblance of truth. You can learn more from a few
experiments than you can with thousands of hours of theory. The opposite is also true, the theory can guide your experiment.
My point here is we have the theory telling us the reaction in general should work, and so it has guided us to this method, but
only experimentation will give us the specifics.
I guess I have an advantage because I have already seen the thermodynamic equations of state for this reaction. I glossed
over them at the time because they didn't inform me HOW to do the experiment, just that it is possible. I have not saved or
bookmarked those files, but they are out there. There is always plenty of theory out there.
Who can tell I loathe physical chemistry, eh? I feel if your not working with chemicals, you are a physicist :)
NGfan February 13th, 2007, 04:27 PM

Well, I AM going to try the experiment, and post my 'trailblazing' discoveries. I will buy the little extra equiptment I need, and
test to see what factors such as; pressure, oxygen content, power, volts and current affect the percentage and also the
efficiency. The website www.signbuyer.co.uk has politely informed me of the transformers that will provide for me a jacobs
ladder without tripping the trip out switch. (The surplus ones have none, which is slightly scary), and I will buy two to three, to
test the difference in relation to voltage and power ect. For all you non-UK scientists, just find Noen sign transformers, and ask
the company. Also remember to post results, as nitric acid is the base ingredient of many explosives and a valuable chemical
to be made purely from electricity, air and water. Apart from this, I have a life, so the results may be delayed or fragmented.
Note: I know it's mainly nitrogen which the content should be higher, but I can't make that, and -apparently- introducing extra
oxygen into the air improves performance.

Mega is right first step is to see if the theory bears any semblance of truth. As of right now what we need is instructions for a
makeshift Jacob s ladder. There a re thous ands of sites that teach you how to build one but I am not intereste d in wastin g my
time figuring that out someone build one and report to the forum with a step by step on this process. That will make it easy
for everyone to build a system for bench tests.
After we have the plans that someone has built and tested with not excessively hard materials to get, or that can be done by
just following a simple set of instructions that the person posts on the forum. Set it up in a glass container or any container
you see fit, personally I will be using a glass. Set up an electrolysis cell for water so you can pump a little excess O2 into the
chamber that has our Jacobs ladder in it.
Run it for a while and check to see if any NO2 does appear. After this find your own way to bubble the gas through water. I
personally am going to try to use my extra O2 house from the electrolysis cell and pour water in it.
After this just check for nitric acid by simple litmus paper of if you want to get technical you could check its specific gravity or do
a titration test with baking soda. It is really your own preference on testing it. After this we just post our results and findings.
So we need simp le (pre-tested) in structions for an inexpensive Ja co bs s ladder that even the most kewl kids can set up. Hey
lets face it if they want to try they will most likely die from electrocution from the NST and that would be like killing two birds
with one stone getting dirt cheap HNO3 and killing some kewls in the process.
Pictu res an d for the love of GOD expla in wha t you are doing just don t send pictu res an d say random shit that m a k e s n o
s e n s e a n d d o e s n t help that just wastes time and my patience.
Post you r work fo r figuring out how mu ch acid you formed if any at a ll formed.
defiant February 13th, 2007, 09:21 PM

"SYNTHETIC NITROGEN PRODUCTS" (Dupont Industries) pgs 215-216 states as follows:
The Birkeland-Eyde or Arc process made nitric acid by 1) passing air through an electric arc, 2) forming nitric oxide, 3)
oxidizing NO with air and 4) absorbing the resulting oxides of nitrogen in water. The reactions are shown in Eqs. (9.2) through
(9.5):
N2 + 02 2N0 (9.2)
2N0 + 02 * 2N02 (9.3)
2 NO2 + H20 ~ HNO2 + 111403 (9.4)
3HN02 + 2N0 + (9.5)
The arc is spread into a disc by an electromagnet. The process operated in Norway from 1905 to 1930. It used hydroelectric
power, but it was made obsolete by the ammonia oxidation process. This process was first used in the United States in 1917.
Presumably fllattening discharge by using an electromagnet increases the yield.
That's all the information contained in the above referenced source - but I recall another book that was in the filesharing
network that went into greater depth.
Does anyone remember the name of the file?
chemdesperate February 14th, 2007, 12:38 AM

This sounds like a project I would like to pursue. I have a 15kv15ma NST that I havent used as much as I'd like to. I
entended to make a tesla coil a while back but never got around to it.
I would build off of magelomania's idea. If Im not fully giving credit to someone else out there, Im sorry. Please excuse any
typos.
This is all theoretical.
I would take a secotion of pvc pipe and cap it on bolth ends. Before hand placeing some sort of efficent plasma produceing
device in the pipe. Then tap bolth ends of the pipe to fit electric solinoid sprinkler valves on each ends of the pipe. this way
the pipe is a more controled enviroment with sealed electrodes and airtight fittings.
Now I would hook up a compressor to your valve thread which is probly 1/2inch. I would adjust your pressure to 2x or 3x your
STD. Or two times your standard atmospheric pressure.
Then on the other end of the pipe, you should connect some sort of flexable non-corosvie pipe to the end of the sprinkler
valve. then run that pipe to your bubbler of choice. I was thinking if you were to seal the water and NO2 in some sort of
container that could be turned up side down over and over again so that the gas could more throughly pass through the water.
The only real difference is that Im useing electronic valves to seal of your NO2 produceing environment. That way you could
get purer NO2 gasses, not loss any of it, and then make a proper timer to open and close the valves and given times for a
beter HNO3 produceing cycle.
defiant February 14th, 2007, 07:46 AM

Found the file, its the "Industrial Nitrogen Compounds And Explosives", Manual of Chemical Technology III. Pages 21-26 are
particularly interesting, but the intro and the work as a whole is interesting. http://www.sciencemadness.org/library/books/
industrial_nitrogen_compounds_and_explosives.pdf or http://mihd.net/9utyb2
This book also cites sources, including:
- A.W. Crossley, "The Utilisation of Atmospheric Nitrogen" (Thorpe's "Dictionary of Applied Chemistry," Vol. III., p. 698). 1912.
- J. Knox, "The Fixation of Atmospheric Nitrogen." 1914. http://www.sciencemadness.org/library/books/

fixation_of_atmospheric_nitrogen.pdf
- Donath and Indra, "Die Oxydation des Ammoniaks zu Saltpetersaure und Saltpetriger Saure." 1913
- Donath and Frenzel, Die Technische Aunutzung des Atmoshpharischen Stickstoff." 1907
- Escard, "Fabrication Electrochemique de l'Acide Nitrigue et des Composes Nitres a l'Aide des Elents de l'Air." Paris, 1909.
- Caro, "Chemical Trade Journal, 1909, 44, 621.
- Haiier and Koenig, "Zeitcsch. Elektrochem." 1910, 16, 17.
- E. Kilburn Scott, "Production of Nitrates from the Air." Journ. Soc. Chem. Ind., 1915, 34, 113.
There may be spelling errors in this list due to legibility issues with the text, nor are foreign punctuation marks included.
megalomania February 14th, 2007, 10:07 AM

I will be attempting the allegedly improved process of forming nitric oxide by electric arc as explained in US patent 4,877,589.
This patent uses a tungsten catalyst on spherical alumina to increase nitrogen fixation and to shield the resulting NOx gasses
from the destructive effects of UV light produced by the electric arc.
If his (OHare) theory hold out, and I have no reason to doubt this process does work, this catalytic method should give
greatly improved yields based on the energy input. I rather like the idea of being able to make nitric acid from little more than
air and electricity. Let the fedgov ban that!
I know a tungsten based catalyst is not exactly OTC from what I know of the availability of tungsten compounds now, but I can
worry about that after I actually get this thing working. I am sure someone cleverer than I will eventually dig up the chemistry
of how to make soluble tungsten compounds from the metal.
I also intend to continue research on my catalytic ammonia burner once I get the design of my improved electric furnace
finalized and constructed. I actually found a picture in a book of a bench scale ammonia burner that is very close to what I
have already. There is hope there, the process does work. Part and parcel to this experiment is a way to generate enough
ammonia to make the process economical. This leads me to my tangential project of making ammonia by the urea-to-
ammonia process (U2A), the current industrial wunderkind of onsite ammonia production made possible by boiling urea under
slight pressure. Ammonia generation (economical at that) has its own uses beyond nitric acid.

Well, I'm following the more simple designs shown here: http://species8472.dyndns.org/no2/no2.html and when I achive
maximum concentration, either sulfuric-distill, or crank up the pressure and see what conc I can get as it goes up. :p
defiant February 15th, 2007, 08:40 PM

NGFan: How do you plan on getting sulfuric acid from that setup? I'm not an expert on the subject, but its designed to produce
nitrates.
Also, as was pointed out earlier, the link you refer to hasn't been updated in years, and the experimenter hasn't posted
results/yields.
Meglomania: You're ahead of me on all of this. I have legal issues and my government protectors watchful eye to contend
with right now. Not that there's anything illegal about producing nitrates - I've simply been focusing my attention and financial
resources on other toys.
Despite my misplaced priorities, I'm very interested in any experimentation you do with producing nitrates from urea and/or
amonia. It's been an interest of mine for some time now, and thus I'm favorably inclined as to the direction of your research.
In short order I'll be joining you in experimentation, thus I'd greatly appreciate you keeping me advised.
c.Tech February 16th, 2007, 01:41 AM

NGFan: How do you plan on getting sulfuric acid from that setup? I'm not an expert on the subject, but its designed to produce
nitrates.
He meant when he gets the max concentration for nitric acid (from bubbling NO2 through water) he would distil it with sulfuric
acid to get 100% HNO3.

That is correct, although I don't see why you can't just distill it off the water... I've heard it destroys it. Anyway, buying NSTs
tomorrow at 10 kv and 5kv. Also, it doesn't matter he's not updated recently, he still has two different reactors. Does matter
about yeild though. I think sciencemadness had something on that.

After a few more searches through every search engine known to man I have found a balanced equation that makes sense.
I already knew this much

N2, O2==> 2N + 2O: plasma breaks air apart and when it cools forms 2N + 2O
2N + 2O==> 2NO2: after cooling it reassembles as 2NO2
2NO + O2==> 2NO2: after exposing the nitric oxide to air yields 2NO2
But what I did not know was what happened when

2NO2 + 2(H2O) ==> ?
Well know I do it is
2NO2 + H2O ==> HNO2 + HNO3
H:2/N:2/O:5 == H:2/N:2/O:5 <== Everything checks!
Now comes a bit of problem we now have nitrous acid (HNO2) in the equation I can not find its boiling point anywhere. We
have to find that after using your preferred method with your arc to separate the nitrous acid from our brand new nitric acid!
This makes home preparation a lot more complicated then I originally thought. But no matter I do have the glassware to
fractionally distill my acid under a vacuum. (I know you can create your own acid with potassium nitrate and sulfuric acid this
way, but where is the fun in that, plus this lets me keep my supplies for other uses and in the long run this is significantly
cheaper too).
I am on my way to figuring out all necessary equations, I know theory does not get you much of anywhere but I find it
interesting! Any and all help would be greatly appreciated Exemplum Gratium ==> Joules of heat, electric circuit design, arc
shape & expansion, and any other ideas that would help in the set up for the Jacobs ladder and a way to process it.
Alexires February 22nd, 2007, 05:11 AM

Fractional Distiller - Congratulations on your research. Unfortunately, I don't think that it is that simple. I can't remember
where I was reading it, but there was a lot of debate about how HNO3 exists in solution, probably from its changing nitrating
and oxidizing capabilities at different concentrations.
I think it is a given that NO2 will form in an arc - Look at lightning. That forms Ozone (O3) and NO2. How much it forms is a
different matter. I think that this is probably a case for experimental results. We can hypothosis all we like, but we won't truly
know if it is feasable until someone makes a BE reactor.
ultma February 22nd, 2007, 04:43 PM

dont know if this helps much
Varation of Equilibrium Constants with Temperature
values of log Kp at variuos temperatures ( oK )
N2(g) + O2(g) <=> 2NO(g)

298oK, Kp= -30.4
2NO(g) + O2(g) <=> 2NO2(g)

298oK, Kp= 12.3
ThimeBom February 22nd, 2007, 06:48 PM

Anybody who is having trouble finding a neon light transformer (NST) could possibly use a small flyback transformer from a
small television or computer monitor. In TVs or monitors that have very large CRT's they can reach voltages of over 30,000
Volts.
fractional distiller February 22nd, 2007, 08:05 PM

Alexeries and Ultma thank you both for your responses. Alexeries I will go and try to check if what you claim is true, I really
hope not. Ultma thank you for you figures can you give a little explanation on what you mean it is a little vague
Well from what I have found Jacob ladders require high voltage at low amps. But what I am finding is higher amps produces
bigger arc, where as high voltage determines how close on your vee shaped structure the arc begins.
Can anyone else verify this, if you do, please cite your sources!
Does anyone live in the Maryland area because I would really like to get a group together to work on this! This might seem a
little taboo but I think it would be for the greater good of the project if we could get together pull are resources and take
pictures, movies and draw up schematics for our designs. Going at this alone is only going to be harder and more challenging
where as if we can work together we all may have very cheap nitric acid all to ourselves!
Speaking of citing my sources for the nitrous acid came from Defiant's web sources that he posted, which are down for some
reason now!?
Does anyone have any progess on there BE reactor yet?

Theory may tell you that combining nitrogen dioxide and water and will form nitric acid and nitrous acid, but only actual
experimentation will reveal that this is, in fact, wrong.
The reaction is:
3NO2(g) + H2O(l) <==> 2HNO3(aq) + NO(g)
I have written about this reaction before because I encountered it in my earlier research in designing a way to make the nitric
acid. The equation is from the Kirk Othmer Encyclopedia of Chemical Technology 4th edition in case you wanted a reference to
double check.
I actually had personalized license plates with this reaction, I wont tell you which part yet. Nobody EVER got it except a few
chemistry professors. I even had a cop pull me over and ask First of all, what does your license plate mean? I almost put
this equation as a bumper sticker to better explain it, but honestly the sheeple would still not understand. I have a new
chemistry themed plate now.
This reaction is important to know because it helps to determine the final design of a device to make nitric acid. Just bubbling
NO2 into water will result in a loss of 1/3 of your precious NOx gas. Industrially they release NO2 gas into the base of a tower
with a water sprayer on top. The water spray then results in a sort of waterfall on the sides of the tower. The volume of NOx
gasses diminish the farther up the tower it gets as it encounters more and more water. The water at the base of the tower
where the fresh NO2 gas first enters is the most highly concentrated acid available. You get dilute acid this way, but you
maximize yield. This is called a countercurrent flow design I believe (gas up, water down, each flow in opposite direction).
Yes, I understand that some nitrous acid may form from reacting NO with water, but thats an entirely separate reaction taking
place. The reaction as I have outlined in the equation happens first. The design of the reactor can force the vast majority of
the gaseous NO out of solution to be reacted with surplus air. Agitate the solution with enough available oxygen and you will
have very little nitrous to deal with.
Nitric-producer February 25th, 2007, 02:45 PM

I have recently been experimenting with the set up described on the "species" website. I have two garden pots stuck together,
with two electrodes entering each side of the pot. The electrodes are powered by a 15KV neon sign transformer which I
purchased from ebay. Then a serious of water bubblers (air is blown through using an aquarium pump). Will take a few
pictures and mabye a video tonight. After 2 days of continious running the PH has only reached about 2. I really did expect it
to be more concentrated by now. Can anyone tell me whether im realisticly going to achieve a higher concentration before I
distill? (i.e Fuming?)
I also had a go at vacuum distillation today using an old vacuum cleaner. I managed to distill at about 75 C. My product had a
PH of about 0. Although the tube going to the vacuum buffer flask had some sort of white smoke - can anyone explain this?
My drain cleaner which is where I get my Sulfuric acid from is coloured purple (it is 91% acid). Did a few quick tests on it with
my Nitric acid solution. When I mixed them, a lot of heat was given out and the purple colour disappeared - can anyone tell
me why?
Thanks in advance.

From what I know of the process it is not very likely to get much more concentrated than 60% or so. The equilibrium of the
reaction does not favor the production of nitric acid as the acid concentration increases. After a certain (low) percentage you
just end up running the NO2 through your acid unreacted.
I suppose if you pressurized a container with oxygen and NOx you could get a higher concentration of acid after some weeks
or months. What they do industrially is a combination of either conventional distillation, or codistillation with sulfuric acid, or
both. The initial distillation gives acid near the 70% mark, and the sulfuric distillation gives a nearly 100% concentration, which
can be distilled again to get 100% acid. Fuming acid is then achieved by dissolving NO2 gas into the anhydrous acid.

Interestingly enough Mega, when talking to my Chem teacher today, he mentioned that the Lab Assistant here makes his own
NO2 for experiments on global warming and smog and other not overly interesting stuff.
How he goes about it is by running a spark plug in a glass jar, and the spark plug is hooked up to a 5kv EHT (extra high
tension). So it seems that it certainly can be done. Maybe something like a starter coil from a car hooked up to a few spark
plugs in a jar, then using an aquarium pump to pump air in, then through a couple of bubblers.
Just thinking about it, one of the main problems with a jacobs ladder approach is the fact that the ladder relies of ionized air
(at the bottom of the ladder) to rise from the heat, creating a pathway for the plasma arc. The problem I see is that the N*
and the O* will be constantly in this plasma arc, and only gets a chance to recombine at the top of the ladder. By using
moving air and spark plugs, more monatomic N and O is produced, hence (hopefully) more NO and NO2.
Hell, even if we can get 10% HNO3 all that is needed for this is electricity and water we could simply distill to get 100%
eventually.
Just add H2SO4 then boil off the HNO3 then just boil off the water to recycle the acid. If you're pressed for water, recycle that
as well by condensing.
A hot plate, temperature probe and some accessories and you could have an almost autonomous HNO3 producer. Add in
some solar panels and you're laughing.
Nitric-producer February 26th, 2007, 07:32 AM

After testing the PH of the gas that escapes outside from the exhaust of the bubblers, I have decided to redesign my bubblers
and add a couple more. I am clearly losing precious Nitrogen Dioxides! I will try several different designs (some of which have
been mentioned above by Mega), and note the efficiency of each.
In my reactor I eventually opted for a spark plug type design, mainly due to always failing at a Jacob's ladder design.
Having never worked with high voltage before I didn t realise how ea sily it will "jump" through supposedly ins ulating
materials. My reactor has a 15mm spark gap - which gives a constant spark across the electrodes - I doubt that this design is
the most efficient design.
Is there a website which gives exact compositions of household products - im sure I have seen it mentioned here before. I
need to know what is causing the colour in my Sulfuric acid - as it is causing problems with my distillations.

Might there be a way to fix the NO2 so that it precipitates out of solution? I don't remember if there are any nitric salts
insoluble in water, but what about a different solution, EtOH or acetone, etc.? How about the Ca(OH)2 route?
Another workaround: How would the yields improve if bubbled through sulphuric acid?
(It won't let me edit my last post.) (but I can - mega)
About the best I can find is that KCl is soluble in alcohol but KNO3 is not. So it would presumably precipitate. Um, lemme back
up, if KCl were saturated into alcohol and our enriched gasses were bubbled through, I'm guessing that some of the K would
react with the recently fixed NOx and precipitate out. I suppose the Cl would evolve as Cl2.
Another route is bubbling the enriched gas in water, through KCl solids. KCl is somewhat soluble in water but KNO3 is highly
soluble. The KCl would saturate but as it reacted with the NOx, supposedly more would dissolve to maintain saturation.
Supposedly the KNO3 would increase in concentration and Cl2 would evolve. You could monitor progress by watching the KCl
solids disappear. When the solution is doubly saturated, it can be dried and alcohol used to remove any KCl left. At least this
last part is real, I was able to verify this separation.
As far as the rest, I really need some better chemist than I to verify (or come up with something better, is OK too)
NGfan March 1st, 2007, 07:21 PM

Anniesland U.K, fractional distiller?
I have begun the task of making HNO3, and I've made a short vid on YouTube which demosntrates the speed the NO2 gas
forms at, but I am putting the project on hold if I have to go out and buy a rotavap to get 100% HNO3. From what
megalomania has said, I understand that agitating the solution with oxygen will minimise HNO2, but do you mean during, or
after you've made the HNO3, and is it 100% oxygen, or can you just push out more air than you do nitrous gasses?
Also, what will the HNO2 do if it was used in making HE's? It'd be nice if there was more research into it. Wikipedia says it
decomposes into NO2, water and Nitrogen dioxide, which can't be that bad, if I knew how it was that it decomposed. Ah well,
looks like a thorough scouring of the internet is imminent.
Wait, this website http://www.ucc.ie/academic/chem/dolchem/html/comp/nitric.html states that if the HNO2 is heated, it forms
HNO3, water and nitric oxide. Now, to find that heat...
fractional distiller March 2nd, 2007, 02:59 AM

Ngfan- I hope this helps you out.
Well first of I would love to see the video of you producing NO2, please post the link! Second do not put your project on pause
because there are many ways to get pure HNO3, it is possible for you to deviate from Megas process. We all will have to very
slightly how we construct our reactors due to budgets, space constraints and endless other restrictions/ramifications.
To answer the purposed question that ,I am guessing you are asking, agitating the mixture with O2 to reduce the amount of
HNO2 in your final product can be done many ways. Agitating it with surplus oxygen as it is being broken apart in the reaction
chamber is what I plan to do, but it can be done after wards as shown in your site ( http://www.ucc.ie/academic/chem/dolchem/
html/comp/nitric.html ) under the Oswald process but that is an entirely different set up, because of my design. Which the as
of this moment two ceramic jars and a Jacobs ladder or spark plug depending on which is more cost efficient, easier to set up,
and most important practical/efficient. A pump will feed air into the chamber and I will agitate the mixture with O2 by just
adding a small inlet hose into my pump and just allowing O2 to feed in, but I will explain that momentarily.*
The problem that the air we are using for the reaction for our HNO3 production is 78% N2 and 21% O2 with 1% trace gasses
that wont matter. So if you have a liter of air you have 780ml of molecular nitrogen and 210ml of molecular oxygen. Since
Mega was kind enough to give us the final part of the formula you can calculate it as such.
1 liter of air consists of 780ml of N2 and 210ml of O2.

N2,O2 => 2NO /a 1:1 ration of molecules 2 Nitrogen too 2 Oxygen
2NO + O2 => 2NO2 / Now the ratio is 2:1 Nitrogen too Oxygen
3NO2 + H2O => 2HNO3 + NO/ Ratio still stays the same, just the addition of water.
So to answer your question yes add O2 to it as it is reacting and I am pretty sure you want to use pure O2 because anything
else will just mess up your reactants and may result in unwanted by products.
* As I had mentioned above the Oxygen will need to be added as the reaction takes place and a large quality will be needed
to maintain a fast and effective and efficient production of NO2. Considering the math I have shown above you will need a 2:1
ratio for the amount of Nitrogen you put in via my method.
So for every liter of air you put in you need 1.56 liters of O2 to keep the equation balanced. I will probably be producing my
O2 by electrolysis of H20. I will be using electricity anyway to run the reactor so a little more plus some tap water and salt as
an electrolyte wont hurt. LMAO If will be using 3.12 liters of water and about 5 amps to yield the 1.56 liters of O2 I require.
Secondly your question concerning the impurity of HNO2 in HNO3 the problem I see with this in HEs is that it cant be beneficial
my RDX creation as graciously introduced to me by mega calls for pure HNO3 so I dont want any HNO2 in it screwing up my
yields. Yes HNO2 does decompose if heated but so does you HNO3 so effectively by trying to purifying you acid by heating ,if
that is what you are implying, will only leave you with a less useful product then you started with. I dont care about the extra
NO from the reaction because it will just be absorbed into the HNO3 (I think it may be wrong) in that case I have fuming nitric
acid at my disposal or I just decrease the pressure with the handy vacuum pump and that pesky NO goes away!
Hope this helps! Anyone if I did my math wrong or made some blatant mistake or any mistake please do not hesitate to point
it out.
Best of Luck.
Nitric-producer March 2nd, 2007, 10:59 AM

After about a week of running the reactor, I have obtained about 3 jars of Nitric acid. No matter how long I left them - the PH
would not go below 1! It's quite cold here just now, between 0 and 10 C most days, so my water was nice and cool. So if you
build your own reactor, stop running after you get to PH 1 - otherwise you are just wasting electricity.
On the subject of obtaining Nitric by using a base solution. I plan on doing this method after I build my "Contact process"
reactor. For me - Sulfuric acid is to hard to obtain in large amounts so I plan to recycle it. However when I can make my own
Sulfuric I will try this:
Having my bubblers filled with a concentrated solution of NaOH - with a PH of 14. As NaNO3 is a neutral salt - when the PH
goes to 7 - you will have used all the NaOH. If you know exactly how much alkali you used, you can calculate yields etc.
However can anyone remember the formula for changing Ph values into concentration of acid values? Just so I can calculate
how much Nitric I have.
More progress next week when the rest of my vacuum set-up arrives.
NGfan March 2nd, 2007, 01:02 PM

Wel, thank you muchly for your reply, fractional, but you ommited wether or not you were reffering to Anniesland in the U.K, as
I live far, but not too far from it.
*Sigh* I hate having to make my own O2, and as well as that, I'll have to make some sort of regulator to control the input, so
as not to waste it... This is turning out to be harder than I first anticipated, so I think I'll overbudget, and buy some more
equiptment.
I also find, as they're are extremely high voltages, that even wood conducts, and I have to use plastic from wall sockets.
The YouTube vid is here; http://www.youtube.com/watch?v=dScqzU7UGHk but the camerawork is shoddy, and YouTube actually
cut off the last thirty seconds, in which it steadily got redder inside. It was also just a shoddy beta-version, a nice B-E reactor
will be in in the not-to-near future.
I am also doing this for RDX, but I think it (HNO2) produces VERY unwanted by-products, rather than poor yeild. Well, RDX
first, then anything really.
Alexires March 4th, 2007, 05:51 AM

Nitric-producer: As pH = -log[H+] ions, then you can say that
[H+]=10-pH
I hope that is what you are looking for. Hence, if you get an answer saying 10, then you have 10mol/L of hydronium ions, and
hence, you have 10mol/L of dissociating acid (doesn't need to be straight HNO3. For instance, if you have HNO2 contaminants,
then it will fudge your answer somewhat)
If you know your acid is pure, then that will tell you the concentration of your Nitric in mol/L.
Also, to anyone whom might be emailing me, you should PM on the forum. My email isn't working at the moment. Also, use
an email that doesn't contain your name for gods sake. You have no idea who I could be.
For all you know, I could be LEO or some other kind of "terrorist".
RTPB people, RTPB.
Also, NGfan, I watched your video. Very interesting after only a few minutes use. What was the input into your NST? Would it
be possible to hook it to solar power or something that cannot be traced?
You might want to try now hooking an aquarium pump up, pumping air into the chamber, bubbling the air/NO2 through a few
water traps and taking a pH test of it, or just simply seeing if you get any result.
I'm pretty eager about this idea, seems like a very possible way to get HNO3.
I cannot seem to find any data regarding the decomp. temp. of HNO2, although an article (http://www.ncbi.nlm.nih.gov/
entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=11237042&dopt=Abstract) I just read says that its concentration in
HNO3 decreases as the temperature approaches 50*C. I'll have a look at a merck index tomorrow and see what it has to say,
and what options we may have.
Another thing that occured to me would be to use some kind of sonic wave to cause the HNO2 to break down, leaving the
HNO3 intact if there is no other way of removing it from solution. This came from the same article that said you can produce
HNO2 by hitting HNO3 with ultrasonic waves. Ill post results soon.

HNO2 will eventually be oxidized to HNO3 given time, but I don't have any references on that at the moment, or under what
conditions it can be accelerated.
There is absolutely no reason to use pure oxygen in this reaction! They do not do that industrially. Use a surplus of
compressed air from a fish pump or air compressor run through a bubbler. NO is highly reactive to oxygen, even in small
amounts, and will form during the reaction at such a rate that it is essentially merely an intermediate.

Not to mention the explosion hazard if you are cracking water *shudder*.
Mega, I thought that HNO2 broke down into its constituants (NO and H2O).
We all admit that from this project, to get nitric acid of a decent grade (80%+), then we are going to need to vacuum distil.
So, personally, I wouldn't worry about the HNO2 in the acid. You aren't going to be making RDX from the acid straight out of
the reacton, you are going to need to distil first.
On a different, I consulted the merck index today to find nothing. No specifications for HNO2.
I am at a loss of what to do.
My chemistry teacher (when consulted) said that it might be possible to use H2SO4 to oxidise the HNO2 to HNO3, but that was
just a vague thought.
Another possibility that just came to me may be freezing HNO3 to seperate it instead of heating it. Just a random thought.
megalomania March 5th, 2007, 07:26 AM

There are other threads discussed over the years about distilling and concentrating nitric acid. That is putting the cart ahead of
the horse at this point. We need to get fixed nitrogen first.
If nitrous acid does break down to NO then that NO would be oxidized to nitrogen dioxide which would then form nitric acid.
Perhaps this is why air is bubbled into colored nitric acid to make it white?
I should mention that the nitrous acid needs to be left out in the open air, uncapped/unsealed for it to eventually form nitric
acid. I have a book here that says nitrous is highly unstable, and readily decomposes to NO with ease. Apparently passing
chlorine gas into nitrous acid forms nitric acid and hydrochloric acid. Also the book says the most concentrated nitrous acid can
get is 0.2N, at which point it is exceedingly unstable.
Also I should qualify my last post by saying adding some additional oxygen can help the reaction since we would achieve a
maximum equilibrium at a 50:50 mix of oxygen and nitrogen. Since producing oxygen might be uneconomical for some, it is
entirely optional. Pressurizing the reaction vessel would also bring more air into contact with the electric arc. Again, that is
entirely optional.
Al Sheik Yerbuti March 5th, 2007, 12:54 PM

I came across some info from
http://www.inchem.org/documents/icsc/icsc/eics0930.htm
concerning NO2 which contained in part:
Boiling point: 21.2C
Melting point: -11.2C
Relative density (water = 1): 1.45 (liquid)
Suddenly I realized what is happening in my "still"! In reacting Sulphuric acid with Potassium Nitrate, I have NOT been making
Nitric acid, but what might be called anhydrous nitric acid; in other words, NO2! Now this is a very important distinction! I have
been optimizing my reactor to maximize the density of NO2 fumes, as evidenced by the visually measured density of the
fumes. These fumes are passing into my collection vessel, where they are cooled by ice packs, which can easily cool the vessel
below 21.2C! That's 70F. Other properties found on that page confirm this assertion, such as the yellow color of the liquid and
my density measurements the other day were at 1.44 something. At the time I thought My measurements must have been
inaccurate because I expected closer to 1.51 for 100% HNO3 but this new info seems to confirm this particular measurement
and its interpretation.
Funny, I had been concerned that I had too much water in the Nitric acid, but since liquid NO2 reacts with water to make HNO3,
I have actually not had enough water! Heck, I could use the liquid NO2 to consume the last 2% of water in Sulphuric acid to
produce an ideal nitrating solution.
No results for the plasma cutter yet. I promise today, though.

__________________________________________________ _
LATER...
I bubbled the plasma from the torch into distilled water. I did this for maybe a minute total. The water became very warm. It
was splashing everywhere and was obviously an inefficient setup. I was unable to detect any change in pH from litmus. There
was the unmistakeable odor of NOX. I'll set up a more efficient method, as the odor is encouraging for sucess. I'll also try
alternative methods of capturing the loose NOX in solution as I have previously discussed. Photos are click-to-enlarge.
http://img251.imageshack.us/img251/5747/plasmanox01vd6.th.jpg http://img63.imageshack.us/img63/6605/
plasmanox02rc4.th.jpg (http://img251.imageshack.us/my.php?image=plasmanox01vd6.jpg) I referenced my "still", here's a
pic: http://img443.imageshack.us/img443/4982/hno3generatoric6.th.gif (http://img443.imageshack.us/my.php?
image=hno3generatoric6.gif)
NGfan March 5th, 2007, 01:12 PM

Well, that is a releif, Megalomania, as I was sure I'd have to put in lots more work to make the HNO3 uncontaminated. I've
also jumped a few hurdles in terms of problems, so I'm fairly optimistic about the project. I still need to find out how long the
transformer runs before overheating.
Alexires, my transformer uses regular mains at 240v, with 2.5A. The output is 10kV at 50mA. The gas takes a while to form
though so it actually got redder after the end of the video, but for some reason YouTube cut it off.
I'm not sure if it is possible to hook it into solar panels or something, but you'd need a pump too.
I will be testing soon, but not too soon as I want the finished product to be perfect, as it involves much dangers: toxic gas,
acids, high voltage electricity and a chance to become homeless if it's too inefficient (electricity bill).
I have decided not to add surplus oxygen, even though a friend of mine actually has quite a few canisters, as it's just too
much effort for little gain.
Chris The Great March 6th, 2007, 03:16 AM

HNO2 readily decomposes in highly acidic conditions, anyone who has ever added a strong acid to a nitrite knows this. Simply
put, I am absolutely sure in saying that there is no HNO2 in the nitric acid and that you should all stop worrying about it.
I think time would be much better spent finding what common materials (plastics and metals) are not attacked by NO2, dilute
nitric acid and concentrated nitric acid. What performance do standard plastics have against the chemicals? Are they destroyed,
damaged above a certain temperature or unaffected? Such information is essential in designing a suitable reactor and really
should be the top priority for this undertaking as experimentation is going to be difficult if nobody knows what can actually be
used to build the setup so it will last and not contaminate the product! Nobody likes finding out the hard way that component X
of their design is not actually immune to NO2 gas and having to start all over...

Thanks Chris, that is useful to know. Anything to back it up? Of course, I wouldn't be suprised as Nitric Acid is a strong
oxidiser, and should oxidise HNO2 to HNO3 (I'd hope).
On corrosion resistance -
http://www.mext.go.jp/english/news/2000/09/000961.htm
States that because of a lowering phosphorous content in stainless steel, it has improved corrosion resistance against nitric
acid.
Corrosion resitstance chart for gaskets and stuff. - http://www.akrongasket.com/chart1/newchart40.html
This (http://ptcl.chem.ox.ac.uk/MSDS/glovesbychemical.html) website thinks that PVC is suitably corrosion resistanct to nitric.
Ofcourse, we aren't just talking about concentrated nitric, we are talking about boiling nitric.... which is about a fucktonne
worse.
Also, mitsubishi metals has this (http://www.mmc.co.jp/alloy/english/products/taisyoku/gijyutsu2.html#15) to say about

corrosion resistance to boiling concentrated acid happiness.
Seriously though, a couple of hundred dollars to buy a decent vacuum setup is sort of a must. Most of these things are
titanium alloys, and you can't afford them over glass. Go the glass.
If you are going for a BIG setup for making nitric, still buy glass *laugh*. Either do it in batches, or use big flasks.
PS. This (http://stainlessandalloy.thomasnet.com/item/special-fabrications/custom-bending/-nbsp-1220?&forward=1) says

that stainless is "satisfactorily resistant" to boiling 65% nitric acid. Include a little low pressure, and as long as you keep the
temperature below 70*C it is "fully resistant" or so they say.
That looks better - http://www.nickelinstitute.org/index.cfm/ci_id/10626/la_id/1.htm
Also, something I picked up as I was looking around was this - http://adsabs.harvard.edu/abs/2005RaPC...73..213K
Unfortunately, I can't find the article. It would be interesting if we could make HNO3 via some kind of EM radiation.
Nitric-producer March 7th, 2007, 05:49 AM

In my chemical engineering book, it states that in plants where Nitric acid is produced, Aluminium is always used. (same for
Sulfuric acid) This is because Nitric and Sulfuric are oxidising acids and when in contact with Aluminium they form an oxide
layer over the metal protecting it!
In my reactor I have used a dessicant chamber to dry any air entering the rection chamber - there has been no corrision
anywhere in the chamber. My problem is my bubblers and corrision! Silicone sealant and epoxy are both eaten by Nitric acid -
they did not work. PVC tubing however is not corroded. My new design mainly encorporates glass and aluminium.
Al Sheik Yerbuti March 7th, 2007, 10:22 AM

I have found that using a liberal amount of teflon tape as a gasketing material resists nitric corrosion. For those few who don't
know, teflon tape is extremely common in plumbing and pneumatic work. It's the white stuff in the white and blue spools.
---------------
EDIT:
Harbor Freight has solar panels up to 50 watts. They output 17V to charge car batteries, but I've seen cigarette lighter power
converters (to household current) at Wal-Mart for (I think) $12.
W=VA so 50=17(3) and 50=120(0.4). And that is only at peak sunlight.

--------------
EDIT #2:
wind power is more advanced than solar.
If you're rich, go here: http://www.bergey.com/
If you're poor (or handy and/or frugal) go here: http://www.otherpower.com/otherpower_wind.html
NGfan March 7th, 2007, 12:57 PM

Well, right now I'm building a prototype to see what factors I will have to account for, such as materials. After letting it run for
a while I'll check to see which materials have corroded and what problems I have encountered and then build from there.
Although it would be nice to have an independent, continous supply of HNO3 that was untraceable, I'd just buy a petrol
powered electricity generator if I was looking for that. As it is, if the piggies can manage to trace me from a slightly incresed
electricity bill, then I'll be impressed.
Chris The Great March 7th, 2007, 09:43 PM

I guess a good idea would be to simply boil different materials in nitric acid of various concentrations to make sure it's
suitable. Hopefully I'll be distilling some fuming and 70% nitric acid this weekend, although I'm sure there are tons of people
here with a bit of extra acid who can do some tests as well.
I was under the impression that aluminum was only resistant to concentrated nitric acid, and not diluted acid. Obviously it
would be very easily to find out by adding a piece of Al to some 70% in a test tube... I imagine that aluminum nitrate is
insoluble in higher concentrations of nitric acid as well, which will keep the oxide layer from simply dissolving away as the
nitrate...
But it's great to hear PVC is resistant, as lengths of pipe could then be used for the absorption tower. I am going to go with
the Ostwald process myself but the actual engineering difficulties are the same (or at least very similar).
(edit) As for the HNO2 thing- no, I don't have a reference, and there probably isn't one since you guys searched and turned up
nothing. It's experimental data from other hobbyists. Also, a method for producing N2O3 is reducing nitric acid with starch.
Obviously the reduction product, HNO2, is not stable and immediately breaks down, otherwise the preparation wouldn't work...
2HNO2 -> H2O + N2O3 (NO + NO2)
I can dig up a link demonstrating that if anyone would like it.
akinrog March 8th, 2007, 01:15 PM

Suddenly I realized what is happening in my "still"! In reacting Sulphuric acid with Potassium Nitrate, I have NOT been making
Nitric acid, but what might be called anhydrous nitric acid; in other words, NO2!
Anhydrous nitric acid is N2O5, i.e. nitric pentoxide. And IIRC from my education (years ago), when you chill NO2 to liquidate it,
it becomes N2O4. Regards.
nbk2000 March 8th, 2007, 02:51 PM

N2O3 is condensed as blue liquid from a mixture of NO and NO2.
http://www.cci.ethz.ch/experiments/darst_N2O3/en/stat.html

Ok just tried making some Sodium Nitrate from the Nitric I have made using my reactor. Neutralised acid with Sodium
Hydroxide, boiled off water. Stopped when I had about 20ml of solution left. The liquid had some kind of orange colour,
almost a precipitate. Any ideas anyone? Anyway baffled by this - I boiled off all the liquid - I then got what looked like boiling
sugar? Once cooled a hard brittle solid has formed.
Its in a big chunk, some of which I powdered and burned with paper - which fizzed nicely. Like an oxidiser. So can anyone
shed some light on this orange colour and do I have NaNO3? It physically does not look like it.
Does my reactor somehow get impurities from somewhere?

Did you use city water, or distilled water? Who knows what evil (ions) lurk in the heart of city water...

I used "city water". However after more observation, the orange colour has precipitated out completely leaving clear liquid and
orange precipitate. It looks like Iron Oxide. Although I dont know where its from as there is no iron in my reactor? Anyway, I
came home early to finish my new bubblers, hooked them up and they would not hold a seal - so I'm back to the drawing
board. Again! I'm really stuck now. :confused:
chemdude1999 March 13th, 2007, 06:51 PM

If you have old galvanized pipes, that could be a source of iron. City water is usually free of iron (at least compared to well
water). However, I have ran my city water on an AA spec, and it does show all the metals. BUT, it shouldn't be near enough to
cause oxide precipitate.
Trace the problem back from the tap. Maybe give the water company a call. Tell them you are worried about a new salt water
aquarium you are setting up.
My guess is the impurities are screwing your seals up. Break everything down and clean it well. Good luck.

When the city flushes the hydrants the level of rust in the water increases significantly, that's why they do it though, to flush
that crap out of the pipes. They are always flushing some hydrant somewhere it seems, so maybe you just got unlucky. Still,
that's why you never use city water in the lab...
I ordered a HV source yesterday, and my electrodes still have not arrived :(

Grab your top hats and get the Delorian up to 88.5 because we are taking a trip back 100 years to find out what the ancients
had to say about nitrous acid.
Nitrous acid is very unstable, this I have mentioned. I now have references Aqueous solutions of nitrous acid upon warming
decompose to NO leaving nitric acid:
3HNO2 --> HNO3 + 2NO + H2O + 30,770 cal.
This decomposition will proceed in the cold in the presence of rough surfaces (sand, glass fragments, etc.). Saposhnikoff, J.
Russ. Phys. Chem. Soc., 1901, 33, 506. Lewis and Edgar, J. Am. Chem. Soc. 1911, 33, 292.
Naturally life conspires against me and my proxy to pubs.acs.org is down At least the first page is free, so everyone can
peruse it at http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1911/33/i03/f-pdf/f_ja02216a004.pdf
The solution of the acid is more stable in the presence of nitric oxide under pressure Helv. Chim. Acta. 1920, 3, 366.
I could go on, but you get the point. The stuff is unstable, it spontaneously decomposes as soon as it exists, and a bottle full
of broken glass would get rid of it nicely, especially if gently heated.

Just been doing some thinking, and have been wondering about Dinitrogen Tetraoxide (N2O4). According to my search below
21 *C it becomes a liquid. If some effiecent way of cooling the gases could be obtained after exit from the reactor, it would be
so much easier just to mix N2O4 with water. Could Pure Nitric be obtained this way (or almost pure) ?
Info on N2O4 : http://en.wikipedia.org/wiki/Dinitrogen_tetroxide

Frunk March 18th, 2007, 08:24 PM
Could Pure Nitric be obtained this way (or almost pure) ?
Info on N2O4 : http://en.wikipedia.org/wiki/Dinitrogen_tetroxide
Info from the same damn page:
Intermediate in the manufacture of nitric acid
Nitric acid is manufactured on a large scale via N2O4. This species reacts with water to give both nitrous acid and nitric acid:
N2O4 + H2O HNO2 + HNO3
The coproduct HNO2 upon heating disproportionates to NO and more nitric acid.
nbk2000 March 18th, 2007, 09:22 PM

A journal article from the 30's about using air to produce high-purity NA, free of NOx.
Nitric-producer March 19th, 2007, 10:48 AM

Frunk: Sorry if my post was unclear, what I meant was if you mixed 1 mol of water with 1 mol of Dinitrogen Tetraoxide, would it
give you 1 mol of HNO3 and 1 mol of HNO2 - as the equation states. The problem I am having is that with NO2 and water, you
need a large quantity of water to dissolve any NO2 in. Giving low concentration acid.
I guess what im gettin at is, if I where to mix a certain quantity of water and N2O4 - would I get anhydrous Nitric acid, with
anhydrous HNO2?
Thanks.

As these things usually work it can be difficult to get the reaction to go to completion, Le Chat's principle and all. It may take
time, maybe on the order of weeks in a sealed container, for the reaction to complete.
Not all reactions are like that of course, it depends on the reactivity of the reagents involved. I don't imagine dinitrogen
tetroxide is all that reactive with water to the point it will react instantly and to completion, but I have no concrete data either
way, so I could be mistaken. With constant agitation and minor heating I bet eventually you could get an anhydrous product.

Thanks Mega, that sounds promising. My friend who is an "overclocker" told me about devices used for cooling PC CPU's. One
he mentioned was a Peltier. Put simply when you give it power one side gets very hot and the other gets very cold. I plan to
purchase said device and possibly a mini fridge. However got to many projects on the go at the moment - Aldehyde reactor,
Contact process, the list goes on...!

Lots of recent developments:
Tonight I tried a Nitric extraction using DCM. Started boiling off DCM, I must have went to far and fairly soon I got thick red
fumes of NO2. I killed the power and sat the whole beaker outside. Got some nice red acid.:(
After some reading of my textbook - I came across this:
O3 + 2NO2 --> O2 + N2O5
As N2O5 is the anhydride of Nitric acid, once dissolved in an exact amount of water it forms Anhydrous Nitric acid without any
HNO2 or other rubbish! :D
I am now thinking feed NO2 from my Nitric reactor into a second chamber filled with Ozone, keep the temperature below 20*C
- and you get some nice N2O5 :D . Imagine pure anydrous without any messy extraction techniques, as detailed above! :(

Since the electric arc makes no small quantity of ozone as well as NO2, cooling the gasses or compressing them in anhydrous
conditions might be a good way to make N2O5. Liquefying NO2 makes N2O5 anyway, but the presence of ozone should
improve the yield... if your reference is really as simple as you have indicated.

An interesting page:
http://www.ijvs.com/volume2/edition1/section2c.html
Nitric-producer March 31st, 2007, 06:06 PM

Ok, here's what im planning next:
The Nitric reactor is run as normal except the NO2 is condensed by cooling to form N2O4. The whole thing is turned off, and
the air pump is swapped for an "electrolyisis of water" device, which feeds the reactor with pure oxygen, which before entering
the reactor is bubbled through a dessicator probably filled with concentrated Sulphuric acid? The spark gap then converts the
O2 to O3, which is then bubbled through the liquid N2O4. What im hoping will happen is that N2O5 is formed and can then be
collected. Mix with water and you get 100% anydrous Nitric acid.
Can anyone see anything wrong with this setup that ive missed, before I spend a week trying to build it?
mr.pyro March 31st, 2007, 07:57 PM

Just wondering how are you going to keep the H2 separated from the O2 and out of the spark gap?
That could cause a nasty mess.
Something like this: http://en.wikipedia.org/wiki/Image:Hoffman_voltameter.jpg
megalomania March 31st, 2007, 11:22 PM

Nothing sophisticated is required to keep the hydrogen gas out.
You could place the electrode generating the oxygen into a plastic pipe. The length of the pipe is longer than the electrode.
When the works is immersed into water, the oxygen gas goes up and is channeled into your ozone generator.
The only problem I see is that you would need tremendous amounts of power to produce enough oxygen to get pure oxygen
beyond a minuscule amount. Why not just use a traditional ozoneator?
I have done many ghetto electrolysies in my day, and you don't get a whole heck of alot of anything despite days and weeks
of running the thing. Your spark gap is already cranking out ozone as well as nitrogen dioxide, why not settle for that.
What I can't tell you since I don't know myself is the percentage of nitrogen oxides produces by the electric arc. Keep in mind
you consume oxygen to produce nitrogen oxide, more oxygen is consumed to produce nitrogen dioxide from the nitric oxide,
and yet more oxygen becomes ozone. From anecdotal observations I have heard many people describe, ozone will be
produced in the most significant amount. I read only one scientific reference that described nitric oxide production as only
being a few percent relative to the volume of air run through the system. My hypothesis is that there is sufficient ozone
present from the spark to react with all of the nitrogen dioxide produced. Some experimentation may be required...
Nitric-producer April 7th, 2007, 04:27 PM

The only reason for seperating the procedure is because of yields. I looked at Ozone producers on ebay, and they only
seemed to produce a maximum of 400mg of Ozone per hour, after some calculations this only amounted to 16ml of Nitric
every day assuming 100% reaction completion. If I had some idea of how much Ozone my reactor makes, I would know if it
was worth just running using air? I guess I will need to do some experimentation. Unfortunately my funds are rather low at the
moment. :p
Darkover April 17th, 2007, 02:58 PM

I've been watching this thread with great interest. Other than Nitric-producer, has anyone done this ?
Heat April 17th, 2007, 06:21 PM

I've done it. It was almost a year ago (I've been busy with personal problems for the last year), but I do intend on making a
new and better one.
The method does actually work, but you have to sweat for it if you want usable amounts.
I used basically the same setup as the guy on species8472.dyndns.org. My power supply was a 7500 volt NST. I had a large
glass jar, into which I pumped air using an aquarium pump. I had a pipe that pulled air out from the top of the jar into my
bubbling chamber. The bubbling chamber was a glass jar filled with distilled water. The bubbler was a glass pipe with some
holes in it, wrapped in fiberglass which was held in place by teflon tape. (This was to reduce the size of the bubbles, since a
simple mathematical calculation showed that reducing the bubble size by a factor of N, increased the effective reaction surface
area by a factor of N. Not to mention that it reduces splashing)
At first, my yields were very low. (It took a few days before I could get baking soda to even bubble.)
So I had to start working out the problems. The first was that my reactor was leaking like crazy. No glue that I could find held
out under the heat of the arc. Not to mention that NO2 itself is quite corrosive. I ended up setting up a 555 timer circuit which
was connected to a relay that switched the NST on and off. I think the duty cycle was something like 30 seconds on, and 15
seconds off.
The next problem was that the NO2 yield was very low. I figured that out, too: I had set up my arc as a Jacob's ladder, but the
top of the ladder was smooth, and too wide, so that the arc couldn't hold itself there. So it was continuously breaking and
restarting (several times a second). Originally, I thought that was how it was supposed to be, but it's not! The idea is that air
has to pass *through* the arc, but when the arc is rising, it's just moving with the same air.
So I changed the design: I had two sharpened nails, wrapped in copper wire to act as a heat sink. The nails were attached to a
simple hydraulic system I made with a couple of water-filled syringes, so that I could manually adjust the distance after I
closed the jar, even while it was running! So I'd hook up the power, pull the nails together, and then pull them out to the
desired arc length.
I think after the first night that I ran this system, I finally had acid that would bubble nicely when I added baking soda.
It worked pretty well, except that sometimes the arc would go out. So I added a timer based system that passed a round
metal object between the nails every few seconds, to "ignite" the arc.
But then everything started leaking again.. and I never found time to fix it.
Anyway, I scrapped that desing and I plan on making a new system. I'm just trying to figure out how to make proper seals..
Last time about half of my connections were leaking.
By the way, I think the NST (Neon Sign Transformer) is very ideal for this kind of project. I bought mine used at a neon sign
shop for about $10. They provide a nice clean supply of high voltage current, and are current limited, so you don't have to
worry about blowing anything, even if you short circuit the output.
I also have a picture, but it won't let me make any attachments. (it doesn't even show the option)
stupid939 April 17th, 2007, 08:01 PM

As soon as I get an aquarium pump I will make one. I plan to use PVC or glass for the spark-gap chamber, and I have a 9KV
30ma transformer that I used for a tesla coil. It should be suitable for the project.
I already attempted to build the blower/spark assembly, but it did not work because I had a microwave fan blowing air through
the chamber and it did not create enough pressure to bubble the gasses through water. I will try to pick up the pump in the
next few days, and I will put up a tutorial or something with lots of pictures (tutorials are hard to find these days, aren't they?).
Nitric-Producer - If you have any suggestions on the construction of the chamber, let me know so that I won't have to find
mistakes and remake it.

Heres some pictures of my first setup:
http://i155.photobucket.com/albums/s296/minioneandrew/DSC00233.jpg
http://i155.photobucket.com/albums/s296/minioneandrew/DSC00225.jpg
The 1st picture shows the entire setup: From left to right, an aquarium pump, a dessicator chamber filled with NaOH, the 15KV
supply, the terracota reactor, and the 2 bubblers.
The 2nd picture shows a close up of the spark gap. Sorry about the low quality images.
This setup has now been abandoned due to the Nitric dissolving the seals of my bubblers. The reactor itself has no leaks, due
to there being no moisture inside, i.e no Nitric. I am in the process of building a website to give better details. Silicone sealant
and epoxy are not nitric resistant. PVC pipe is however. Hope this helps.
Frunk April 19th, 2007, 10:00 PM

I assume the flexible pipes are some form of transparent PVC?
Anyways, good job. I like your setup, and even more given that it cost 50$. :D
This forum may get pics of my future setup during the summer.
Nitric-producer April 20th, 2007, 09:58 AM

Yeah just flexible PVC pipe. Bought from hardware store. Id say if I didnt have the failures this time I could go out and buy
the whole lot for 20 dollars, not including the NST. Id advise anyone wanting to build a reactor, just make sure everything is
dry. Sealing is so much easier, without having Nitric dissolving things.
++++++
Id is a psychology term. Perhaps you meant I'd, as in I would? NBK

On the previous page...
http://www.roguesci.org/theforum/showthread.php?t=4181&page=4&highlight=electrochem%2A
nbk2000 has an attachment in one of his posts, a rar file of a 1930's journal article.
I cannot get that attachment to download. Right-click and 'save as' did not work; and a direct click on it also did not work.
Both actions did bring up my 'download' menu, but all that was saved was something called "attachment.php"; which is very
small and not a rar.
I tried opening it in another tab (Firefox), to see what kind of error-msg I might be getting; but that didn't work either. It
again opened my download window.
Has anyone successfully gotten that attachment; and if so, what procedure did you use?
thanks!
EDIT: Found the answer, sort of. Just opened that "attachment.php" page in Notepad, and discovered that it's trying to put up
the "You are not logged in or you do not have permission to access this page" message.
Does anyone know if that journal article is on tmp's FTP; and if so, which directory it's in? thanks.
stupid939 April 21st, 2007, 01:46 AM

Hey Nitric-Producer, did you seal the terracotta pots with epoxy? It looks like you sealed the air inlet, nuts, and joined the pots
together with epoxy. I know that the epoxy won't hold up to the nitric acid, but your setup leads me to believe that as long as
no moisture is present, the epoxy in the reactor should stand up to the NO2.
I went out today and gathered everything I needed, and I started assembling it. I have the bubblers done, and I am going to
work on the reactor next. I am only waiting to see if the epoxy will be fine to use in the reactor.
I may end up using the terracotta pots instead of PVC, but the only problem I see is disassembling the reactor.
Everything for the project, besides the NST, cost me $18.82, and I even bought some extra stuff. I am taking pictures, and
once it is done, I will put up a tutorial on my site and probably create a PDF.
hydra April 21st, 2007, 04:17 AM

mega, in regards to oxygen-production...
Perhaps your trouble with getting useful quantities was due to not using enough current? The process actually can produce
quite a bit of gas per Kwh of energy...about 150g/kwh for a normal 2-gas cell; and double that for depolarized cells. Another
advantage of using an air-depolarized cathode is that no hydrogen is given off at the anode; so the "separation problem" is
solved.
The type of cell I'm talking about also does not consume any reactants other than water.
One must realize tho, that at the cell-voltage involved (1.5 volts), even a single KwH represents a pretty high current....i.e.,
660 amps!
That's in a realm that's a little hard to work with... :D
Anyway, if you were running just a single cell, and weren't running more than 5-10 amps, you can see that the output in
grams/hour would be disappointing, for sure.
However, 50-100 amps is entirely doable with common equipment and materials. And that would be about 30-50 grams/hour
per cell.
Since it's inefficient to lower a 'normal' voltage PS to 2v with resistors; the common solution is to run several cells in series.
A properly made depolarized cell will run 1.2 - 1.5 volts per cell; so 3 cells would be just about right for a typical high-current
5vdc surplus PS; like a PC PS.
7-8 cells is probably optimum for a 'typical' 12vdc battery charger (which runs 16-17v no load, to about 11-12vdc at max
current).
fyi, here is a good early writing on producing oxygen with an air-depolarized cathode instead of a regular cathode:
GAS-pat2390591- ELECTROLYTIC METHOD FOR PRODUCING OXYGEN - Janes.pdf
It also includes some info on making the cathode itself (methods and materials are well within range of home-shop, btw)
If I have my numbers right...
1 gram mol. weight of any gas is about 22.4L at STP.
So O2= 32g/22.4L, and a cuft= 28.25L. So a cuft of O2= 40.35g
Assuming a 50amp current-level through 8 cells @ 1.4v/cell, your power-rate would be about 500whr; so about 150g/hr of O2
production.
That'd be roughly 100 liters/hour...not too shabby. (equals 4 cuft per hour)
The nice part is that the price is right. At 10 cents/khw, you're looking at only 5 cents per hour to run at this rate; or about a
penny per cuft. That'd be about $2.50 for the typical 250 cuft welding cylinder...which the welding-gas place charges around
$30 bucks to fill.
I believe those little $15/12vdc tire-inflator compressors are totally oilless (teflon ring I think?), so with a little care, you
should be able to compress the O2 to around 100psi, into an empty 5-gal freon or propane tank for example. It'd probably be
prudent to flush either of those tanks with N2 first... :D
That'd give you a decent storage-volume; and a more convenient pressure for later use in experiments.
The biggest problem with air-cathodes is their fairly low current-density capability. However, a LOT of work has been done on
this issue over the years. If there's any interest, I'll post some info I have on that; but this may not be the right thread for it
anyway...??
In any case, with a cell that doesn't evolve hydrogen, physical design and construction constraints are much relaxed; making it
a lot easier to just use large-area electrodes to get around the low current-density limit.
fyi, I did a search for 'electrolysis', but did not find a thread specifically about producing oxygen. So, since it has already been
discussed in this one, I went ahead and posted here. But if there really isn't an oxygen-thread yet, perhaps it'd be worth
starting one?
edit: but in another search, just came across " Generating Oxygen Gas for the Production of Nitric Acid - Archive File"; which
seems like it's still an active thread; so maybe this belongs there.
Nitric-producer April 21st, 2007, 11:39 AM

All the reactor seals are done using Silicone sealant, I bought the all purpose stuff for sealing in kitchens. This includes all the
inlets/outlets of the reactor. Most seals used PTFE tape alongside the above.
The terracotta pots where dried in an oven before construction started, to remove any moisture. The dessicator dries the air
entering the reactor, which means water content is very low. After weeks of running the inside of the reactor showed no signs of
corrosion anywhere - apart from the aluminium electrodes - but I assume this is because of the high energy spark.
I used epoxy resin on the bubbler seals, it seemed to stay in hard lumps, but lost its adhesion to the surface. I then tried
silicone sealant, which dissolved even quicker. The current design use's nuts and PTFE tape, which so far has held up
completely, however was difficult to make.
However although it took a while to setup, this method actually works. If left on for a few days I could produce 1L of 50% acid,
and it feels good knowing you made it from air and electricity. The project is currently on hold, as I am attempting to design a
unit which produces anhydrous Nitric. :D
Alexires April 22nd, 2007, 02:42 AM

While looking for a source of NST in Aus and comparing microwave high voltages with them, I found this (http://
www.rtftechnologies.org/emtechnologies.htm). Rather interesting. I think I'd rather get a ignition coil from a car than buy a
NST.
This site (http://amasci.com/weird/microwave/voltage2.html) is interesting too
stupid939 April 22nd, 2007, 04:00 PM

OK, I finished making the setup similar to N-P's, and it is running right now. I took a lot of pictures, and I will upload them to
rapidshare or create a web page if someone would like them.
After I built it, I laid it out on the table, and I decided that it takes up way more space than it needs to. This is mainly due to
the rigid, braided PVC tubing that I bought, because it does not alloy me to push everything together. I also do not want to
stick the current set-up outside because I do not want it to get drenched and ruined in the rain (if I forget about it).
These reasons have all caused me to take on a similar project, but instead of spreading it out on a table, I will compact it into
a small, box-like setup. I will have a roof to protect it from the rain, and when I want nitric acid, I can just flip on, let it run for
a few days, and replace the jars.
One problem with my current setup is that the PVC reactor housing gets too hot after awhile, so I will switch to the terracotta
pots and see how that works. Another problem is with my bubblers. I am currently using brass tubing to extend down into the
water, and this may be a problem because it contains copper, zinc, and sometimes lead. These may lead to nitrates being
formed, so I will need to switch to pvc or aluminum.
stupid939 April 23rd, 2007, 05:42 PM

Ok, I let my reactor run for about 12 hours and today I tried to neutralize a little bit of it (it was acidic to litmus). I tried
barium carbonate and sodium bicarbonate, but the reaction was very slow, and I could only see a few CO2 bubbles.
I am remaking my reactor using all pvc and aluminum for the bubblers because the brass is not holding up too well, and I
thought about something. Since the reactor works so slowly, could it be that the NO2 is not making its way to the bubblers as
efficiently as it should? A quick check showed that at 21C, NO2 has a specific gravity of 1.58. I do not know if this would affect
the production that much, but would it help to move the "out" tube towards the bottom?
megalomania April 23rd, 2007, 07:23 PM

Moving the air inlet to the top and the the exit tube to the bottom might not be a bad idea.
UV radiation emanating from the electric spark will decompose some of the NOx gasses. Considering how large the container
is, and the likely flow rate of air from an aquarium pump, I would say the NOx gasses are exposed to UV for a significant
period of time, especially if they are dense and tend to mix downward. Reversing the flow of gas such that the air that is
exposed to the arc, and thus contains the NOx, is removed from exposure to UV light as rapidly as possibly should increase
yields.
The formed NOx gasses are also heated longer if they must pass up into the container and then into the tubing connecting
the bubblers. By forcing the gasses directly into the tubing and into the bubbler with the shortest delay you might avoid some
decomp.
Heat April 23rd, 2007, 07:40 PM

By the way, keep in mind that one way to increase yield is to use a DC arc under a magnetic field in order to spread the arc
into an oval shape. To do that, you would build a simple 4 diode rectifier, and connect it to the output of your NST (or whatever
you're using). And place two strong permanent magnets on both sides of the arc to create the magnetic field. This is what they
did in the industrial reactors.
Oh, and I remembered the biggest problem I had when I had my reactor going: People coming to my house and saying
"What is THAT?! What the hell are you doing?". Anybody else have this problem?
I can't just tell everybody that I'm making nitric acid, and no other explanation really works. I remember telling the stupid
ones that I'm doing an experiment, and they would shut up. The slightly smarter ones, I made up something about
generating NO2 gas for a study on air pollution.
Since I live in an apartment, I can't really hide it any more than putting it in a corner of my room. So any friends or family that
come to my house will see it.
EDIT: I don't think that moving the air inlet to the top would be a good idea. I don't imagine the flow from an aquarium to be
strong enough to overcome the hot air's tendency to stay at the top of the container. What I'd imagine happening would be
that you'd have an accumulation of NO2 gas at the top of your container, which would slowly creep downward until it reached
the exit tube at the bottom. So I think you would actually be exposing the gas to the UV light for much longer. Another
problem is that the top of the container would get VERY hot. I remember that my exit tube (at the top) was very good at
removing the hot air. If you put the exit tube at the top, the NO2-rich hot air would get sucked out of the container very
quickly.
Another problem with NO2 accumulating in the container is that NO2-rich air cannot sustain an arc as well as normal air. (So
the arc will go out.) Try it, set up a jacob's ladder under a jar. When the concentration of NO2 gets above a certain point, it will
stop working.
stupid939 April 23rd, 2007, 09:20 PM

OK, well I thought about both sides of this (hot NO2 rising vs. the density of the NO2) and I am not quite sure which one would
work the best.
I will use the setup that I am currently constructing and see how it works. It will have the desiccant chamber directly below the
reactor, and it will pump (slowly) the air directly up, through the arc, and into the tube leading to the bubblers. The reactor will
be constructed from two terracotta pots with holes on the top and bottom so that the air will make a path straight (hopefully)
through the chamber. I hope that I explained this well enough, and if need be, I will provide a crude diagram.
BTW Heat, that is an interesting idea to spread the arc out. I may try it, if time allows, and report my results.
megalomania April 24th, 2007, 01:04 AM

Nitric-producer, in the close-up picture of your spark gap are those square things ceramic standoffs, or what?
Darkover April 24th, 2007, 07:01 AM

Just fyi, while Heat is right. It's not nearly so easy as put some diodes together. Your gonna need to find 4 scrap microwaves
for there HV, 12kv+ diodes (or buy em, but I'm poor). Use corona dope or pot the diode bridge (again I'm poor, submerge
the bridge in mineral or motor oil) to keep the spark from jumping between diodes.

I don't really think 12 hours is enough time of operation. It took me 3 days of straight running to produce about 1L of 50%
acid. There are too many factors which cause the NO2 to "disappear". Until we work out the most efficient way of doing this, Im
afraid your just going to have to leave it running a little longer :( .
Mega: After many failed attempts of producing a reliable spark, I made these "ceramic standoffs" ( as you refered to them). I
had such a high voltage that occasionally the spark would jump onto the outside of the pot, and sometimes to ground (very
scary). They are simply white plastic nuts. I made them from a chunk of heavy duty plastic and tapped them - so the
electrodes would screw through! They turned out to be very good at holding a seal as well as being insulators.

I am aware that running the reactor for 12 hours is not enough time to produce a very large amount of acid. I have to run it
on and off because I do not want to leave it running while I am at work. Just in case something goes wrong, like tubing
becoming corroded and slipping off, leaving the house to be filled with NO2 and NO. I also do not want to put it outside
because it may get rained on.
I will have it run continuously when I finish my new setup, because it will be contained in its own little wooden house (it will
even have a roof). I am working on the CAD drawings right now to get the layout how I want it, but it will come together soon.
The reactor is almost complete, it is mounted on the desiccator, and the bubblers are done. While I am working on my project,
you can see what kind of progress I am making. Some of the pictures have bad shadows because the lighting where I am
constructing it sucks.
Current Setup 1 (http://www.free4up.com/ShowImage.aspx?fn=120027009164225.jpg)

New Assembly (http://www.free4up.com/ShowImage.aspx?fn=136206090231249.jpg) - This is basically my new setup. The NST

and pump are not in there because they are being used.
Bubbler Pieces (http://www.free4up.com/ShowImage.aspx?fn=195155078066252.jpg) - This is what my bubbler is composed

of. PVC and aluminum are the only materials that nitric acid will touch, with the exception of the teflon tape that seals the lid
to the jar. The aluminum tube is pressed in on an arbor press, and is air tight.
Bubblers Assembled (http://www.free4up.com/ShowImage.aspx?fn=224148195128188.jpg) - Here are the assembled

bubblers. After I glued them with the PVC cement (PVC resin dissolved in Acetone/MEK), I epoxied them for strength.
Desiccator and Reactor (http://www.free4up.com/ShowImage.aspx?fn=092085189248227.jpg) - As you can see, the desiccator

bottle screws off for replacement, and there is a hole directly under the spark gap. The gap is not evenly spaced in the picture
because one bolt it adjustable for the size of the spark gap.
Spark Gap (http://www.free4up.com/ShowImage.aspx?fn=079003151178071.jpg) - A close-up picture of the spark gap and

the hole leading in from the desiccator.
The only thing that I am worried about is that the nitric acid may eventually attack the PVC resin (the cement) and then the
epoxy. I may also end up putting in a acrylic window so that I can see into the reactor. It will make it a lot easier to adjust the
gap.
BTW, On my reactor, I have noticed that the PVC near the top of the chamber has reddened and this tells me that the NO2 is,
in fact, collecting at the top. There is also some slight leakage at the adjustable bolts, but that is nothing that a wrap with
teflon tape wouldn't fix.
What do you all think?
Alexires April 25th, 2007, 07:13 AM

Not a bad set up Stupid939. Might I make a few suggestions? (I'm going to anyway)
In both setups, your reaction chamber is WAY too big. Think about how much NO2 can be contained in there compared to a
chamber just big enough for the reaction. Looks like (just guessing) that your spark gap is about 10mm. Why not have that in
a 15-20mm ceramic/plastic/whatever chamber instead of a pot. That way less exposure to UV light.
If you can't do that, consider getting a piece of stainless steel plate (only needs to be thin), drilling a few holes in it (just
enough for the air to get through) and putting it over the top of the spark. Make sure it is insulated, and that is another way
of preventing UV decomposition (not as good as the original).
Hot air rises and all that jazz. If you really wanted meaningful data to try and work out the spec. density of NO2 in the
chamber, measure the temperature.
Let the fucker run for a few hours with the hoses and air pump/filters/blah connected and again for a few hours but with the
reaction vessel fairly sealed (don't seal it tight otherwise you will have a problem with pressure build up). The temperature in
the vessel with the pump attached is what I would call the "real" value and probably what the average specific density/
temperature of the NO2 would be, but also take into consideration the temperature in the reaction vessel without air running
through it. This will tell you what you might expect in "hot spots" or peak temperature.
I'm expecting the NO2 to rise out of the chamber, so you might as well have the air intake near the bottom and the vent at
the top.
If you wanted to be really tricky, you could then pass the NO2 fumes from the reactor through a "condenser" set up. Maybe a
PVC tube coiled in water with a few "baffels" in it to mix up the air as it goes through.
After this, you could pump the air into a cooled "settling chamber" where the (hopefully) cool NO2 fumes would sink to the
bottom of the chamber. These are then passed through the water setup.
Remember, spheres (bubbles) have a shit Surface to Volume ratio. Either find a way to make smaller bubbles, or strech them
out (another plate in the water to flatten the bubbles). Here are a few ideas for that.
When the bubbles are being pumped into the water chamber, have the chamer mostly full with a mechanical stirrer in there.
Magnetic would be SO much easier for this.
As the bubbles come into the chamber, they are caught in the rotating water (thus breaking them up a little). On the
outermost part of the water chamber, have a kind of mesh maybe, or a sheet of metal (verticle) with a few holes drilled in it.
This will help to a) flatten the bubbles (increasing surface area to volume ratio) as well as b) break them up as they go
through the holes. Just before the bubbles leave the first water chamber, have another sheet of metal (on the horizontal
plane this time) with some holes drilled in it. Again the bubbles need to flatten out and increase the surface area.
Instead of this (if you're cheap, like me) you could fill the bottom of the water chamber with ceramic chips/glass chips/
something non-reactive. Pump air into the bottom of that and as it rises, it will be mixed fairly well with the water and divided
into smaller bubbles. You might have some trouble with all the water in between the chips have a higher HNO3 concentration
than those outside the chips, but I doubt this will be an issue, or just fill the whole container with chips.

Just what I expected to happen, did. While I was at work, I think my dog pulled on the tube leading out the door, and pulled
the whole setup over. Both of the bubblers fell off of the table, and one tipped on its side. Luckily, everything is sealed, and it
only pumped about 750ml of my ~2L out of the first bubbler. Everything is fine, and this just gives me one more reason to
construct my outside reactor.
Alexires, you have some good ideas. I will design a reaction chamber in CAD, and I will post a few JPGs for everyone to look
at. I will most likely construct it in the same manner, but I will use 3/4" or 1" PVC tube with at least one acrylic window. The
nice thing about the reactor is that you can epoxy as many things as you want, and it is not affected by the NO2. I also
considered plastic welding, but I figured that I may be able to do it with a modified soldering iron that blows hot air. Below is a
link to a kit.
Plastic Welding Kit (http://www.malcom.com/products/pwk.php)
I could also make my own reactor out of anchoring cement, and it would be similar to the terracotta pots. This may or may not
work, because I have not exposed the cement to nitric acid or NO2 (it seems to be fairly inert though).
If I use PVC, the only problem that I can see is that it may get to close to the arc, and possibly melt. I noticed that in my
current reactor, the PVC softened up where the bolts touched it, yet the epoxy was fine. I will work on it and report back with
updates.
I may also build an aluminum plate screen above the arc to prevent UV exposure. This would be fairly easy to incorporate into
my smaller design, and it should take some of the heat off of the tube leading to the bubblers.
I have a hot plate/magnetic stirrer that would be perfect for the bubblers. The heating element went bad, and I can't find a
close enough match for it, so I can't use it much for syntheses. I have some teflon stirring bars that would also be suitable,
and I do not use them very often. I may just incorporate this into my new "house" design as an optional luxury.

OK, I have been working on drawing my setup in Inventor for the last few days, and it is looking pretty good. Inventor does
not have a good capturing program built in, so all of these are edited screenshots. Here they are:
Assembly - Isometric View (http://www.free4up.com/ShowImage.aspx?fn=201100168238038.bmp)
Another Full Isometric View (http://www.free4up.com/ShowImage.aspx?fn=229104049020143.bmp)
Assembly - Front View (http://www.free4up.com/ShowImage.aspx?fn=138177007217229.bmp)
Reactor and Desiccator (http://www.free4up.com/ShowImage.aspx?fn=110022178052092.bmp) (the desiccator is the bottle

below the reactor chamber)
Reactor Cutout View (http://www.free4up.com/ShowImage.aspx?fn=015255082116249.bmp) (notice the aluminum screen to

cut down on UV exposure)
Bubbler (http://www.free4up.com/ShowImage.aspx?fn=234013208135122.bmp) (The only thing nitric acid will touch will be
PVC, aluminum, and glass)
I couldn't really draw the tubes, but I'm sure that you can understand how it works. The black thing in back on the bottom
shelf is the NST, and the black thing in front is the pump. And above that, I even drew in the magnetic stirrer. I have
everything built except the wood pieces, but that would not take long.
I would enclose all of this, and change the roof so that water would flow off of it, but this is the basic idea.
Suggestions?
Alexires April 29th, 2007, 08:58 AM

Stupid939 - Excellent work. I especially like your representation of the small grate/grill in the upper part of the reactor. Exactly
what I imagined it to be. Maybe you could have a 90* piece on the PVC just before the grill there. Light travels in straight
lines(ish), so any that does get through hopefully get stopped there.
The next step is to build it and see how it goes with temperature dissipation. You might want to think about having a kind of
cooler/condenser set up running thorugh it just after the reaction chamber, otherwise you might have a problem with your
water boiling in your collecter vessels.
Also, while in a pet shop the other day getting my water pump and air pump for this project, I espied one of those stone
bubblers they have in aquariums. If it is resistant to acid/acid proof, it would be perfect to increase the surface area/volume
ratio of our collection vessel.
If I remember correctly, gas solubility is the opposite of solid solubility. Eg. The lower the temperature of the liquid, the more
gas you can get to dissolve in it. Henry's Law I believe. Hence, the colder we can get the water, the more NO2 we'll get
dissolved in it.
Cooling will definately need to be a part of this experiment.
Looking at your design stupid, perhaps the reactor outlet can lead directly into a freezer where the tube circles a few time
through acetone in there. Perhaps have a junction point that is metal to improve dissipation of heat and have the collection
vessels in there as well. The only problem you might have with that is that the water in the vessels freeze, but if the air
coming through was above 0*C (which I'm sure it will be) it probably wouldn't be a problem.
I expect that with everything stated above, you probably can make this for about $200-$300 (if you use an ignition coil
instead of an NST).
You can get ignition coils cheap on ebay and find various plans to make a spark gap with them on the net. If someone with
electrical know-how (I'm hopeless) could PM me in regards to making an ignition coil work for a spark gap, that would be
great.
jpsmith123 April 30th, 2007, 11:13 PM

I came across the following reference that makes me think it's possible, but I have no idea of the efficiency/practicality of the
process. Maybe somebody can get the paper?
Nitric Oxide Formation by Ultrasound in Aqueous Solutions

Misik, Vladimir; Riesz, Peter
Radiation Biology Branch, National Cancer Institute, Bethesda, MD,
J. Phys. Chem. (1996), 100(45), 17986-17994
stupid939 May 2nd, 2007, 05:48 PM

I have been busy for the last few days, but I have some bad news about my latest design.
When I finished building it a few days ago, I put it together and let it run for about 20 minutes. I noticed that the bubblers
were filling up with what looked like water vapor, but I could smell burnt PVC. If you looked closely at the exhaust, you could
even see little puffs of smoke come out of it. Damn...
I guess that I will either make a similar chamber out of aluminum, or I will use a large reactor with a better design to cut down
on NO2 breakdown. I may try the flowerpot reactor, because I know that it will work, but this really disappoints me. I based
this design off of suggestions made by Alexires, so do you have any suggestions other than a cooling system. I don't think
that the bolts and the chamber could be cooled fast enough to keep the PVC from burning.
Darkover May 2nd, 2007, 06:30 PM

I've both magnetically ballasted a pair of MOT's and used an ignition coil. Believe me you don't want to use either. One very
simple reason in both cases extensive wiring is needed and were talking voltages and currents way beyond what is needed to
kill you with a single jolt. Anything much past 20kv will instantly paralyze you btw, meaning your ignition coil looks very cool
but wired the wrong way or with the wrong parts and it is very lethal. A neon sign transformer is designed to produce the
voltages needed at the required amperages and do so forever without overheating or shorting out. Ignition coil driver circuits
need (usually) 12 to 30 volts DC at a few amps, so in addition to the crazy ball of wires and parts thats hanging off the side
of the coil you need a transformer and rectifier sitting beside them. A neon sign transformer can be had used from a lighting
place in any major city for peanuts. By the time youre done scrounging for parts and soldering everything together both of the
alternative power supplies (if they havent killed you) will cost more than the used NST.
Nitric-producer May 2nd, 2007, 07:20 PM

I am in the process of building a high voltage power supply using an ignition coil, just for fun :D .
Darkover: I can understand where you are coming from, but at the end of the day high voltage experimentation is always
going to be dangerous. If you give it the correct respect it can be safe. It took me ages to track down my NST, mainly because
everyone wanted it for experimenting! The parts to build my ignition coil, where bought for about $40. And I plan on enclosing
it in a case with proper cooling. If you can get an NST easily, then I do however recommend it!
I will post back my results on using this power supply in the Nitric reactor.
Darkover May 3rd, 2007, 02:39 AM

I take some of that back, I went to the usual watering hole for a NST and the prices have spiked, I picked up another 15kvolt
nst but this one for 100 bucks. Still a good deal refirb in new condition, but not the 15 dollars I paid for his same era Allanson
12kvolt brother 2 weeks ago.
If youre going for budget high volt power supply, use a TV fly back or an ignition coil. Stay away from a MOT controlling the
raw current these will draw is difficult and dangerous for those who don't know how.
Alexires May 3rd, 2007, 06:18 AM

Urgh. Sorry about that stupid, I was worried about something like that happening in regards to the PVC.
Is it burning where the bolts come through (contact), or is it burning worst near the spark all the way around and tapering off
(radiation)?
Either way, you will either need to increase chamber size or use something that can take higher temperatures (like Al). An
enlarged reactor will lead to decomp of NO2, so probably end up going aluminium, huh?
Again, sorry stupid. I haven't built one of these. I'm working on it, but I need to pick up a transformer to attach to my ignition
coil. I am just expanding on your original set up. This is just an exercise in logic at the moment for me, until I get all the
parts to start work.
I suppose the reason that we aren't using aluminium orignally is because of fear of hot nitric eating it away. Either try it with
just Al, or you could actually heat the air coming in or Aluminium up. This way, even if there is moisture in the chamber, it
won't matter as it won't condense on the sides.
If you are willing to give it a go, that would be great. Otherwise, you can wait for me to buy all the shit I need (probably a few
weeks) and I'll do it.
Any other problems besides that?
PS. If you find that you still need PVC, you might be able to replace just the small holes where the bolts come through.
Instead of just screwing them through the PVC, perhaps use something temperature resistant that is also a good insulator to
screw the bolts into, and then this is screwed into the PVC.
This will only work if the burning is from contact though.....
plutobound May 3rd, 2007, 11:46 AM

Maybe somebody can get the paper?
Nitric Oxide Formation by Ultrasound in Aqueous Solutions

Misik, Vladimir; Riesz, Peter
Radiation Biology Branch, National Cancer Institute, Bethesda, MD,
J. Phys. Chem. (1996), 100(45), 17986-17994
I downloaded a .pdf copy of it. I'll post it on rapidshare this evening.
stupid939 May 3rd, 2007, 08:22 PM

OK Alexires, I dissected the chamber and the burning was where the bolts contacted the PVC. There was also some burnt PVC
above the holes, and because I only ran the reactor for about 20 minutes, I think that the chamber needs to be replaced
anyways. I will try to make the reactor out of aluminum, and I think that it will turn out fairly well, especially because I can
braze aluminum now (see my post in this thread (http://www.roguesci.org/theforum/showthread.php?t=4531&page=2)).
I would like to follow up on this project to be able to make nitric acid very cheaply, and also to contribute something more to
this forum. I will follow a similar design using mainly aluminum, and I think that my dessicator should not leave any water
vapor in the reactor, and like my first reactor, the chamber should be fine.
Nitric-producer May 4th, 2007, 06:11 AM

I apologise if this is a dumb question. However when reading up on simple transformers, it occured to me why not make our
own step up transformers? Can anyone explain to me why you cannnot just build a simple step up transformer - and use it for
high voltage experimentation? Sorry my knowledge on electronics is limited.
Alexires May 4th, 2007, 08:38 AM

Nitric-producer - I think you just stumbled upon why some of us buy it instead of making it - because we don't know how to
make it.
Personally, I don't know a resistor from a brick. Certainly, if you had the knowledge of how to build it, you might as well do it
(probably heaps cheaper), but for those of us that don't know and don't have the inclination to learn at the moment, best to
buy the cheap parts. An ignition coil for $30, a variable step down transformer for the same and you are set....
Stupid939 - Again I apologize, I should have expected that to happen. You might have turned it of at the right time, any
more and there might have been a case of PVC fire :eek: .
All the advice I can think of now is that it might be possible that whatever you use to weld the Al might not be resistant to
NO2. Only really one way to find out. If it isn't resistant, you might get away with coating it with a 24hour 2-part epoxy (if it
doesn't get too hot).
Also, your Al should hold up to NO2 if the air is dry. If you have something lying around that you can make cold (constantly),
try putting that before the desiccator. The H2O in the air should condense on that and reduce the work the desiccator has to
do.
Other than that, good luck and I look forward to hearing of your success.
Darkover May 4th, 2007, 08:22 PM

I've wrapped my own transformers. Couple reasons why buying is easier than making, imagine wrapping a wire the thickness
of 10 human hairs around a metal core 10,000 times. Transformers like the type used in car audio to output power to cold
cathode and electroluminescent wire have secondary wires the thickness of a human hair imagine breaking a wire on turn
number 9,543 and having to start over.
The transformers Ive done were all toroidal, that is, donut shaped. With a power supply like an NST the voltages require that
the finished transformer be potted (submerged in a material of extremely high dielectric strength, under vacuum yet)
otherwise the transformer may just arc within its own wires rather than where its supposed to go. It comes down to price, even
at 100 dollars with the ability and experience to wrap my own NST the great lengths which a transformer like that needs buying
it is cheaper.
For the curious a transformer is simply many wraps of one wire (the primary) and many more (step up), or many less (step
down) of the secondary. Only ac voltage may be used in a transformer as its the (very simplified) push pull effect of ac
voltage that magnetizes the core and makes the transformer work. Transformers with many more wires than the simple 4
have whats called center taps, that is a wire is connected to say halfway along the secondary giving you half the voltage
output of the secondary if needed. Computer power supplies and audio equipment do this very often. It allows a single 110v
input to provide power at several voltages and amperages. NST do this on the secondary to limit the potential with respect to
ground. Look on the side of your NST you should see a screw with no visible purpose just screwed into the side of the asphalt.
Confused yet ?
plutobound May 5th, 2007, 01:04 AM

I downloaded a .pdf copy of it. I'll post it on rapidshare this evening.
Sorry I'm a day late. Minor emergency. Here is the link to the article from the Journal of physical Chemistry:
http://rapidshare.com/files/29552933/jp961522x.pdf.html
Heat May 7th, 2007, 08:22 AM

Like I said, the heat from the arc is a real problem! You have to realize that we're talking about 3000 degrees Celsius. You
can't just glue your electrodes to a plastic container.
What I did was suspend my electrodes in the air using copper wires. 15cm or so of wire is enough. I also wrapped copper wire
around my electrodes to act as heat sinks and help cool them down.
I can't stress this enough: The arc is *very* hot; comparable to a small blowtorch. My container was about 30cm tall, and still
the plastic and glue at the top couldn't take the heat. So I don't recommend a small container at all!
If you're worried about UV light destroying the NO2, you can try to put a few sheets of aluminum around and above the arc to
block the light. Just don't get too close, since the arc will burn through aluminum. In the end, losing a little NO2 due to UV
light is much better than losing your reactor due to heat.
By the way, I strongly advise against leaving your electrodes sticking out with no insulation.
tareg_3d May 11th, 2007, 09:36 AM

in this project Birkeland-Eyde reactor i need some explantion ,about the plasma arc .we know we have in the air netrogin andd
oxygen and hydrogen .this acr it is inif to contact hydrogen with oxygen and i it can be do ,this water effect to electolet

I just have a bit of pedantic foolishness I would like to get off my chest regarding the Birkeland-Eyde reactor. This is NOT the
proper name to describe this particular method of generating nitrogen or nitric acid. In doing my formal writeup of this
procedure I have acquired just about every book that has anything to do with nitric acid manufacture, including a rather
complete history of the process.
More properly this should be called a Cavendish sparking apparatus, or a Cavendish reactor. Lord Cavendish was the first to
pass electric sparks through air to produce nitrogen dioxide and nitric acid from 1781-1784. He developed the sparking
apparatus, which is identical to the process we are using here.
The first nitric acid manufacturing process to take advantage of Cavendishs experiments was an English patent in 1859 by
one Madame Lefebre. Although this patent included specifications for a large scale manufacturing operation, electrical power
generation was still too much in its infancy.
The first actual manufacturing process of nitric acid by the electric arc was the Atmospheric Products Company, in Jersey City,
NY, run by Bradley and Lovejoy in 1902.
It was not until 1903 that Birkland and Eyde first began to develop their process, construction of the actual plant was a few
years later, and it was quickly superseded by other electric arc operations. Every electric arc method was eventually doomed by
the Haber process.
There you have a brief history of the production of nitric acid by electric arc, with the Cavendish reaction/method/reactor.
Now then, tareg, just rephrase your question in English and we may be able to help
nbk2000 May 12th, 2007, 01:43 AM

Looks like a machine translation to me. IP resolves to Germany, as I've been inviting people from a german forum here.

Mega and NBK, I think that he is concerned as to whether H2O produced in the reaction (from atmospheric hydrogen and
oxygen) would has some effect on the electronics? Perhaps the spark gap itself?
Tareg_3d - The amount of hydrogen in the air is 0.00005% as compared to nitrogen's 78% and oxygen's 21%. The amount of
water produced as an unwanted byproduct would be so small and insignificant that it would have no effect on the outcome.
The spark gap would be so hot that water wouldn't precipitate on it, and other than that, your reaction should be sealed so
that air pressure (used to push the NO2 gas through the water) wouldn't be lost. Anything condensing in the reactor during
initial operation would evaporate as the temperature rose.
Fear not the horrors of Dihydrogen monoxide...

Actually, with the presence of water vapor in the air due to the days humidity, and the long term use of this device pushing a
rather large volume of air through it, there is the distinct possibility of nitric acid attacking metallic components.
This is why placing a desiccant bottle inline with the air flow, before entering the spark, can in all practicality eliminate this
problem. As you may observe in the pictures stupid939 provided in post 123 ( http://roguesci.org/theforum/showpost.php?
p=90105&postcount=123 ) he uses a mason jar. I myself use a large 3-quart pickle jar filled with calcium chloride with a length
of glass tubing glued into the lid for the inlet, and a short bit of plastic hose barb glued in for the outlet.
Alexires May 12th, 2007, 08:35 PM

Megalomania, I made my post with stupid939's setup in mind, sorry if that was unclear.
Just curious, how often would your CaCl2 need to be changed (on average)?
stupid939 May 12th, 2007, 09:47 PM

Sorry that I haven't posted my progress in awhile, but I had a little setback. Too much rain and no sump-pump caused my
basement to flood. This included my shop and downstairs area, so it is a little hard to work until everything finds its rightful
place again (it was in need of a cleaning anyways).
Just before the disaster, I finished most of my reactor made of mainly aluminum. I used homemade threaded teflon bushings
to support the bolts. When I took temperature readings on my big reactor, I got a maximum of 180C. Teflon has a melting
point of 342C, so I should be fine (side note - the is made by: alt + 0176). It looks pretty nice (except the fact that it is
covered in epoxy), and I just need to finish up the inlet and outlet tubes. I will still put in a screen to cut down on UV
breakdown, but I think that I will also put a bend in my tubing going out. I will attach pictures if anyone would like.

Hit me with your pictures stupid939, I'm always eager.
Hopefully the teflon holds up. Spark gaps can get pretty hot....
stupid939 May 16th, 2007, 12:40 AM

OK, I finally overcame my laziness and depression of my shop getting flooded and I took pictures of my new reactor. All of the
joints are covered in epoxy because the Aluma-Weld stuff that I used left a few small leaks. There were also some leaks
where the "bushings" slid into the aluminum tubing.
Top View (http://www.free4up.com/ShowImage.aspx?fn=095163160113158.jpg)
Isometric View (http://www.free4up.com/ShowImage.aspx?fn=078156014128150.jpg)
Side View (http://www.free4up.com/ShowImage.aspx?fn=115051205018164.jpg)
Another Top View (http://www.free4up.com/ShowImage.aspx?fn=157049201243134.jpg) - Notice the homemade PTFE

"bushings/nuts"
Now I just have to make and fix a top and bottom to the body and it should be ready to use. OK, now it is suggestion time. I
was thinking of a taller tube for the reactor body, and I want to use something else for the bushings, but it cant be conductive.

Thanks for the pictures stupid. Looks like you go a little excited with the holes in the aluminium *grin*.
Next time you take a picture, would you be able to put a ruler next to it so we have an idea as to how big it is?
Looks quite exciting. That chamber is going to get hot, thinkest me. I think you might have some problem with the PTFE
decomposing...
*sigh* What a pain in the arse. Perhaps we might need to change our approach in regards to the placement of the sparkgap.
Instead of running it through the outside of the chamber, perhaps we need to have the leads running on the inside of the
chamber but insulated?
What do you think stupid? Give it a test run and watch out for the flourine....:eek:
nepsco1 May 16th, 2007, 10:55 AM
I have not been on in a while so I apologize for chiming in at this late date. I have some anecdotal information that may be
helpful. I ran a DC Plasma Arc facility for several years with a Plasma Energy Corp. plasma torch operating at ~300kW, 400A,
and a sinusoidal fluctuation of voltage from about 580 to 700 VDC. If we ran air as the plasma medium we created in excess
of 100,000ppm of NOx in the reactor exit gas. (That was the limit of the analyzer, by a crude dilution I believe that the actual
concentration was about 130,000ppm.) We scrubbed the gas with NaOH and water and created a solution containing high
concentrations of both nitrite and nitrate.
Thus, the acids created on water contact were both nitrous and nitric. As I remember the break down in the reactor exit gas
was ~60/40 NO to NO2.
The reactor was refractory lined and operated at ~1,200C.
This all could be mocked up using a welding shop plasma cutter and a small reactor lined with a cheap castable refractory with
an insulating board layer between the refractory and the steel shell. If the plasma cutter is available, then the rector materials
shouldn't cost more than $100 and could be a lot less.
I don't know if this is helpful, but I thought some of you may find it interesting.
nightandday May 16th, 2007, 03:09 PM

@stupid939
For sealing the electrode feedthrough, you can use gypsum. After solidification, drive out free water by heating to ~200 C for
1 hour. When dry, gypsum is a good insulator and is heat resistant up to 800 C.

Hey, stupid939, don't they sell T or cross fittings where you come from? Wouldn't using one of those make life simpler and
less epoxyified?
atlas#11 May 17th, 2007, 12:05 AM

Microwave ovens all have a nice powerful ~2Kv transformer in them. The voltage isn't high enough to jump a great distance,
but if your pumping air through it you should be able to rig something up.
I've had plans to do something like this for a long time, but never put any effort into it, I just cracked open my fourth oven
this morning so I may give it a go. I've got plenty of transformers laying around from my Tesla coil experiments. If your
looking to turn an ignition coil into a source you may want to learn how to make driver circuits for solid state Tesla coils,
roughly the same thing.
Microwave transformers will draw a lot of juice and should be quite efficient at turning nitrogen and oxygen to nox, You'd
probably have to pump quite a bit of air through it to keep it cool. I'm thinking I'll just go over to the art center and grab a big
block of pottery clay to make the reactor and use some tungsten welding electrodes for the anode/cathode. Could make a
nice weekend project.
stupid939 May 18th, 2007, 02:00 AM

Mega - I am not sure where you can buy aluminum T or cross fittings. Copper may be usable, but I am not sure how it will
react with NOx.
We do need to come up with a new design that will cut down on heat, UV exposure, and ease of construction. I may try the
reactor that I just built, but it may take awhile because I still do not have much of a shop to work with (since the flood). An
alternative that I mentioned earlier would be to construct it from a cement/ceramic material. Plaster of paris or Anchoring
cement would be easy to cast with threading/electrodes incorporated into it.

I was going to wait until I actually get the thing build, but I have a few tools for the project on backorder for a few weeks, so...
My design for the reactor will use fluorescent light bulb tubes. These bulbs are cheap, plentiful, and seemingly easy to work
with. They are made of Pyrex glass, which enables them to withstand high temperatures, and being glass, are inert to
chemicals and non-conductive.
The thinness of the glass should make them easier to handle, but mine is giving me trouble. I have all the parts I need, I
just need to cut the glass to shape. Bottle cutters are expensive it seems, glass cutters do not work well on curved surfaces,
wrapping the glass in string and setting it on fire does not give a very straight cut all the time... I spent a lot of time looking
into DIY glass cutting over the last couple of weeks, there are many techniques, but I am going with the tried and true
favorite, a diamond cutting tool.
Seeing as how I am cheap, or rather I want to stretch my limited funds, I ordered a kit containing a variety of diamond coated
cutoff wheels and grinding tools for working with glass. The Dremel is my friend, yours too, but the cost of one bit at the big
orange hardware store was only slightly less than a whole kit with several pieces. I just have to be willing to set aside instant
gratification (I got the cheapest shipping, and I think it must be coming direct from Hong Kong).
Anyway, let me tell you my vision. The main reactor consists of a glass tube. The ends are capped with clay that is cut and
molded to perfectly fit the ends of the tube. The clay is low temperature firing stuff that can cooked solid in the oven. I will
mortar the clay ends on to the glass. By pressing the glass tube into a thick plug of clay I can create a good seal even before
applying adhesive. The clay also allows me to mold a threaded nut and a hose barb into the material before firing. I found
about 10 pounds of this clay while cleaning out something in the garage. How serendipitous.
I will fit two lengths of a threaded rod through the center nuts in the clay caps. These will help make the spark adjustable by
moving the rods closer together or farther away as necessary. One of the threaded rods, the one opposite the inlet of air, will
have a pair of nuts and a large washer attached to it. This metal shield fits inside the glass tube, but still allows the reacted air
to flow around it at the edges. This is a UV shield that will block the light after the reaction is complete. This means I don't
have to have some permanent screen fixed inside anywhere, it fits quite nicely within the tube.
The tube itself is placed inside a cheap semi-disposable plastic container. I cut round holes into the rectangular container so
the tube just fits into them. The container is filled with cold water, and depending on how hot this water gets, I may hook my
garden-hose-to-tubing-barb adapter, along with a pair of hose barbs for the container, to circulate a constant flow of cold
water. The electrical contacts and air inlet/outlet never contact the water, the tube is submersed at all times, and I can still see
inside the reactor and gauge the progress of the spark.
I hope I thought of everything... Go ahead, start your criticisms of my using a light bulb. And, yes, I did clean off the white
stuff on the inside.
Alexires May 18th, 2007, 09:15 PM

Mega, If I may?
As I understand it, you have two nuts embedded in the clay which you will screw the threaded rods into. The will be both
slightly off the vertical axis, allowing you to screw them in and out to adjust the spark gap. The large washer will be attached to
the one afar from the air input and this washer will sit above the spark gap on the end of one thread (obviously threaded a
few extra cm above the other rod to allow for this).
How were you planning to submerge it all in water? Were you going to just cover the clay end cap and all associate
attachments with the epoxy god?
How are you going to pass the NOx fumes from the end of the pipe into your mother liqueur?
stupid939 May 19th, 2007, 02:23 AM

I think that Mega was going to have the glass tube going through his water container, and have extra tube stick out of the
container. The clay and electrode ends will then be out in the open so that he can adjust them. Here are a few sketches that I
made (this is how I interpreted what Mega said).
Iso View (http://www.free4up.com/ShowImage.aspx?fn=026139010114212.bmp)
Front View (http://www.free4up.com/ShowImage.aspx?fn=005132087181202.bmp)
The large block is water, the tube going through it glass, etc. I think this would keep everything cool and it is a good idea. It is
also cheap, but the only down side is that it requires a cooling system. How close to finishing are you Mega?
in_flames May 20th, 2007, 01:41 AM

Mega, assuming stupid's digram of your reactor was correct I have a few suggestions to make.
My first idea would be to cut the flourescent tube (if possible) into shorter lengths. I do not see any point of having a gigantic
tube where the reaction is only taking place in a few cm. With that you could possibly even go without the washer as the clay
cap is close to the arc blocking UV.
My second suggestion would be to make multiple of those small reactors placing them in parallel with eachother (assubing
your power supply will allow for this). Thanks to your simple and small design I would say it is highly possible to integrate
many reactor units into the one cooling tank.
My final suggestion would be to change the cooling tank to a flowing water system attached to a radiator and also cooling on
the outlet pipe. Needing an extra pump would be an issue here but if its not too expensive I think it would enable the system
to run much cooler encouraging NO2 formation.
Overall I think it is a good idea and if it works well I will be constructing something very similar.

While I could not view stupid939's pictures, I think you guys have the gist of what I wanted to do. I cut a hole in the side of a
plastic container, seal in the tube so that the ends stick out at either end, and I can manipulate the threaded rods to adjust
the spark gap because it is not in any water.
Using multiple sparking tubes might be a good idea, especially if one wanted a higher production environment. I guess one of
those very long but skinny plastic troughs you use when wallpapering would come in handy for that (these things allow a roll of
wallpaper to be submerged in water, about 3 feet long, 6 inches wide, 6 inches deep, and dirt cheap). A parallel configuration
would have the same voltage from your power source, of which a high voltage is needed to produce a spark, so only the
current would divide with the addition of each apparatus. I don't know how a reduced current would affect the system, could be
good for a few, bad for a lot. Anyone with electrical knowhow care to fill me in on that one?
There is no reason to have a long fluorescent tube, it only needs to be long enough to contain the spark. I wanted a longer
tube to keep some of the heat away from the end plugs and the epoxied fittings therein. A longer tube should also facilitate
better cooling of the inside air. I never really planned on building a million of these, so I have enough glass to last a while
even using a long one.
The washer in the tube is entirely an optional feature. The total cost of the washer and the two nuts that hold it in place was 17
cents, so I was willing to splurge. This is a minor feature that may have only a marginal impact on yield, but for 17 cents there
is nothing to lose by adding it. UV light does have some measurable impact on the decomposition of NO2 molecules, but it
can also promote the oxidation of NO.
I won't speculate on a flowing water system until I see how hot mine actually runs. It will be simple enough to add if need be.
stupid939 May 27th, 2007, 03:01 AM

I re-uploaded the files to a reliable site (imageshack). Sorry about that.
Iso View (http://img412.imageshack.us/img412/1908/iso1mn8.png)

Side View (http://img155.imageshack.us/img155/6879/frontmc3.png)
From what you further described, I feel that I accurately drew what you are building. I would agree with keeping the tube longer
because of heat dissipation. I would also try to keep the diameter of the threaded rod as small as it can be while still being
able to support itself and possibly a nut/washer assembly. I would think that this would keep the assembly as cool as
possible. This assembly could also be built vertically to allow for small diameter rods.
Also, remember to seal the threaded rod with teflon tape. When I didn't, I could notice trace amounts of NO2 reacting with my
epoxy.
I have not been able to work on this project lately because I have had to move everything around because of the flood. Now
that everything is finding it's place, I will be working on and testing some designs. As usual, I will take pictures and share my
experiences with all of you.
Bodypain August 13th, 2007, 07:43 AM

Few years a go i use Rumkorf coil, but there was only o3 not no2, there is another way like in circural welding use two graphite
electrods, in this way dont need coil.

This discussion has grown greatly. My congratulations to those who are experimenting with the small scale production of a very
useful material.
Much research has been done, particularly in Russia, on such small scale nitraters and the results are very encouraging. What
you are seeking is definitely within your reach.
It is possible to obtain very high voltages with ordinary transformers. The key is to energize them with "non-sinusoidal" input
pulses. This is how automotive ignition systems work and the voltage multiplication in an ignition coil so driven is many times
the "turns ratio" increase that would be accomplished with a sinusoidal input - such as from the home power mains.
Due to the heat problems many of you have verified, and the need for keeping the reaction products sufficiently cool so as not
to waste energy, pulsed high energy arcs are much more efficient. The continuous, low energy arc produced by the Neon Sign
Transformer, while impressive in appearance, is very inefficient for the purposes you desire.
The high voltage output of whatever transformer system you use is best rectified with a high voltage diode string and applied
to a high voltage capacitor to store enough energy to drive an intense high energy arc in very brief pulsations.
The diodes themselves need not carry a large amount of current as they will not be in the capacitor discharge path which
sustains the arc briefly when the voltage has built up sufficiently.
The high voltage capacitors can easily by constructed and only about 40 Picofarads is sufficient at a voltage rating of about 50
Kilovolts.
An ignition coil system driven at several Kilohertz would be capable of producing high energy discharges at a rate of about two
to three hundred per second.
The heat generated would be quickly dissipated in the normal air flow and the efficency of the process will be enhanced.
There is a trade-off however. The high energy discharges are noisy and may be an irritant for some. But, it is possible to
design the system such that the noise is sufficiently attenuated, or muffled, so as not to be a great source of distraction.
May I encourage you to keep up the efforts?
In time you will find the secrets to good success.

In the above description I inadvertantly said two to three hundred discharges per second, when it should be per minute.
Two to three hundred discharges per second would be far too rapidly.
jpsmith123 October 24th, 2007, 12:27 PM

Hello,
I'm wondering, can anyone get the following paper and upload it? Thanks.
Title: Nitrogen Fixation into HNO3 and HNO2 by Pulsed High Voltage Discharge
Author(s): Bian Wenjuan and Yin Xiangli
Publication date: June 2007
Volume: 9 Start page: 288
Publication: Plasma Science and Technology
URL: http://stacks.iop.org/1009-0630/9/288
Abstract:
Plasma processing induced by discharge offers a unique way to activate nitrogen molecules. Direct nitrogen fixation into water
can be realized through this approach. In this study, air or pure nitrogen gas was used as the major nitrogen source bubbled
into the discharge reactor. When a discharge occurred, nitrogen was dissociated to active species to take part in the aqueous
chemical process. HNO3 and HNO2 were produced. The nitrogen fixation process was influenced distinctly by the presence of
hydroxyl radicals. During a discharge of 21 min, HNO3 was the main product and occupied 95% of the total nitrogen content in
water. Its concentration was 1.36 10-3 mol/L-1 with bubbling air and was 1.53 10-3 mol L-1 with bubbling nitrogen, while
the yield was 2.32 10-8 mol J-1S-1 and 2.06 10-8 mol J-1S-1, respectively.
I found two issues online in my journal center, but only up to Feb 2007. I thought it odd that there would be only 2 issues
ending 8 months ago, so I checked a little deeper. It seems they were sent by accident, and the library does not have a
license for them. Of course this does not help you, jpsmith123, but I tried.
The article sounds interesting, though, so I have requested it the long way. It will take a few weeks most likely.
jpsmith123 October 25th, 2007, 11:35 PM

Thanks for your efforts, mega.
Alexires November 4th, 2007, 12:56 AM

Sorry jpsmith123, I tried to get it too with our subscription, but no go.
It is a new journal, and they don't seem to have a subscription to it yet. I tried to buy it, but not being a sheeple and owning a
identity card (read credit card) makes these things difficult.
black mamba November 4th, 2007, 02:18 PM

jpsmith123 I believe this is what you're looking for. I just got access to this journal. If you need anything else, let me know.

This is a very interesting article indeed. I especially like the simplicity of the design, acupuncture needles as electrodes inside
capillary tubes as gas bubblers. If an American had written this experiment they probably would have had glass blowers build
them a custom delivery system made of platinum costing thousands of dollars.
I am a little disappointed at the yield, but this is a small scale laboratory experiment, so it is not optimized for quantity
production. I assume based on the abstract that their intent with conducting this research to begin with is to determine if it is
economical to conduct this type of reaction. Certainly the conclusions of the article are not breakthrough, it has long been
known that electricity air and water produce nitric acid.
The calculation of the rate of reaction seems to be the real heart of the paper. Using their calculations, a rate of formation of
nitric acid of 2.06 x 10-8 mol J-1S-1 means a 100 watt system would produce 2.06 x 10-6 mol/S, or 7.416 x 10-3 mol/hour. It
would take 134 hours of constant operation, for a 100W system, to produce 1 mol of nitric acid.
Since more wattage means more acid being produced per second, does anyone happen to know what a reasonable upper
wattage limit would be for a improvised home based apparatus of this type? A 100W system should be obtainable at the low
end, a system of several hundred watts, maybe even a few thousand could be doable, but I dont have the electronics
background to say how high one could reasonably expect to go. I say reasonably meaning using the kinds of electronics
the average person can be expected to have on hand, or to acquire without much trouble or cost. I am also lowballing my
estimates because there are many other cost factors involved here, the most significant of which is the energy used to distill
the dilute acid.
A 562W system would be required to produce 1 mol of nitric acid every 24 hours. Also of concern is how concentrated the acid
can get. I would expect some nitric decomposition at increasing concentrations. This system may only be feasible in producing
nitrate solutions by periodically flushing the zapper water and neutralizing with an appropriate base (ammonia, sodium
bicarbonate). At least it can produce nitrate salts from which nitric acid can then be obtained.
Assuming you do have a 562W system running for 24 hours, and assuming an electricity cost of $0.08 per kilowatt hour, it
should cost you $1.08 to produce 1 mole of nitric acid. Factoring in 1 mol of nitric acid is 63.012 g, and pure nitric acid is 1.51
g/mL, then 1 L of 100% nitric acid would cost you about $23.96 in electricity. Thats comparable to what you could buy it from
overpriced scammers, but I think industrially they can make nitric acid for about $1 per gallon.

It'd be worth $26/L to have NO ONE know you've got nitric acid. :)
jpsmith123 November 4th, 2007, 11:39 PM

The apparatus is interesting as it seems relatively simple and compact (and BTW I fully agree with your assessment regarding
the equipment implications of this work being done in a country other than the U.S. - I've made the same observation many
times regarding the use of off-the-shelf materials and clever improvisation).
Anyway, the main value of this paper, IMHO, is the innovation of putting the HV discharge, air and water all in one spot.
As far as yield is concerned, it looks they didn't get around to trying to optimize anything yet, so it may be possible to improve
the efficiency substantially.
Lastly, perhaps a neon sign transformer will work as-is for this application...there may be no need for spark gaps, pulsing,
rectification, etc.
megalomania November 5th, 2007, 12:49 AM

I have been briefly reading up on the rotating spark gap they mentioned, that might be a useful thing to use to increase the
life span of electrodes. As for the yield, two things occur to me. First, since this is a pulsed system it is not continuously
operating, so the energy usage might be substantially lower. Thats probably why they calculated their yield in joules. Second,
given the small volume of the reactor (100 mL) yields of a larger system would likely be much greater. A higher voltage
should produce longer sparks, which in turn should lead to greater yields.
Now here is a system that could benefit from the Nafion nitric acid concentration method. Make up water could be slowly added
to the reactor causing the dilute nitric acid to overflow into a water tank. A coil of Nafion tubing, or another suitable water
permeable membrane, is immersed in the acid solution. The air for the capillary bubblers is blown through this tubing pushing
wet air back into the reactor.
A low powered lab scale system could conceivably remove enough moisture from the nitric acid reservoir that it becomes its
own source of make up water. A suitably inexpensive length of Nafion tubing would be measured to remove sufficient moisture
approximately equal to the rate of nitric production. The reservoir acts as a cooling system as well, as the warm overflow water
trickles into the large reservoir it cools to room temperature, and the cooled moist air inside the Nafion tube acts as the main
source of cooling for the reactor. Evaporation of nitric acid could become a problem at higher concentrations unless the
reservoir is sealed.
With nothing but an air pump and a neon sign transformer as the big equipment, and electricity, air, and water as the
reactants, the system I just described could eventually produce 75-80% nitric acid on a continual basis. The rate of acid
production would depend only on the scale of the device. Conceivably, experimenters could produce sufficient nitric acid for
basic lab work, small scale experiments, and chemical tests using only a small scale system. Those desiring greater quantities
of acid would have to invest in a much larger system, but I think this could be at least be divided into multiple systems using
multiple transformers if a gigantic single system is impractical (multiple reactors in parallel with a common reservoir using
inexpensive surplus transformers vs. an exponentially more expensive single system with an industrial transformer).
It is well worth it to have a means of producing nitric acid independent of fedgov regulation. Factoring in shipping and handling
costs of acid shipments alone, which greatly exceed $26 per liter, and you are already ahead of the game. A large
manufacturer might not benefit from this technology, but it is economically feasible for the small scale producer.
gaussincarnate November 23rd, 2007, 12:43 PM

This is a little off-topic, but this is the most relevant thread that I could find. If nitric acid is produced commercially via the
oxidation of ammonia at 850 degrees C (or thereabouts) with a platinum gauze catalyst, then would it be possible to produce
nitric acid in a somewhat related manor (via oxidation)? I was wondering if electrolysis of a water/ammonia solution would form
nitric acid, since water will break down before ammonia, releasing oxygen and hydrogen and hopefully oxidising the ammonia
in turn. I think that it may have to be carried out at a higher temperature to encourage the oxygen to react instead of just
bubble out. I used the search engine and meandered about the internet for some time, but I could not find anything on this
process. I hope that means that it is not used often and not that it does not exist, but there is only one way to find out. I was
just wondering if anyone has ever heard of this before, if anyone has ever tried it, or if anyone thinks that it might (or might
not) work. Thank you.
megalomania November 23rd, 2007, 05:53 PM

Electrolysis of a water and ammonia solution would produce hydrogen and oxygen. If you are lucky, you will decompose your
ammonia as well. Any nitric acid that did form, and it would be a very small quantity, would react with the excess ammonia to
produce ammonium nitrate.
A higher temperature would only serve to vaporize the ammonia in solution, which has a rather low solubility in hot water.
Again, I am not saying you can't make nitric acid this way, just that you will have a virtually nonexistent yield. Unless you
employ some rather fancy solvents or exotic setup, no nitric this way. Don't take my word for it though, if there is a method to
do this, you would be most likely to find it by checking the US patent database for ammonia electrolysis
(freepatentsonline.com).
What you can do is electrolyze nitrate salts in a divided cell to obtain nitric acid and alkali hydroxides. This is probably a lot
more trouble than it is worth considering you can do the same thing by heating the salt with sulfuric acid. If you can go through
all the trouble and expense of setting up a divided cell electrolysis, you can get sulfuric acid and glass distillation equipment.
ProdigyChild February 20th, 2008, 07:02 PM

I've been playing with pulsed power quite a lot, recently. Thanks to wind power plants and hybrid cars, extremely rugged
electronic devices have become affordable to the home experimenter: IGBTs.
I've build a ferrite rod core transformer, that can produce peaks of up to 60kV, 20us, exponential decay. Not that impressing,
you'd say. Right, but:
The transformer can be build easily: single layer of wire on cardboard tube (toilet paper)
No insulation problems, because it's 30cm long
Easy power dissipation
Not too much windings, only a few hundreds, single layer
Only a few Ohms of DC impedance
The core can be built from ferrite torroids or other cores by stacking
Secondary output ist still a few amperes peak.
The major drawback is the electronic part. To get 100..200V of voltage per winding, you have to switch about 1000V at
500..1000A at the primary side. This is, where the modern IGBTs come in. 1200V/800A device can be obtained for about 60$
from EBAY. Driving these parts isn't too easily, but I could provide a schematic and layout. It can be powered by 12V or 24V
This approach gives me the freedom to build HV-pulse-generators accoriding to my specification. However, I can't produce DC
with that.
I wonder, if this device produce NO3- in the way described above. I should check that.
At least, it can act as the ignition part of a high power arc, directly powered from the 230V line. I can't run that beast for more
than a few seconds, without well venting the room (NOx) :D
nightandday February 22nd, 2008, 05:41 PM

You dont need such efforts. Microwave oven transformers (MOT) are best suited to build up power supplies for driving electric
arc furnaces.
Two MOTs should be connected in series on primary and secondary sides, to reduce current and avoid overheating. Use 3 or
better 4 such pairs parallel. Then you will have enough power (2000 V and 2 A). So, the first thing to do is to collect MOTs from
old microwave ovens. 12 MOTs are sufficient, 16 are better.
megalomania February 22nd, 2008, 09:43 PM
Some months ago I learned the lifetime of transformers quickly degrades when used for long periods of time in the type of
usage making nitric acid would entail. This means you will likely need a constant infusion of transformers even for casual
production of nitric acid. I have been trying for months to get my hands on microwave ovens of any stripe, and I only have a
few. Only a very few people could reasonably expect to scrounge enough electronic parts, and they are likely well connected to
electronics sources already.
ProdigyChild seems to offer a preferable alternative by using an inexpensively made sacrificial transformer made from other
robust components. I don't know that much electronics, but I gather an IGBT should last for quite some time.
nightandday's suggestion of multiple transformers in parallel might also alleviate premature transformer degradation. It is
unnecessary, and probably unsafe, to have higher amps. The voltage should be quite high only to initiate a spark, and the
current be minimized to reduce the cost of operating the device.
Ideally I would think producing as long of a spark as possible using as little energy as possible would maximize NO production
per dollar spent.
ETCS (Ret) February 23rd, 2008, 12:08 AM

The Microwave Oven Transformers as sources of the high voltage are promising. In fact just one with a sufficient number of
voltage multiplier stages (diodes and capacitors) would be able to generate enough stored energy to produce a 20KV or more
pulsing arc.
If the primary of the Microwave Oven Transformer were driven electronically with a capacitive discharge circuit of 300 volts by
means of a Thyristor, then the pulsed output voltage at the secondary would be in the vicinity of 10KV or more before
multiplication.
The historic Nitrogen Fixation Processes using the electric arc are:
Birkeland-Eyde process (1905) successfully implemented in Norway used water cooled electrodes with a magnetic control field
at D.C. 5000 Volts, 200 Amperes.
Bradley and Lovejoy process (1902-1904) implemented briefly at Niagara Falls used a rotating hub with spikes style electrode
that produced 9,250 arcs per second at D.C. 8000 Volts, 750 Milliamperes.
During the time those processes were in successful use the efficiencies were limited by the thinking, electrical capabilites and
knowledge of the period. Modern research and trials have produced Electrical Nitrogen Fixation processes which are more
efficient but still not competetive with the ammonia process for industrial scale production. However on a small scale for
modest production they are very attractive.
The modern processes are based upon the Nitrogen Fixing power of lightning and have shown that very brief high current
electrical discharges through air are very effective.
The electrical energy is stored in high voltage capacitors, then the high voltage discharge into air is either stimulated or
allowed to occur spontaneously in a repetetive manner.
A very interesting and enlightening paper on the chemistry of lightning produced Nitrogen Oxides is the Yujin Wang Thesis.
ProdigyChild February 23rd, 2008, 07:54 AM

I'm itching to read the pdf ETCS provides, which is awaiting approval at the time of my writing.
Thanks Mega, for clarifying what I failed to communicate clearly: The aim is to build an arc generator that's easy to build from
easily available components and that does not suffer of degradation.
Right at the moment I'm addressing the problem of how to reduce the electrode wear. We all know, that needle-shaped
electrodes perform very well in terms of igniting a long arc. However they're vaporized in the twinkling of an eye if loaded with
a current (pulse) that can produce noticeable amounts of NO. That's why I use rather smoothly shaped electrodes. I put up
with the fact I have to use extreme voltage to ionize the air. But with these electrodes I still have considerable wear, mostly (I
hope) because I'm using a rectifier/capacitor/inductor-circuit to limit the power drawn from the 230V power line. This
construction results in short pulses of 1-2ms of current at about 50A at a repetition rate of 50Hz. I hope, I can reduce the
sputtering of the electrodes by using a switch mode electronic regulator to limit peak current. More precisely: to SHAPE the arc
current to whatever turns out to be the best compromise between electrode wear, efficiency and speed.
The Jacobs-ladder approach can be applied to my system, too, although in a slightly different way: if a strong magnetic field is
applied at the arc's location, then an arc that normally looks like ball of 8mm in diameter is spread out on bent area of
estimated 2cm^2. This improves electrode durability and probably efficiency. I hope this is still applicable, when I reduce the
peak current.
megalomania February 24th, 2008, 01:15 AM

ProdigyChild, do you have and published material or advise to pass along concerning the magnetic spreading of the arc? I
searched for this some last summer, but I didn't find much since I am not exactly sure where to begin or search terms to use.
The greater the volume of the arc, the more NOx gets produced. I found the theory, but I could find any information on how to
use a magnet to spread an arc. The theory is nice, it seems very sound, but where are the practical details, the how-to, and
applications of the theory?
Since I am really unsure as to how I could test the spread of the arc, how am I supposed to tell if just sticking some magnets
near the electrodes works or not? I highly doubt it is that easy...
Indeed the ammonia route (Haber process) is more efficient, but the start up costs for all the specialized equipment is very
prohibitive. If you have anything less than extreme high pressure tanks, furnaces, syn gas production, hydrogen and nitrogen
reclamators, ammonia liquefiers, etc., you will waste a lot of money. Can all this equipment be made on a small scale? Not
without a very significant investment of money and materials. The electric arc route wins hands down on the small scale
because it uses cheap readily available materials.
What's your option, do it yourself and gripe about spending a few cents extra per liter of acid compared to what it costs
industry, or spend 1000x what it costs and have some chemical supplier ship your acid?
ETCS (Ret) February 24th, 2008, 01:27 AM

The Yujin Wang Thesis can be downloaded here:
http://www.ireap.umd.edu/ireap/theses/YujinWangThesis.pdf
It took me a little digging to find the URL for the download, but fortunately, it was still on the list.

Takes some time to read the Thesis. I wonder, what electrodes they uses to discharge a 1000uF Capacitor @ 10kV :eek:
@Megalomania: No, I don't have much published material. What I know comes from much experimenting and some reading
about HID lamps. High pressure sodium vapor lamps raised my interest recently because the have up to 140 lm/W, while
LED's are still below 100lm/W.
Spreading an arc is really as simple as putting a medium strong magnet below the arc. If the north pole is on top and the
south pole on the bottom and the arc is in the middle of the magnets pole, then the arc will spread horizontally. Same is true
if you exchange north and south or invert the current flow. The effect is pretty strong. You don't need that neodym style of
magnet.
Todays activities:
I have a prototype running, and made a few experiments. Let me describe the setup a little bit. It consists of 2 parts: the
ignition circuit and the main power supply circuit.
The ignition circuit is connected in series with the main power supply circuit and strikes through the air 50 times per second,
when I press a button. It creates a 0.5-1mm thin 'thread' of ionized air. I use at most 0.1J for this on the primary side of the
HV transformer. No idea how much I have left of it on the secondary side. It's basically discharging a 220nF capacitor (FKP1)
charged to 600..1000V over the primary of the transformer.
The main power supply is a 'step down' 'buck' topology constant current regulator. Key parts for those who care: UC3845,
IRF840, DSEK60-06, 6.8mH coil. I use a rather low switching frequency at the moment, because I want that toy to withstand
short circuit for a long time. What is does! :D
If no load is present, the voltage rises to 320V. If I short it, the the voltage drops to zero, while the adjusted current is
maintained. When I open the short, a massive arc appears. The current can be adjusted from zero to 5A at the moment.
Shorting the supply isn't spectacular at all, since it's output is mainly inductive, only 150nF of capacitance in parallel. Although
the analog input would allow current shaping, I only switch constant current on or off.
So, what have I found so far?
a) I cannot keep a low current (e.g. 0.5A) arc burning. I have to use 3A or more to reach a length around 10mm. I'm a bit
disappointed about that.
b) Similar problem: In a setup, where I can strike through 20mm of air with the ignition circuit, I can keep the main arc
burning only up to 10mm. The main arc does not appear at all! (I believe, it's roughly the same arc length I can reach, when
shorting the power supply and then slowly pulling apart the electrode bars). Increasing the maximum current helps a little bit,
so does using more energy for pre-ionization.
c) Spreading the arc with a magnetic field is counter-productive in terms of stable arc length. A strong magnetic field can
reduce the maximum arc length to nearly zero. :eek:
d) I have the impression that steel electrodes allow much longer arcs than copper ones. I should examine using electrodes of
the same shape and size and only different in material. I do not use Tungsten electrodes although I have some. NO2 can be
removed by venting the lab, Tungsten dust can't.
e) The good news is: I definitely have much less electrode wear, although still far from an acceptable level.
Experiment details and calculations:

1) Ignition transformer secondary coil: 0.8Ohms (DC), wire diameter 1.0mm, 200turns, coil length 220mm, diameter 44mm;
reliable arc-over (ignition) about 8mm.
At an electrode distance of 8mm and a current of 5A I read 50V of arc voltage. Reducing the current to 2A results in 70V arc
voltage and somewhat unreliable ignition. The power released is roughly 250W in the first case, 140W in the second. Power
dissipation of the coil is 20W and 3.2W respectively.
2) Ignition transformer secondary coil: 15Ohms (DC), wire diameter 0.4mm, 500turns, coil length 220mm, diameter 44mm;
reliable arc-over (ignition) about 20mm.
At an electrode distance of 9.5mm and a current of 2A I read 90V of arc voltage. At 3A I read 85V arc voltage. The power
released is 180W in the first case, 255W in the second. However, the high DC resitance of the coil eats up 60W and 135W.
The measurements show, how difficult it is to release power into the air, rather than into the the equipment. It's remarkable,
how low the arc voltage is. It's surprising to me that I can't stretch the arc longer. Perhaps it's because my circuit isn't ideal - it
presents a positive resistance to the output.
The current is not that constant. Apart from that I can see, that the arc is really hot and the air flows upwards and extinguishes
the arc. When I arrange the electrodes vertically I can indeed get considerable longer arcs. Of course, all the hot air hits the
upper electrode then with obvious consequences...
Any suggestions about extending electrode lifetime?
ETCS (Ret) February 24th, 2008, 07:44 PM

In order to minimize the large power losses as heat it is necessary to use a stored energy discharge system of pulses. The
electrical process of charging the high voltage capacitor with a relatively low current will be quite efficient.
When the voltage becomes high enough to arc across the electrodes (selt-initiated) the discharge current will be very high and
very brief. This generates a huge instantaneous power and very high temperature to form the nitrogen oxides and ozone, and
because of its brevity allows for rapid cooling of the gasses to preserve the oxides before they decompose.
The pulsed discharges will greatly prolong the life of your electrodes since they won't be overheated by a continuous arc.
You'll find a great deal of useful info in Yujin Wang's extensive tests and analysis.

I read somewhere that using spinning metal disks as electrodes reduces wear because the hot arc only contacts a point on the
metal briefly. This is one of the reasons I incorporated a steel washer into my glass tube reactor design. Rotary spark gap is
the proper term for this I believe.
ETCS (Ret) February 25th, 2008, 03:02 PM

The high powered Tesla Coils built by Tesla Experimenters still use the "Disruptive Discharge" method Tesla used to feed the
primary winding.
There are several very good Tesla Coil websites that go into good depth on the construction of durable spark gaps, and some
of them explain the use magnetic field quenching to control the discharge.
When you find one of the Tesla Coil sites via search engine, it will have links to several others. They're a very supportive and
cooperative community, not to mention very capable technically.
You'll find a lot of very helpful info.

I've read parts of Yujin Wang's thesis. Really impressing, lots of ideas that will help me!
But I'm a bit disappointed that he reached only 4cm main arc length, even though the Marx-generator could strike through
20cm? An why the hell wait for 80us after the Marx-generator triggered? Probably this is the reason. Or the cascading of 2
spark gaps (main arc+SF6 triggered gap).
If I can get nearly 1cm with 320V he should be able to ignite a main arc of over 10cm I would say. Give me that capacitor
bank, I'll have a try! ;)
I've thought about my limited current approach and I fear it's a nice experiment but not efficient in the end. A better approach
could be to ionize the air and then send a burst of medium current pulses - say 20A - through the channel. The time between
two pulses tweaked to let the air cool down a little bit so that the next pulse has a large voltage drop again. That way I could
transfer much more heat to the air.
A disc electrode need not rotate all the time. If the rotation is an oscillation only, you still have the benefit of a better
distribution of stress. Such an oscillation can be excited by a coil from outside the reaction vessel. No trouble with sealing,
wiring or motor corrosion.

Hi all, I want to provide a photographs of the arc under the influence of the magnetic field.
1. photo
I placed a strong N52 magnet at 7cm below the arc. The image was made by exposing for about 1s at daylight with tiny
aperture and switching on the arcs repetitive ignition for as short as I could do by hand.
2. photo
Same as above but magnet removed. Also there's no chance to have a short period arc as it does not quench any more
without the magnetic field. This image gives you an idea on the size of the arc without B-field.
[Updated:]
3. photo
Now using electrodes arranged like a Jacobs ladder. On the bottom you can see the N52 magnet again. Again a long term
exposure.
The arc lives for about 1second and travels in that time from bottom to top. The initial few cm are heavily accelerated by the
magnetic field. Otherwise it would stay at the bottom and melt down the electrodes. The arc you see uses no more than 200V
after ionization.
Holy shit! I can't write down all that comes to my mind right now. I think about using an array of magnets all along the
electrodes to speed up the travel of the arc.
I also wonder if the arc would leap over a gap. Over to another pair of electrodes of low voltage (100V?) but obscenely high
current easily controllable by a few power MOSFETs. The more current the stronger the propulsion of the arc in a magnetic field
- we could accelerate the arc like a projectile of a rail gun! This propulsion could be used to let the arc travel through the air at
enormous speed and leave behind a low pressure area that 'freezes out' the NO as described in the thesis pdf. Finally fresh air
is sucked in again and we give it another high energy flash!
I stronly believe, that modern electronics has just given us the tools to produce NOx with an ease and efficiency not imaginabe
before!
[OMG this sounds like the words of a politican...]
[Updated again:]
Yes, the arc can leap over a gap!
I placed a 500uF capacitor charged to 300V on to of the arc shown on photo 3. It discharged with a loud bang, i.e. the
inductance of the transformer coil was skipped and the arc found a ultra-low impedance current path. I have to check the
reliability of such a leap over a gap of course. In case of success, I need to shorten the Jacobs-ladder setup shown on photo 3
and optimze it to a plasma 'gun'. This plasma gun can then be used to inject ions between the rails-electrodes of a high
current arc. The high current arc supply does not need to be able to produce thousands of volts any more - this makes the
design much easier. High impedance coils can be omitted allowing for extremely efficient power conversion from AC line to the
arc and for MUCH higher currents at even lower power dissipation.
Another experiment to carry out soon will be the measurement of the arc's traveling speed at the lower end. At the lower end
its considerably faster than at the upper part.
nightandday February 28th, 2008, 04:32 PM

If you use it right, MOTs are well suited to build up power supplies for elecric arc furnaces.
MOTs used in general type microwave ovens (not inverter type) are single-phase dry-type transformers with iron-cores and
copper coils, designed to operate at 50 - 60 Hz.
Here are some technical data of a typical MOT (from Microwave oven 230 V~, Input: 1150 W, output: 700 W):
weight: 3.2 kg
transformation ratio: 10
ohmic resistance of primary coil: 3,0 Ohm
ohmic resistance of secondary coil: 250 Ohm
reactance of primary coil: 1.5 Henry
reactance of secondary coil: 65 Henry
nominal voltage: 170 V~
rated power: 300 VA (derived from weight)
At 230 V~ primary voltage:
no-load loss: 75 W
no-load primary current: 2.1 A
secondary voltage: 2.1 kV
short circuit current (secondary): 1.7 A
At 115 V~ primary voltage:
no-load loss: 15 W
no-load primary current: 0.26 A
secondary voltage: 1.16 kV
short circuit current (secondary): 0.93 A
MOTs in microwave ovens are overboosted. This is only possible for short periods of time and with forced cooling. For
continuous operation of MOTs, primary voltage must be < 170 V~ and output power < 300 W or secondary current < 300 mA.
This arrangement of MOTs is good enough as continuous power supply for electric arc flames.
http://rapidshare.com/files/95715669/MOT_Batterie.pdf.html
Note: reactance is required in the circuits of an arc furnace to give stability and to limit the current. Using DC, an ohmic
resistance (e.g. 500 W Halogen lamps in serial and parallel connection) is required, causing heat losses.
nightandday March 1st, 2008, 03:25 PM

The dissertation by Yujin Wang (University of Maryland) gives the following information about the NO yield of laboratory
sparks.
"... studies ... reported ...the number of NO molecules per unit of discharge energy ... as 2 to 17*10^16 NO/J" (p.8)
"... the NO yield of a lightning stroke is usually determined by two parameters: the NO mixing ratio when NO is "frozen out"
from a spark channel and the amount of air mixture involved." (p.90)
"...correlation between NO production and spark energy is very complicated..." (p.91)
"The observed pNO (NO production per unit energy) is greater than the previously reported results of simulations or
observations in laboratory sparks. ... The pNO by a simulated spark with peak current of 30 kA ... is 40*10^16 NO/Joule in our
experiments. This discrepancy of the pNO values may be caused by the different energy accounting used in our results. In
most previously reported works, the stored energy was used as the energy to calculate NO... In our experiments, only the
energy dissipated in a spark was used as the the energy to produce NO. The diagnostics of experimental sparks ... has
showed that less than 1% of the energy stored in the capacitor bank was dissipated in the discharge channel. If this stored
energy was accounted as the energy to produce NO, pNO would be 0.15 - 0.30*10^16 NO/Joule ..." (p.92)
"...water has little effect on NOx production..." (p.94)
Notes:
Conversion: 10^16 NO/J is equivalent to 3.77 g HNO3/kWh. (1 kWh = 3.6 MJ)
The maximum yield reported for sparks in air is 17*10^16 NO/J. (Chameides, Nature 280, p.820)
This corresponds to 64 g HNO3/kWh.
The maximum yield reported by Wang is 0.3*10^16 NO/J (with respect to real input energy stored in the capacitor bank),
which gives only 1.13 g HNO3/kWh.
For comparison:
The reported yield of Schoenherr reactors (using a single arc flame in a long vertical tube without magnetic field) is more than
80 g HNO3/kWh (best values are about 100 g HNO3/kWh).
The Birkeland-Eyde reactor is more complicated and less effective:
"... the yield was between 500 and 600 kilogrammes of anhydrous nitric acid per kilowatt-year". (i.e. 57.0 - 68.4 g HNO3/kWh)
K.Birkeland, Proc. Faraday Soc. VolII-T5, p.108 (1906)
ProdigyChild March 1st, 2008, 05:59 PM

I've tried to build a suitable reactor. For the first try, I used a cylindric glass of 10cm diameter, 22cm length. For the electrodes
I used copper pipe, 8mm diameter, 20cm length. To get the vessel sealed, I used a PCB-board with 2 separate areas of
copper. Through each of the areas a 8mm hole was drilled, an electrode tube put through it and finally the tube was soldered
to the copper area. The copper area serves as current connection. The class vessel is put onto the PCB-board with the
electrodes sticking 18cm into the cavity to the vessel. As the electrodes are tubes air can be pumped into one of them and
sucked off the other. This serves both gas throughput and cooling.
I'm really convinced that using a magnet to move the arc is the way to go. So I'm using a STRONG magnet like in photo 3 of
my previous posts to accelerate and guide the arc all the way along the electrodes. This can be done from outside the reactor.
On the last 2.5cm the electrodes are kinked outward so that their distance increases to 3cm and the arc is quenched there.
The shortest distance between the electrodes is 3mm and I must tell you this is still too much for reliable ignition with the
current circuitry! The smooth surface of the electrodes makes it much more difficult to ignite the main arc even though the
preionization arc strikes reliably. Even worse after maybe 20seconds of accumulated use of the first run the main arc refused
to ignite at all!
I hople I can get over these problems by welding a small pin to the electrodes the make them ignite more easily.
From direct measurement of arc voltage and current I have to assume that up to 900W will be released inside the vessel
thanks to the magnetic spreading of the arc :)
The total area the arc travels through is approx 7cm2. Not that bad, really.
Does anyone know if silicone rubber will withstand NOx so I can use it on the outlet of the reactor?
What kind of materials do you suggest at all?
Someone (nightandday I believe) proposed gypsum for fitting electrodes.
Is there a nonconductive nonvolatile liquid I could use to submerge the lower end of the reactor to have no NOx escape into
my room? Destilled water has for too high conductivity for the high voltages used, unfortulately.
ETCS (Ret) March 1st, 2008, 06:18 PM

Good points.
It seems Wang was trying, on a small scale, to duplicate the current densities of lightning discharges, which are enormous.
Lightning itself is not particularly efficient, by apparent design, because of the great excess of overcurrent.
The description I have of the Schoenherr reactors is that of a "long filament arc of low intensity through the tube," which,
coupled with optimal airflow, probably produced the higher efficiency.
The setup can be "tuned" for greatest efficiency by limiting the stored energy, and therefore the current intensity of the
discharge, to minimize losses associated with excess current flow produced heat, thus enabling more of the oxides to survive.
Interestingly, other studies have shown that Nitrogen alone, by electrical discharge, may be made to react with water to
produce Nitric Acid.
Many fascinating possibilities spring to mind.
megalomania March 2nd, 2008, 06:46 PM

I have never heard of the Schoenherr furnace until now. After a little research this apparatus sounds very similar to the setup
used in US patent 4877589, Nitrogen fixation by electric arc and catalyst, that I want to build. The patent incorporates a
tangentially added air tube that doubles as the holders for the electrodes. The air is circulated in a vertical chamber filled with
tungsten catalyst coated alumina spheres. The air passes directly over the electric arc as it enters the reaction tube.
The Schoenherr furnace seems to be a vertical iron tube, a pipe most likely, with a central electrode in the middle along the
entire length. The spark spirals up the electrode like a Jacobs ladder while air is inserted tangentially.
Adding the air at a tangent creates a vortex like effect (tornado) that circulates it more, increasing the likelihood that
something will contact the electric arc, and this fast moving air will have a limited contact time. The longer the contact time the
great the possibility of your nitrogen oxide decomposing back to nitrogen and oxygen.
I found this nice google book that had a chapter about electric furnaces, including a section devoted to nitrogen fixation
furnaces. Electrician's Handy Book: A Modern Book of Reference by Thomas O'Conor Sloane is available in its entirety from
google at http://books.google.com/books/pdf/Electrician_s_Handy_Book.pdf?id=SvUOAAAAYAAJ&output=pdf&sig=iA9DeCfWCZ-
NoQCuGoD1Xlo6rzY
This book just makes the cutoff for public domain works it seems. I have attached the relevant pages about nitrogen fixation
furnaces, pages 782-786.
This book reports the yields of nitric acid for the Schoenherr furnace at 65g/kWh, and for the Brickland Eyde (their spelling) at
67-70g/kWh.
I did see a study (I probably have it in my folder of nitric acid files somewhere) about producing nitric acid from an underwater
electric arc with nitrogen gas being bubbled in. I forget what the conclusions were of this reaction.
jpsmith123 March 3rd, 2008, 09:38 AM

The process described in the paper by WENJUAN et al. (using HV pulses in water) has apparently been patented (or is in the
process of being patented) in China...so the inventors and their sponsor must think it has some commercial potential. Here's
the abstract from the European patent office:
Abstract of CN1903705
The present invention discloses a method for making nitrogen fixation in water and its device. It is characterized by that the
nitrogen-contained gas is aerated into water, at the same time the high-voltage pulse discharge is made, the discharge
electrode is positioned in the water. The pulse width of the described pulse discharge is 200-500 NS, the rise advancing edge
of pulse voltage is less than 20 NS, the pulse frequency is greater than 50H2, peak voltage is greater than 10 KV and
discharge time is above 3 min so as to obtain nitric acid solution. The device using said method includes the following several
portions: gas chamber positioned in the bottom portion of main reaction chamber, several aeration micropores and several
upwards-projected needle discharge electrodes which are set in the top portion of gas chamber, grounding electrode placed in
said main reaction chamber, the output of high-voltage pulse power supply is respectively connected with discharge electrode
and grounding electrode.
Unfortunately it seems that the full text of the patent is not available from esp@cenet.
################################################## ###########
Edit: There are several interesting sounding patents at the European patent office. Here's the abstract of an interesting
Russian patent (unfortunately the document itself is in Russian):
Abstract of RU2116960
FIELD: nitrogen compound production. SUBSTANCE: nitrogen-containing gases are brought into contact with catalyst at
atmosphere pressure and low temperatures, where catalyst consists of carbonyl complexes of transition metals, in particular,
platinum group metals, in the form of solids, solutions or suspensions with neutral, acidic or alkaline medium. Nitrogen-
containing gases may include reducing and/or oxidizing agents. Final products are ammonia or nitrogen oxides. EFFECT:
enhanced process efficiency

The general theme of the various furnaces and technologies seems to be air heated to nearly 3000 degrees and rapidly
cooled gives the best yields of nitric oxide. I am of a mind to attempt a hybrid magnetically expanded arc combined with a
tungsten catalyst system. The early 20th century was only just beginning to utilize catalysts when these technologies were
being used, but modern chemistry has advanced catalyst technology to a formidable level.
I do not recall, beyond the O'Hare patent I just mentioned above, any type of nitrogen fixation process that actually
incorporates a catalyst into the design. O'Hare uses a sparking apparatus similar to the Cavendish design, but with a catalyst.
This simple structure benefits the third world locales it is intended to be deployed in.
A catalyst area immediately following a magnetically spread plasma arc might substantially increase yields. The O'hare design
of air circulated catalyst spheres might interfere with such a spread arc, but a catalyst coated screen or honeycomb should be
just as effective.
Incorporating something like a water cooled jacket outside the container that holds the catalyst might also help increase yields
by providing a steep temperature drop for the formed nitric oxide. I wonder even if a tapered constrictor, like a funnel, could
hold the catalyst, the wide end has a metal screen to hold in the catalyst spheres, the arc just below it, and the air is forced
into a small area at the narrow funnel end where water cooling would be more effective because more of it is near the outer
container. This design might also reduce the quantity of alumina catalyst spheres necessary, filling the volume of a cone
rather than cylinder, and it might increase catalyst agitation because air pressure would be greater in the smaller volume.
ETCS (Ret) March 4th, 2008, 11:34 PM

The Experiments to Fight Hunger page has been found again:
http://www.frontier.net/~ohare/
There you'll find many thought provoking possibilities and innovations in dealing with the various methods of making useful
materials.
Many downloadable diagrams and explanations.
Tried uploading a couple of samples,but as they are htm files, no joy. :eek:
ProdigyChild March 9th, 2008, 02:58 PM

At about year 1900 there was a lamp called 'Nerst lamp' produced by Westinghouse. It was better than carbon filament lamps
and disappeared only when tungsten filament lamps become available. It used a rod of ZrO2 heated up by electric current.
This rod is conductive thanks to the O2- ions that can travel though it quite well when heated to 1000-2000 Celsius.
So why not use this material as electrodes? It melts at 2715 Celsius. No problem with oxidation, because it's already an oxide
:)
It's a bad conductor for heat - no idea if this is good (not that much heat loss) or bad (overheating of the electrode).
What's the drawback? Why does no furnace use that stuff?

The only drawback I see is the fact, that ZrO2 is an insulator at room temperature.
nightandday March 10th, 2008, 05:58 PM

Extracting information about the yield obtained by:
Bian and Ying, Plasma Science and Technology, Vol.9, No.3 (2007)
"Nitrogen Fixation into HNO3 and HNO2 by Pulsed High Voltage Discharge"
In their paper they write:
"...the applied voltage was 20 kV at a frequency of 150 Hz.

The distance between the electrodes was 20 mm" (p.289)
"...the energy input into the reactor was 52.3 W" (p.289)
"...100 mL of distilled water was pured into the reactor..." (p.289)
"After a discharge of 21 min, nitrate nitrogen concentration was 1.36*10^-3 mol*L^-1 with bubbling air..." (p.290)
"The content of nitrite nitrogen did not exceed 5%" (p.290)
Translation:
100 ml aquous nitrate solution of 1,36*10^-3 mol*L^-1 NO3- contains 8.57*10^-3 g HNO3
52.3 W during 21 min is 1.83*10^-2 kWh
Yield: 8.57*10^-3 gHNO3 / 1.83*10^-2 kWh = 0.47 gHNO3/kWh
Probably thats not good enough.

Alumina Aerogel, and other catalysts, is capable of producing Nitric Oxide by heat alone without any electrical power, by means
of thermal cycling and controlled airflow.
As it converts to Nitrogen Dioxide in the air stream it may be used either for creating a Nitric Acid Solution or for Direct Nitration
of Carbohydrates.
O'hares web pages have the details of the process and several ideas on enhanced efficiency of electrical production of Nitrogen
Oxides as well, using bundles of Tungsten welding electrodes as both plasma electrodes and catalyst among them.
http://www.frontier.net/~ohare/solar_powered_nitrogen_fixer.GIF
http://www.frontier.net/~ohare/vortexplant3.GIF
http://www.frontier.net/~ohare/aluminanitr.htm
http://www.frontier.net/~ohare/threetogthr.GIF
http://www.frontier.net/~ohare/Nitrogen_cellulose_fertilizer.GIF
http://www.frontier.net/~ohare/Fertilizer_from_Air.GIF
http://www.frontier.net/~ohare/biogasnitrogen.htm
FUTI March 11th, 2008, 06:15 PM

Just a random thought...are the various methods (or at least some of them) proposed and used for NOx generation mutually
incompatible or can they work in synergy kind action? Rapid heating followed by discharge followed by UV light (or any other
tool and source arranged in any possible way)... I hope I explain this in an understandable way. I like idea of using metallic
oxides and also magnetically spread plasma. Those ideas bring little life in this thread.

Prodigy Child's demonstration of High Voltage (~20KV) initiated Charged Capacitor (300V) plasma discharge, in #188 above,
is very productive.
This is the method used for "Plasma Ignition" in certain automobiles for greatly improved operation of the Internal
Combustion Engine. The Charged Capacitor for this application will work with as little as 110 Volts of charge.
So a rather feeble Very High Voltage source could be effectively employed to "trigger" a charged capacitor high current plasma
discharge through air in repetitive pulses. That would significantly simplify the power source to the Nitrogen Fixation device.
As it turns out, there are a lotta ways to skin this ol' Cat!

@ETCS: when the triggering device uses P = 800A x 1kV it is not exactly 'feeble'. It must not be feeble, otherwise it can't drive
the parasitic capacitance of the electrodes.
But of course you're right when comparing the average power of the two supplies. The trigger power is neglectable.
I observed a few days ago, that a very high voltage pulse (2cm..4cm arcover) could NOT trigger a high current discharge of a
capacitor at 300V, but between 600V and 1kV the capacitor was again happily discharging, even if I limited the current with a
series resistor of 50-100 Ohms (i.e. 20A discharge current at most).
So I've built a powerful line voltage booster that can step up rectified AC to 500V easily. I fed the 500V output voltage into the
circuit shown in post #188. OMG! I could draw vertical arcs of 9cm length at estimated 2-3A of (now really constant) current.
I thought I could ignite such long arcs with the high voltage ignition device, too. So I pressed the HV ignition button and tried
to adjust the electrodes to the maximum HV arcover length. Obviously I had no third hand free to press the main power
button at the same time. But the arc ignited anyway?! The MOSFET got into avalanche conduction and exploded in a huge
fireball along with the PWM driver, a small capacitor and ALL resistors in their vicinity...
Yes I'm stupid, because I should not use a varistor with a voltage rating greater than the MOSFET's!
The curcuit is really damaged, even some PCB traces have vanished.
What a bad setback.
However from the short experimenting time I'm quite convinced, that using a moderate high voltage of 400-800V would be
very advantageous to yield much longer arcs. 800V is well above any recitfied line voltage. Using a step-up converter to boost
line voltage makes the people using 230V line voltage and those using 115V more or less equal. Power factor correction is
possible, too.
@ETCS: have you read this? http://carambola.usc.edu/research/coronaignition/coronaignition.html

(I searched the web using your keywords ;-)
ETCS (Ret) March 20th, 2008, 12:22 AM

Prodigy Child,
The sudden discharge of a capacitor can unleash a spectacular and very destructive explosion - not what we're looking for
necessarily, but impressive in its power.
It is very gratifying that you witnessed the event without any bodily harm!
I'd be very much interested in seeing a schematic drawing of your test circuit. I'm having some difficulty visualizing how the
MOSFET fits in.
I'm uploading a small graphic file that illustrates an effective Plasma Discharge Ignition System for an internal combusion
engine courtesy of Tero who is a member of the Hydroxy Group. To get really good control you need a pair of High Voltage
Diodes (5KV or better at 3 Amperes rating) in both sides of the circuit. This circuit would also be a good one to use for Pulsed
Nitrogen Oxide generation in a suitable enclosure such as O'hare suggests.
The Study you linked to is very interesting and the conclusion reached is surprising. Solid State Tesla Coils make excellent
sources of corona disharge and can be easily pulsed. Maybe it is time to pursue this further...
You're clearly onto something!
ProdigyChild March 21st, 2008, 01:14 PM

The schematic below shows the key components of my arc power supply.
The controllers are not shown. The frequencies at the gates are typical values I've used so far.
T201 is really oversized. T401 is not.

T301 is a bit feeble, I'll replace it by a IRG4PC30U.

I've rebuilt my arc power supply and improved its ruggedness. In the following measurements no HV ignition is used. The arcs
are created by shorting the electrodes and then stretching the arc by hand.
It's very promising that the measurements have shown that long arcs (more than 2cm) have voltage drops of well above
100V. This implies that a supply of 3A current can dissipate over 300W of heat in air. Not that bad.
The measurements and photos were all made at short circuit of 3A and a maximum voltage of 500V. To be precise: if no load
is presented then 500V output. If shorted, then current limited to 3-4A. In between the supply tries to deliver 3A (calibrated to
3A@300V). At above 400V it drops below 2A.
The photo shows an arc drawn vertically the coil-shaped electrode down to the table's surface. The photo was shot with speed-
light enabled to show the ambiance of the arc. No, the arc is not as feeble as the photo might pretend. It's blinding bright in
reality - I used an appropriate aperture to show the details.
The first DSO screen shot is the V/I versus time of exactly the arc shown on the photo. CH1 is arc current, 5A/unit. CH2 is arc
voltage, 100V/unit.
The second DSO screen shot shows a slowly stretched arc's V/I versus time.
It can be calculated, that the power dissipation approaches 500W at the time the arc quenches.
I should note that such long arcs at such low ;) voltage are not stable. They move around a bit out of control. A slight air draft
wipes them out. This is why I can't produce horizontal arcs of that length - the plasma moves upwards to quickly! 2cm to 3cm
horizontally at most. That's why a HV ignition will be required for a 'production system'.
ETCS (Ret) April 22nd, 2008, 05:47 AM

Very nice work ProdigyChild!
Here's an interesting brief of the NOx generation process with photo:
http://www.kronjaeger.com/hv/hv/exp/no/index.html
His main page has a wealth of info too:
http://www.kronjaeger.com/hv/index.html
megalomania April 22nd, 2008, 11:28 AM

I've had this guys page bookmarked for awhile. I think there is a video that goes with his NOx production. Seems to me he
shows how he arranges the aluminum foil in the cups and zaps it showing the formation of orange-brown gas. I think the video
was on YouTube, I don't see the link if it is.
ProdigyChild April 27th, 2008, 07:15 PM

I've seen this page some time ago, but lost it again. However, I've never forgotten the intense brown color in that image. To
be honest, I've never got such intense color in any of my own experiments :o
I also remember the photo inside a school chemistry book - also an intense brown color was shown in a glass vessel maybe
15cm in diameter.
Why that? I must do something really, really wrong.

When I re-visited kronjaeger's page, I realized he used aluminium foil as electrodes. Perhaps some catalytic effect as
mentioned earlier in this thread? I'm always using copper electrodes for their good heat conductivity. I wonder if these are
responsible for my low yields.
Being a bit frustrated about the complexity of building a reactor for a high power arc (water cooling 2 HV electrodes, pressure
waves, excessive heat, cracking glass vessels,...) I gave a simple design a go: I used the highest voltage spark (50kV+) I
can produce at the highest repetition rate (200Hz), covered with a large (2.8l) cylindrical vessel. The (primary) power is about
30W. This system produces NOx without heating up everything. After about 10minutes the maximum color intensity is
reached, running the arc for 20more minutes doesn't change the visual appearance any more. That was still not as brown as
on Kronjaeger's page. And yes, copper foil electrodes.
ETCS (Ret) April 29th, 2008, 08:14 PM

ProdigyChild,
For my NOx experiments I've always used Aluminum wire for the gap. Mainly because I've got a fairly good supply of it and it
doesn't tend to corrode. I suspect your raising the possibility of some catalysis going on with the aluminum is probably correct.
Kronjaeger's photo may be slightly enhanced to show the effect. My results have not been that intense either.
A really simple "line powered" capacitive discharge unit can be made using a Lamp Dimmer (TRIAC phase control) unit. A
small capacitor ( 2 to 4 Microfarads ) is placed in series with the wiring to the primary of the Ignition Coil to limit the charge/
discharge current to a safe level. Then the spark output and intensity can be adjusted, within a certain amount of the range of
the control, as if dimming or brightening an incandescent lamp.
Did you mean to say that you'd used Aluminum Foil Electrodes?
megalomania April 30th, 2008, 01:19 AM

I would think any catalytic effect in a system of this design would be negligible. This reaction is caused by the formation of
nitrogen and oxygen radicals at the very high temperatures of the arc plasma. One of the most significant aspects of this
system is the ability to cool the NOx gasses before they decompose at high temperatures. It is more likely the shape of the
electrode influences the formation of NOx gasses.
If you trap and hold the NOx gases inside a container at elevated temperatures then a catalytic effect could be observed.
Heated metals will accelerate the decomposition of NOx, and copper would be far more effective at this. In the catalytic
oxidation of ammonia, copper has a very low residence time (length of time the formed NO gas can remain in contact with the
metal before it decomposes). Copper would probably make a superior catalytic converter except it gets oxidized under such
conditions where platinum does not.
The reason the metal should only have a minimal impact on NOx yield is because so very little gas comes in contact with the
electrode compared to the arc. This case works for a flowing system with fresh gas constantly being brought in. In a confined
container, stirring caused by thermal currents could bring a great deal of NOx gas in to contact with the electrode.
I am interested to see if the process patented by O'Hare actually works. His method uses tungsten oxide coated alumina
spheres as a catalyst to increase the yield of NOx after passing air through an electric arc. I have a method now of preparing
tungsten compounds to impregnate the spheres, I just need to find a reasonable source for the spheres. Alumina spheres
cost a few dollars a pound, but all the companies I found only sell them in bulk. Sigma sells a pound or so, but for over $100.
I don't want to shell out $60 for a 50 lb sack of spheres when I will likely never use 49.5 pounds of it.
ETCS (Ret) May 2nd, 2008, 08:37 PM

In the not too distant past I observed an interesting phenomena in one of my Negative Ion Generator units.
The high voltage generator circuit is simply a line powered capacitive discharge into the primary winding of a Xenon Flashtube
trigger transformer via a DIAC. The High Voltage secondary is multiplied by a four stage diode-capacitor array to
approximately 10 KV.
The original diodes were very fragile and had burned out so I replaced them with 6 KV, 250 mA units. Unfortunately, when
finished I didn't coat the exposed diode wires (#22) with high voltage insulating compound. I installed the repaired unit into a
clear plastic jar so the circuit board would be visible and observable. Upon powering up in a darkened room I observed that the
output voltage was normal, would draw an arc of about 6 mm, and that there was corona discharge on the exposed diode
leads. As the leads were tinned I expected that the corona would have little effect on the integrity of the wires.
After about six months of what appeared to be normal operation into the ion emission array, it suddenly failed. When I
opened the plastic jar to examine the circuit board the escaping air smelled strongly of ozone, as expected, but the wires
which had been emitting the corona discharge were completely eaten through by the corrosive gases! The ends of the wires
which remained were the greenish color of oxidized copper and on the surfaces were small droplets of a deep blue liquid. It
would seem that the rather feeble corona discharge had produced enough ozone and NOx over that length of time to form
small globs of copper nitrate.
After cleaning the "mess" up and repairing the eroded wires I completely covered all the wiring with a high voltage insulating
compound and the unit is back to normal operation again; however, this time without the destructive corona discharge!
Even tinned copper wire is incapable of withstanding the assault of a rather feeble high voltage discharge and the ozone and
NOx which results.
Moxus May 27th, 2008, 08:33 AM

In my birkelandreactor, I use a 1400 watts microvawe oven transformer (MOT). My problem is that my electrodes just burns
up.
I tried configuring them in a jacobs ladder, letting the arc travel over a larger surface and hence distributing the heat over a
large area.
This works, but it also has a problem. The arc constantly breaking and reforming causes considerable radio noise wich is
annoying when you try to watch tv or talk in your cellphone, where the interference from the arcs noise is obvious.
So my thought was to use a stationary arc again, from watercooled electrodes. So my electrodes is simply copper tubes wich
runs water through.
I expect the copper to corrode, but I dont know how fast yet so that will be interesting to see.
Anyway, I came up with an idea wich allows me to run electrode 1 and electrode 2 within the same water circuit, but yet having
the "waterline" physically broken to awoid parasitic currents in the coolant water. And of coruse, also to awoid 8000 VAC from
going into the houses water supply, if ran from a water outlet.
What I did was putting 2 pipes into a soda bottle. one to the bottom, and the second just inside the top of the bottle. Then
making sure the bottle is 100% airtight. Now, you can run water-in in the top pipe, and water-out in the bottom tube, and the
water-out will be totally electrically insulated from water-in, as long as the waterflow is kept at a low level, to allow the
waterbeam to beak into drops before reaching the bottom. To increase flow capacity of the device, it is possilbe to fit some
kind of spray nozzle to the water-in pipe, letting drops form much quicker.
I hope my idea can be of help, because i read some people over at sciencemadness talk about watercooled electrodes, but
the idea stopped right there because the problem of parasitic curents through the coolant water.
Herro June 4th, 2008, 12:33 PM

mega-
I'm not sure what the bulk prices look like, but I know McMaster(.com) sells alumina spheres down to 1/8"D for ~$1.50 each I,
believe. Fairly steep, but you'd have the precise quantity you need. Just a thought.

That's not the same kind of alumina. The kind McMaster-Carr is selling are ceramic spheres, not activated alumina with a very
high surface area. The cheapest I found is a 50 lb sack of 1/8th inch activated alumina spheres, F-200 grade, with a surface
area of 355 m3/g for $65.00. It is the very high surface area that is important, as this is to be used as a catalyst substrate. F-
200 isnt even catalyst grade technically, it is a drying material grade, but the catalyst grade has only slightly higher surface
area at a significantly greater price.
willowmp June 15th, 2008, 12:49 PM

@Moxus
To eliminate the rf radiation comming off the jacob's ladder build a faraday cage around it. This should prevent most if not all
the rf from leaving the inside of said cage. Its been a while but if I remember correctly its basically just wire mesh making a
"cage" around the rf producing object that is grounded. So a grounded screen of metal window mesh would be good.
As for arc length, I havent read through this whole thread but my solid state tesla coil produces quite a long arc, maybe 3
inches or so? I bought said SSTC from information unlimited if you want to go check out their guides on how to build it or
preassembled versions.

Improvised Manufacture of Nitric Acid > How lame, but easy!
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View Full Version : How lame, but easy!
SantasL.Helper S e p t e m b e r 5 th, 2004, 07:19 AM

Ey, i lately discovered the m ost lam est thing.
My parents where using these little rub ber stoppers on wine bottles and this handpum p that fitted on the stoppers with which
you can vacu u m p u m p wine bo ttles to preservate it.
Now i'd never really thought of using it, but yesterday i tried them on my setup and these things actually work. They fit
perfectly on m y 1L 3neck distilling flask so i just use that one as receiver and put such a stopper in and closed the other neck.
I m ixed 222 ml nitric with 444 m l sulfu ric, close d the setup and started pum ping it with the wine bottle pum p. When i figured i
created a nice vacuum, i started heating it to 140/130 degrees celsius, as i also do withou t vacuum when distilling n itric.
I just regulated m y pum ping, just everynow and then to c o m p e n s a t e f o r t h e g a s s e s a n d h eating. I noticed that the nitric acid
started to distill W AY faster (lower bp) then norm ally, so i lowere d the tem perature of m y b a t h . I ' v e n o t b e e n s o h a p p y i n m y
little science life seeing drop after drop nitric and withou t a single tint of yellow, not even in the gasses in m y setup. Everything
was just clear!
W hen i m easured 43 ml of the gained nitric, I found out it had a concentration of about 98%, though i can't fully conclude it
was THAT high due to m e w e i g h i n g s u c h a s m a l l a m o u n t of nitric with a n ot very precise (1gr) scale. Anyhow, I'm pretty sure
the concentration was som ewhere up in the 90.
So to everyone with a vacuumless setup, go to the store and get yourself these winebottle stoppers and ha n d p u m p s . W orks
like :eek:
Oh, btw can anyone tell me at what gas tem perature (therm o m eter located above the exit of m y d istilling flask) i should distill
the nitric under vacuu m and at what tem perature i should set m y frying pan? thanks
Ps, frying pans work great for (am aturistic) hea ting!
hereno S e p t e m b e r 5 th, 2004, 09:05 AM

Check your pump, it will dissolve pretty fast if it isnt made for nitric (which it obviously isnt!). Your m u m m y wont be pleased.
tmp S e p t e m b e r 5 th, 2004, 11:29 AM

SantaL.Helper, there are numerous threads on nitric acid production all over this
forum . Perso nally, I like m y hydroaspirator, cost about $9(USD), and does a
great job of providing vacuum as well as washing those noxious fum es down the
drain in the process. I wouldn't risk using m y vacuum pum p due to the corrosive
nature of HNO 3. Look around on this forum. You'll find plenty of information on
m aking HNO3 with or without vacuum. IIRC, Brainfever had a vacuum - l e s s
m ethod that did a good job.
SantasL.Helper S e p t e m b e r 5 th, 2004, 12:49 PM

yea but vacuum less synths ve ry often end in a pretty NO2 rich m ix. W hich yield crappy in producing RDX.
Anyhoo, i don't get how it works... W hen i distill nitric under vacu um with a gasstem perature of 80 degrees, i get a just as pure
nitric acid as when i heat the gas temp up to just 60 degrees celsius. I'd expected a lot of water to be distilled over when i
heated till 80 degrees but that didn't happen... Anyone has an explanation?
Dave Angel S e p t e m b e r 5 th, 2004, 03:14 PM

Certainly this could have been posted in an existing HNO 3 topic, but the results a re still in teresting. If you can make a litre of
it Santas, then please do so; as you know, you r measurements will be le ss affected by error.
I'm currently distilling w/o vacuum , (hoping to eventually get very pure HNO 3 via the DCM/dry ice method), but these
h a n d p u m p s a r e n o t a l l t h a t e x p e n s i v e a n d I h a v e a s c a le accurate to 0.1g, so I'll see wha t I can do about trying this out
m yself. Is it 19/26 joints they fit? It looks that way from the wine bottle neck, and I have a suitable three-neck. I can see that
large batches might be quite tedious/tiring to produce with a ma nually operated vacuum t h o u g h .
I think the reason you don't g et water com ing over with a vacuum is that the effect of the H2SO4 on water is a chem ical one,
and you are only altering physical properties by applying a vacuum .
SantasL.Helper S e p t e m b e r 5 th, 2004, 08:26 PM

yup, they are 19/26 necks the stoppers fit in. I got 100 ml now of (calculated again) 94% nitric i guess. I'd like to create a litre
of the stuff, but at my current rate, that will tak e 20 distillations :p as m y b i g e s t f l a s k i s a 1 0 0 0 m l one. Bum mer...
T h e s t o p p e r s h o we v e r cost 4 p e r 2 i f n o t m i s t a k e n . T h e p u m p s are a bit m o r e e x p e n s i v e ( 1 0 ) b u t i guess you can g e t t h e m

a lot cheaper cause the one i saw in th e shop looked pretty stylish and shit, we got like an ugly one, gotta be cheaper.
here's a picture of the pump + stoppers (our pum p looks exactly the same but is coloured white though, details details... lol):
http://www.winestuff.com/acatalog/W 1116full.jpg
thelasttrueone Novem ber 5th, 2007, 08:03 PM

I a m t h i n k i n g o f m a k i n g a n a p p a r a t u s o u t o f a m ason jar, a ma rtini glass, a beaker, that pump and a copper valve . C o u l d I
have a picture of your apparatus for comparison?
festergrump Novem ber 5th, 2007, 08:25 PM

SantasL.Helper hasn't been back here since June 12th, 2005 08:44 AM.
Alwa ys a goo d idea to pay close attention to when posts were m ade. This thread is 3 years old and by dredging it back to the
t o p o f a s e c t i o n t o a s k a q u e s t i o n o f s o m eone who doesn't stop in anymore and not really have anything o f value to offer
yourself... that's calle d necrom a n c y ( a b a n n a b l e o f f e n s e , I ' m a f r a i d ) . : e e k :
thelasttrueone Novem ber 5th, 2007, 10:42 PM

Thanks well I'll look out for that in the future (or past?). *goes to read rules again*
megalomania Novem ber 6th, 2007, 04:33 AM

R e i g n i t i n g a n o l d t h r e a d i s g o o d , a s k i n g q u e s t i o n s o f t h e l o n g d e a d , n e c r o m ancy, is not g ood...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > white
nitric by ultrasound?
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CO2 can be expelled from water by powerful ultrasound.
Why shouldn't it be possible to expel excess nitrous gases from concentrated nitric acid in order to obtain 'white nitric acid' :) ?
Ultrasound devices are easily available as living-room humidifiers creating strange looking cold steam.
100 people should have had this idea before me - why can't I find any post about it?
Boomer November 11th, 2004, 01:06 PM

Because you are a genius! :)
Only tests will show whether it works. The thing that makes me pessimistic is that CO2 is a gas dissolved in water under pressure. It probably is driven out by US in the same
way it is driven out by shaking a coke.
In contrast, NA is a real solution, it is liquid at RT even if pure, plus it is hygroscopic. Moreover, the "strange looking cold steam" is no vapour but droplets thrust out by the
shock waves.
Still worth a test IMO - it would be soooo convenient! :D
FUTI November 11th, 2004, 01:57 PM

yes as I remember CO2 suposedly should dissolve in water with chemical reaction and make carbonic acid and giving true solution with higher concentration then in some other
solvent...but it dissolve in benzene and water in same amount so I guess this theoretical story that we are spoon-fed true school is bullsh*t. Ultrasound is used for chlorinated
hydrocarbon removal in drinking water process units.
Marvin November 11th, 2004, 06:40 PM

Hmm, 2 thoughts occur. Firstly this seems like a high tech solution to a low tech problem, whats wrong with bubbling dry air or oxygen through nitric acid?
Secondly you are trying to expell nitrous gasses by accelerating the process that produces them and drives them out of solution, but you need to avoid accelerating the reaction
that decomposes nitric acid producing oxygen and drives that out of solution. I have the feeling ultrasound will not discriminate too well.
vurr December 4th, 2004, 05:43 PM

H2CO3 is much much more unstable than HNO3...(well:shaking results for HNO ??)
Y gonna get near x% nitric ac mist from x% nitric ac with US

to vurr: What I meant is that HNO2 and NO maybe can be removed by ultrasound as they are more unstable then HNO3. You are right about possible aerosolic dispersal of acid
if device is not properly made and operated.

HNO2 decomposes readily with carbamide { (NH2)2CO } to N2 , CO2 , H2O / eliminating nitrous acid traces in orgsynth /
not sure about NO...
but is it suitable for HNO3 cleaning?
FUTI December 7th, 2004, 08:23 AM

I agree about adding urea remove HNO2...but it looks to me that US is easier way (you don't add nothing to mixture just do thermical/mechanical tretment). I believe that NO
can certainly be removed by US being dissolved as neutral molecule more like chloroform or CO2, HNO2 is trickier in that way but energy supplied by US can decompose it.
It is not best idea to use US for HNO3 cleaning, but if you going to make a small scale production it will do the job.

ouF! it's NO2, that brown contaminant, that we want out...
and test shall be done to be sure.
solubility of NO is 7.4 ml/100g H2O @ 0C and 2,6 @ 100. presence should not hurt...
HNO2 - unstable;visual experiment:NaNO2 + HCl in water and heat,should decompose readily,showing lot bubbles.
================================================== ===
urea nitrate decomposes @ 152C

and giving off kind a acidific fumes(what? UN to urea+HNO3? without water)
over 16xC (???) ammonia starts form from pure carbamide...(smell)

NO2 is the same thing that makes HNO3. When dissolved it makes HNO3 and HNO2 through disproportion. HNO2 as you said is not hard to remove, but I wondered will US shift
the some balance. If some kind of balance formed in solution is responsible for reaction not going to completion maybe nitrite and NO removal can shift it to white nitric acid.
Anyway NO2 is also a neutral molecule so US could possibly remove it to.
You are wrong about NO and HNO2 presence can't make any harm. HNO2 can change nitration ussualy by slowing it down. It also can alter the reaction mechanism from
cationic to radical.
If you will use it for production of metal salt or urea nitrate then I guess it is safe because nitrite will decompose or they are more soluble then nitrate.

industrial:
a) 3 NO2 + H2O -> 2 HNO3 + NO (or maybe here should be = instead of -> ? reversable reaction?)
b) 2 NO + O2 -> 2 NO2
in b) O2 is from air,so adding US, esp.when mist is formed ,should affect formation of NO2 and over that affect also reaction a).

Super!!!
This exchange of opinion finaly get some results. Congratulations vurr, you have just make fantastic remark. With this we could combine two strategies and possibly combine
its effects/mechanism...both bubbling of the air and US.
Only problem that remains is acid aerosol formed but with some kind of particle removing design this can be overcome. Filter of some kind...glass frits, fiberglass curtain, some
of those cyclonic filtering device. Anyone with idea?
Mr. Pseudo December 11th, 2004, 02:48 AM

If reaction is carried out in a sealed vessel, steam can be injected into the reaction chamber, and the resulting aqueous HNO3 condensed.
Say the reaction is carried out in a large roundbottom with a ground glass joint at the top. Set up an apparatus which will force steam into the beaker (perhaps through an
insulated glass tube, and keep a small vent open to the air to release pressure. Reaction vesel could be submerged in cold water for cooling.
If it's impossible to get the bubbler into the flask while it's in a bath, you could probably just run cold water over it.
I don't think that any filtering device within our price range could effectively remove an acidic aerosol.
meselfs February 7th, 2005, 10:24 PM

Hmm, 2 thoughts occur. Firstly this seems like a high tech solution to a low tech problem, whats wrong with bubbling dry air or oxygen through nitric acid?
I don't think that would work. Industrially, clear nitric acid only forms when the oxygen/water/NO2/NA mix is subjected to 5 MPa (about 50 atm). But note: Common oxygen
cylinders come fresh with around 14 MPa, so it may be possible to just wiegh the ingredients, put them in an aluminum cylinder (magically, NA doesn't attack aluminum), and
add the oxygen under pressure.
Concerning the ultrasound, I think it might rid the acid of NO2, but that would leave behind around 60%-70% clear acid. The concentration never goes higher unless you do
something drastic, eg apply pressure as previously noted.
But who knows, the awful high frequency shaking might work a miracle. Somebody with one of these ultrasonic things please try it :-> .

The early part of the thread does not discuss increasing the concentration of the nitric, just getting rid of nitrous gasses to produce white nitric, a pinch of urea and dry air is a
standard method for this. High pressure oxygen has been discussed in other threads, its extremely unlikley a pure aluminium container would be able to take 50 atm.

Okay, sorry.
But don't be fooled... an aluminum tank definitely can withstand that. I've been doing pnuematics experiments since I was 12, compressed gasses are way overrated. I once
made a pump that held back 15 atm without any noticeable leakage.
I've seen medical oxygen cylinders made of aluminum, and they are designed to hold back the 14 MPa that welding oxygen cylinders do.
Meawoppl September 10th, 2006, 02:22 PM

I think this whole concept is great, just as long as you have coated you humidifier in teflon. Humidifiers use peizoeletrics to make their high frequency vibrations. I am not to
optimistic about the resistance to those materials to Fuming Nitric Acid. PZT ( a common peizo material) has to be manufactures under vacuum and other demanding
conditions.
I do think however that if you set up a pair of peizoeletrics similar to that used in these sonoluminescence experiements, you might have a promising technique.
http://www.techmind.org/sl/#behaviour
Of particular intrest is the following quote:
"With very gassy water, small bubbles may form in the vicinity of the trapped bubble, and feed it, sometimes to the point of instability (bubble dissolves/rises to surface)"

I have done some more research on that avenue, but most things I have come across tell me that "the mechanisim is not well understood" The bubble seems to form at
antinodes of the standing wave, so I guess if you used the process to pull a bubble together, then turn it off, it may just float to the surface before being absorbed? Really this
is more of an impractical mental exercise than something that would be economical. Those peizoeletrics are not cheap either, but if mounted outside the flask, they will
basically last forever. I have some itty bitty ones, but no fuming nitric handy, I may give that a go at some point in the distant future.

Improvised Manufacture of Nitric Acid > Steam distillation
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Pb1 January 15th , 2 0 0 5 , 1 1 : 2 7 P M

W ould it be feasible to steam distill concentrated nitric acid from a mixture of XNO3 and H2SO4? Not with water, of course, but
with an inert, imm iscible low-b oiling solvent (chloroform, m a y b e ) ? T h e h i g h e s t t e m perature required would be the boiling point
of the solvent, so the re would be little or no decom position.
megalomania January 16th , 2005, 02:00 AM

I wouldn't see why no t . I t d o e s s t r i k e m e a s s o m ewhat wasteful of solvent to try that since final distillation would require extra
work in the e nd. There is a reason the tried and true m ethods are best: they are tried and true.
knowledgehungry January 16th , 2005, 10:22 AM

Don't forget fire hazards and poisoning from vaporized solvents.
tom haggen January 18th , 2005, 03:59 AM

W hat exactly is steam distillation? I was reading up on isolating safrole from natural products and it said that steam distillation
is th e only way this can be done. My first thought is why wouldn't you be able to soak the plant ma tter in th e proper solvent to
form a n e m ulsion, and then vacuum distill obtaining the pure product.
Pb1 January 22nd, 2005, 02:47 PM

S t e a m distillation is blowing a v a p o r i z e d s o l v e n t ( u s u a l l y s t e a m ) which doesn t m ix with what you re trying to distill into t h e
crude reaction product. The vapor picks up anything volatile, leaving with a sm all portion of it on its way to the condenser. You
condense the vapors and the distillate contains the solvent and your product. As an example, say you want to get som e
essential oils out of a flower. Pass steam over it and the oils will come over with the steam . C o n d e n s e t h e s t e a m a n d t h e o i l s
come with it, form i n g a n i m m iscible layer.
Thin king abo u t t h i s s o m e m ore, you wouldn t e v e n n e e d a n i m m iscible solvent if y o u d o n t c a r e a b o u t s m a l l l o s s e s . J u s t u s e

an inert low-boiling solvent an d boil it off, leaving you with nitric acid.
FrankRizzo January 22nd, 2005, 07:14 PM

A date with the search engine will turn up a thread where exactly this is discussed (using m ethlyene chloride).
S t e a m distillation is blowing a v a p o r i z e d s o l v e n t ( u s u a l l y s t e a m ) which doesn t m ix with what you re trying to distill into t h e
crude reaction product. The vapor picks up anything volatile, leaving with a sm all portion of it on its way to the condenser. You
condense the vapors and the distillate contains the solvent and your product. As an example, say you want to get som e
essential oils out of a flower. Pass steam over it and the oils will come over with the steam . C o n d e n s e t h e s t e a m a n d t h e o i l s
come with it, form i n g a n i m m iscible layer.
Thin king abo u t t h i s s o m e m ore, you wouldn t e v e n n e e d a n i m m iscible solvent if y o u d o n t c a r e a b o u t s m a l l l o s s e s . J u s t u s e

an inert low-boiling solvent an d boil it off, leaving you with nitric acid.
Pb1 January 23rd , 2005, 11:55 AM

Thin king back on what I said, it wouldn t quite work that way. The s a m e principle that gives you the acid would als o carry it
off. You d n e e d a f r a c t i o n a t i n g c o l u m n t o k e e p t h e a c i d .
Fran k: Are you referring to that last line? I searched the forum without finding anything about steam distillation of nitric acid.
I t h i n k y o u re confusing this idea with the final step in the MeCl2 procedure where the MeCl2 is b oiled off. O therwis e , t h e i d e a s
have nothing in com m o n .

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Nox
Purging Reaction
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mongo blongo February 15th, 2005, 07:41 AM

Does anyone know what the reaction is for purging Nox from HNO3 with urea? I'm sure I have seen it here before but this certain post is proving very elusive.
I'm assuming that urea nitrate is formed first but I can't see what happens when O2 is introduced. Is the reaction catalytic?
If urea nitrate is the first reaction product then I presume that higher concentrations of HNO3 could be achieved by using urea nitrate instead of urea.
simply RED February 15th, 2005, 04:48 PM

Little urea is added to red nitric acid to lower the Nox content in it.
The Nox react with urea to produce N2, CO2 and H2O.
Urea nitrate in such low quantity is not formed due to urea nitrate solubility in the acid.

Wouldn't that then make it less concentrated with more H2O in it? I remember reading posts stating that after titrations, it was more concentrated after purging.
cyclonite4 February 15th, 2005, 10:57 PM

Wouldn't that then make it less concentrated with more H2O in it? I remember reading posts stating that after titrations, it was more concentrated after purging.
The H2O probably escapes as water vapour
simply RED February 17th, 2005, 05:48 PM

Water reacts with NOX to form HNO3 again. It exists in balance.
Even white nitric acid will turn red if it stands in warm place.
Urea can not make it more concentrated...
Anyway my reaction is from chemical manual. Correct or not...
"The main purpose of adding urea to red fuming HNO3 is to purge it of HNO2 (formed by NOx) which could influence out-of-control reactions:
H2N(-C=O-)NH2 + 2 HNO2 --> CO2 + 3 H2O + 2 N2 "
The usanet article helped to translate the manual.
FUTI February 21st, 2005, 05:11 PM

Bubbling air through acid will make it concentrated, if it is dry and warm, and remove NOx in process too. Bubbles that comes out of solution contain a small amount of water
depending of water vapour pressure...if it works for sea-salt producing facilities that use wind to speed the evaporation I can't see reason not to work here also.
grendel23 February 22nd, 2005, 05:23 AM

Dry air will remove NO2, it will not concentrate acid that is already over 68%. At concentrations above 68% more HNO3 will evaporate than water,
below 68% more water will evaporate, but it would take forever and you would lose acid in the process.
DF90 June 20th, 2007, 01:05 PM

Would it be possible to place the acid in a vacuum flask (a buchner flask with a solid bung) for a short period of time, to "suck out" the NOx? It's just an idea but I think it could
work :D I'm sure I have seen it on the forum before but I have spent the early hours of the morning searching for it with no results :(
mike16 June 21st, 2007, 07:55 AM

I once put 10ml of yellow 70% HNO3 in a desiccator with 98% H2SO4 as the desiccant, in the hope that the H2SO4 would suck the water out of the HNO3 to concentrate it.
The next day as expected I had the 10ml back, so it was still only 70% HNO3, but it was crystal clear!!
The H2SO4 had somehow taken the NOx out of the nitric acid.
alancj July 17th, 2007, 05:31 AM

Would it be possible to place the acid in a vacuum flask (a buchner flask with a solid bung) for a short period of time, to "suck out" the NOx? It's just an idea but I think it could
work :D I'm sure I have seen it on the forum before but I have spent the early hours of the morning searching for it with no results :(
Yes, I have tried that before. It takes a while; from my one time experience :). I used a side arm flask, with a rubber stopper in the neck, a vacuum pump (for food canning)
and pulled a vacuum while gently warming the acid.
From a couple hundred mL of yellow acid at start I got a water clear acid after about an hour. My acid wasn't very concentrated, less than azeotropic, but it still ate up the
stopper. Agitation would help a lot.

blues.....
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lowjack February 18th, 2005, 12:01 AM

Well anyone who's had enough experience with Nitric acid knows that wearing heavy duty chemical protective gloves is a must. It usually only takes one time of spilling any
amount of N/Acid onto human skin and the poor victim has branded themself with that ever-so-nasty Yellow skin stain for what seems like for ever.
Anyone got a remedy for Nitric oxidization yellowing on human skin? :confused:

I think you mean nitric acid yellows...
The nitric acid has mucked up proteins in your skin. If there's a better cure other then leaving it alone, I'll eat my hat.
c0deblue February 21st, 2005, 01:28 AM

You could always try a DIY "chemical peel" with NaOH, "as recommended by dermatologists". Of course you'd be substituting "beefsteak pink" for "nitric yellow" - at least for a
while - but you DID ask. :D
Seriously though, you might be able to reduce the stains somewhat with 240 or so grit silicon carbide paper. Get your hands as clean and dry as possible (e.g. using a hot air
drier) and have at it. Careful though, a new sheet of 240 takes off skin layers pretty fast.
Skean Dhu February 21st, 2005, 09:56 AM

If your going the abrasive route, you may want to consider the various abrasive shop soaps designed to get things off your skin that want to stay there. Cherry bomb made by
Zep is a good one, it has a nice cherry scent, There is also the Lava soap sold by gojo I believe.
vlodjak February 21st, 2005, 02:06 PM

I`ve got those nasty stains too, but they usually don`t stay for a very long time. Usually they wear out in a couple of days.
Jacks Complete February 21st, 2005, 04:16 PM

Take up smoking roll-ups. :-)
lowjack February 24th, 2005, 01:37 AM

It wouldnt be so bad had I spilled the stuff on myself being clumbsy. No, an acquaintance of mine didnt feel I was capable of pouring off a few liters out of the keglike
container we acquired it in. This damn nitric container keg was so damn heavy, but I had enough experience pouring off bits here and there. Anyways long story short, he sees
its an acid and assumes that if it touches his body/hands in any way ,that they'll sizzle off or something. I really didnt think he was as weak as he obviouly was because after
;glug glug and near 5 or 6 glugs till were done, he twitches and my hands holding the funnel caught a nice little splash from what he later claimed was a mosquito buzzing in
his ear.
Little price to pay for the $10 I charged him for the 40 oz. bottle full of nitric.
I had a guncotton mission a few years back but I never saw it through. Good thing too cuzz I'd probably have wound up in pieces blown about the room.
FUTI February 24th, 2005, 12:36 PM

No known cure for that I think. You nitrate protein of the skin and that made skin coloured. Base or reduction can sometimes made thing worse from yellow to redish. In a two
week time when your skin replace the surface skin cell layer your problem will vanish.
EDIT: The name of the thread lead me to false assumption that you meant blues as in state of mind caused maybe by NOx...and that is a head-ache that is loooong
remembered. :eek:
Elucifer March 1st, 2005, 02:26 PM

shoot down to your pharmacist and ask for some gentian violet, spray it on with a mister and the purple/violet covers the yellow
Well anyone who's had enough experience with Nitric acid knows that wearing heavy duty chemical protective gloves is a must. It usually only takes one time of spilling any
amount of N/Acid onto human skin and the poor victim has branded themself with that ever-so-nasty Yellow skin stain for what seems like for ever.
Anyone got a remedy for Nitric oxidization yellowing on human skin? :confused:
The_Duke March 7th, 2005, 05:20 PM

When Nitric acid comes into contact with the skin it causes the yellow coloration and stains because of certain proteins in human skin are oxidized by the HNO3 and produce
yellow xanthoproteic acid.
I dont know if there is any way to actually get rid of the yellow stains without removing skin layers. :(
DYK, that when severely poisoned with HNO3 that the yellow xanthoproteic acid is secreted through the skin mainly around the mouth?


malzraa March 8th, 2005, 01:18 AM

If these weren't proteins, we could just reduce them. Unfortunately, the acid not only oxidizes them, it also denatures them. Your skin is fucked, buddy. High grit sandpaper is
your best option. Speaking of yellow stains, has anyone ever stained their hands with picric acid? That is a bitch to get off too, and it is yellow as hell.


Child-of-Bodom March 10th, 2005, 10:38 AM

TNP is the most horrible yellow stuff I've worked with...
Stains can best be removed with acetone, but trow away the papers you used! I used (latex) gloves during my TNP syntheses, and it even went through them!
I was most surprised by the following, I let the TNP dry on the filterpaper, placed on 7 layers of tisseu paper, which layed on a plastic, transparant mat on the table, with under
it a cotton sheet. After 24h even the cotton sheet was yellow!!
Ontopic, there is no reasonable cure against the yellow stains... But how toxic is it?
Not that I am scared of anything toxic, but more carefull... NO2 is not taken up by the skin, so a spill means nothing more than yellow spot on the skin for a few days,
afterwhich the skin will harden and fell off... f the spot is not too big of course.


atlas#11 October 3rd, 2006, 02:46 PM

Haha, this reminds me of about a year ago when a 500 gallon tank of nitric acid exploded on the railway down town. So much yellow! literaly, yellow clouds of mist
everywhere. I bet the cars in the vicinity are rusted to hell about now. Yeah, alot of pedestrians were stained hardcore, I'm not sure of the casualties, but I know a few went to
the hospital. Either way, a damn waste of good nitric.
Your skin problem will be gone in 28 days (I think thats the time it takes for your skin to change layers.) or less. What are you worried about any ways? You think anyone will
assosiate yellow skin with explosives? Just tell them a highlighter broke in your pocket or something.

I have been stained by picric acid, nitric acid, and silver nitrate. I always wear gloves, but a few drops here and there, or picking up a bottle after you deglove can get you. The
best cure is to wait for the skin to regrow. The staining is not dangerous or toxic in moderation. If you are yellow from stem to stern, you might want to see a doctor...
Cindor October 11th, 2006, 08:20 PM

If you don't care about your cells and just want to get the yellow away try with H2O2... maybe 30 vol., 50 vol. or so...
Not that it will eat up your skin, but it wont help, and will oxidize it a little bit.
sbovisjb1 October 20th, 2006, 07:09 PM

I suggest you getting the skin treated or try washing it with a mild acid such as lemon juice. Then try to remove the skin, but as megalomania said, the best way is to let the
skin grow back.
Universal November 13th, 2006, 02:54 AM

From what I have found with nitric acid burns, is that they turn into a sort of blister and peel off :o. They last for a while but it depends how severly stained you are. They
don't hurt though, thankfully.

Improvised Manufacture of Nitric Acid > A New Take on HNO3 Prod.
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Meawoppl September 10th, 2006, 04:54 AM

I was thinking about this for some time now, but am not quite sure how feisable it is:
One of the ways to produce NO and thusly strong nitric acid is by spark discharge generating plasma and an elusive bit of 03
and thusly NO. I ran into a website that describes in detail, a way to make a steady plasma arc inside of a microwave
oven(http://jlnlabs.online.fr/plasma/gmrtst/), specifically noting on the site "the plasmoid generates ozone (O3) and nitrogen
oxydes ( NO and NO2), so you need to do this experiment in an open and well ventiled area."
I have been thinking that this arrangement required far less prep than some sort of television transformer or car winding that
I had heard described earlier, and only an old shitty microwave that you dont mind punching a few small holes in and some
glass that I think I can get at home depot. Does anyone here think that this arrangement could work?
Secondly, you could use a pump to apply a small forward pressure or ideally build a small stirling engine pump that works to
dissipate the heat on the plasma container. That would be way cool, as the process would only have the cost of running the
microwave.
Also notably, "the plasmoid is produced in a spherical vessel, it is self-confined ( like a ball lightning ) by spherical pinch effect
and thus the hot plasma is not in contact with the glass vessel" so the glass wont get to hot too quickly and if I understand
the physics correctly, the graphite rod is only necessary for starting it, from there, the microwaves can continue to excite the
gas.
Do you think this sounds like a reasonable enough experiement to spend $50 at the flea market?
simply RED September 10th, 2006, 05:02 AM

Even you have NO or NO2 in excess you can not make conc. HNO3 at home.

Another page regarding the same phenemonon:
http://jnaudin.free.fr/html/oa_plsm2.htm
Also the addition some water vapor should make the setup complete.
From my understanding, under plasma conditions, molequels split up and become monoatomic b/c its thermodynamically
favorable.
Thusly:
3 O2 + 7 N2 + 5 H2O ---- hv ----> 11 O + 14N + 10H
Other than recombining into their previous compounds, these reactions would take place:
11 O + 11 N ----> 11 NO
3 N + 9H ----> 3 NH3
The NH3 could be condensed out, leaving a higher net oxygen concentration in the system.
Recirculating the gas through chilled water would begin the acid formation process and eventully exhaust the Nitrogen in the
system, thusly serving as the oxygen bubbling process.
I doubt that this process is energy efficent if feisable, but if its possible, it could be performed with some simple glassworking,
and has a plesent by product of ammonia.
[edited for a typo]

This sounds like it has some potential, but that is something experimentation will have to bear out.
One problem I foresee is how to use this for production of significant quantities of nitric acid. The best way to do that is with a
constant gas flow of air, but if the plasma ball relies on vaporized carbon particles in a confined sphere, any air flow may
disrupt plasma formation. In a closed system all you would get is a small quantity of trace NO2 gas and ozone.
Another problem may be too much UV light from the plasma breaking down a significant portion of the NO we do get.
It may be more appropriate to use a catalytic material that lends itself better to NO formation besides carbon. Such a material
may need to form an oxide while in the plasma, and the microwave emitter will need to be specially tuned to the materials
particular resonance frequency.

I have the spare cash to fund at least some inital inquiry into this project, so I think that I will.
I am going to keep a lookout for acheap ass microwave, and do minor bit of disassembly/violation of the fcc. There is some
mention that the actual microwave magnetron is switched on and off 60 times a second to keep it from overheating. I think
that I will hardwire it on and add some additional cooling to keep from frying the anode too quickly.
Also I am going to need to find a borosilicate sphere, or blow one from a test tube. If I do one smaller than that huge sphere
thing, the heating problem i think will dissapate largely as the V/S.A. ratio gets better. Perhaps a series of small spheres . . .
we shall see.
If anyone has any thoughs or experience in this area, please tell me anything you know. There is nothing worse than
repeating another persons mistakes and failures.
simply RED September 11th, 2006, 06:47 AM

If UV does the trick. Use directly UV source (Hg lamp, etc). Find what wavelenght does the trick (UV spectroscopy or by theory)
and chose source that emmits mostly there.
Russian scientists experimented with this ("Plasma or UV for HNO3" in 1973 with absolutely no success).
Original article in:
"1975 RADIO (DOSAAF) magazine" forget which month.

There is already plenty of experimental data online about people generationg NO and NO2 via this method. The question is
can I somehow form ammonia from those conditions. My suspision is that normally the NO/NO2 pathway is perferred over the
NH3 route, as the amount of ozone generated created a very oxidising atmosphere. I bet if the O2 were removed from the
vessel, at least some NH3 would come about.
So I am buying a $20 microwave from craigs list, we shall see.
Alexires September 13th, 2006, 10:23 AM

Meawoppl, I had exactly the same thought last night. If the O2 was burnt out of the air, or somehow removed, then NH3 would
probably be produced.
At some point in the following you would need to find a way to input H2. After the bunsen burner stage, maybe have
something electrolysing water to form the H2. Not alot of input would be needed, so this is probably better than having a H2
tank.
My idea would be running the air through a dessicator (remove H2O) then burn it using a bunsen burner (the little hole that
you open at the bottom). Cool it if necessary, then route it through your microwave gizmo (drill a hole in the door and stand
the hell away). Then pass it through a condenser running the dry ice/acetone slurry that is talked about in another thread
(http://www.roguesci.org/theforum/water-cooler/5667-dry-ice-acetone-slush.html).
This will hopefully cause some amount of ammonia to be formed, and then liquified through the condenser. Probably most
ineconomical, but then the used air could be passed back through the device (this will do away with the dessicator and the
oxygen remover).
Leave it going for a while might produce NH3.
sprocket September 13th, 2006, 12:00 PM

My idea would be running the air through a dessicator (remove H2O) then burn it using a bunsen burner (the little hole that
you open at the bottom).If the goal is to produce a dry stream of nitrogen you might want to do it the other way around
seeing as the combustion is going to produce a lot of water. Perhaps it would be a good idea to remove the carbon dioxide as
well by bubbling it through an alkaline solution, then this needs to be done before the drying as well. The hydrogen inlet
needs to be after the combustion step (obviously), but before the drying.
The big problem with removing oxygen through combustion is getting the fuel/air ratio just right.

I have been thinkining for a while now, and I think that this process has become a bit more complicated that originally
intentioned. However it could be greatly simplified by splitting the process into three different loops:
Loop 1:
Atmospheric air + O2 --> 03 ---> NO + NO2 ---> Nitric (fuming) + excess NO/NO2 To be recycled through loop
(I know that this loop works)
Loop 2:
Atmospheric Air + H2 --> NH3 + O2 --cooling--> O2 (For the bubbling)
(Looking at some thermodynamic data [and making an estimate of the arc temperature from black body spectra] I think that
this could work.)
Is there a way to estimate your K eq from dG (dH and dS data). I seem to recall a link between the two, but I am not sure
what to search for.
Loop 3:
Electrolosis of H2O ---> H2 + O2 (For supplying above processeas)
(I KNOW that this works. In fact I have parts for most of the apparatus)
I played with the idea of making loop two utilize some sort of hydrocarbon, but the idea of carbonated nitric acid was enough
to turn me off to the process.
Is CO2 a weak base?
Any more thoughts? My first experiment when I pick up the microwave today, will be trying to make some ammonia from
water, and air. I will put ingredients in a closed sphere covered with a balloon and then chill the products after some amount of
reaction time. Hopefully (if my balloon dosent melt/explode) there will be a bit of dilute NH3.
Any other experiments that you guys would suggest?
[edited for a missing ")"]

I just love some of the things scientists do in journals. While looking to see if there is any prior published work on microwave
production of ammonia I found this
Microwave irradiation at 4kW for 0.4 sec applied to the heads of mice produced an increase in brain ammonia.
Your mom might not like you sticking firecrackers up a frogs ass, but saying you are testing the effects of application of
propellant base to anterior portion of Rana catesbeiana sounds educational.

So what you are saying is that I need a small box full of mice w/ spinal taps? :p
In the relm of meaningful news, someone beat me to the microwave *shakes fist*, but I am sure I will be able to scrounge
one up soon.
Meawoppl September 21st, 2006, 12:00 AM

A large amount of the heating that mircowaves do is due to alignment of dipoles w/ the microwave em feild. I think that this
would discourage the formation of NH3 under such circumstances as it is fairly polar. In any case, there is still no progress on
the microwave front *shakes fist*. I will keep you all updated.
nbk2000 September 21st, 2006, 08:25 AM

Microwave irradiation at 4kW for 0.4 sec applied to the heads of mice produced an increase in brain ammonia.
Maybe there's more to it than meets the eye.
Perhaps part of larger research on microwave HERF weapons and their use as lethal, or less-lethal, weaponry?

I have read that at Raytheon they are working on something very similar to this, but is is more directed. Some sort of
microwave laser.
http://www.defensetech.org/archives/001219.html
Altroman December 8th, 2006, 11:06 AM

Microwaves are often used to "fix" (i.e. cook) brain tissue in order to preserve the locations of certain neurotransmitters in the
cortex. Subsequent sectioning and staining can then reveal these substances. [See: http://www.ncbi.nlm.nih.gov/entrez/
query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16176062 Typical RF powers used to cook a rat's brain: 5kW
for about 3 seconds - Ouch!
Although far off topic, I mention this because it illustrates how difficult it is to actually use microwaves as a lethal "weapon,"
since it takes many kW for many seconds to denature just a few cc of gray matter.
Formation of a stable plasma in air with continuous water scrubbing of the exhaust to extract the NO/NO2 gas mixture should
far easier to arrange. Either oxide produced in stoichiometrc excess will simply remain undissolved.
PeterB2 January 16th, 2007, 11:49 AM

If you want to make NO2, I read about a way in "The Golden Book of Chemistry Experiments" (page 34 I think). Gently heat a
mixture of sodium bisulfate (used in pools) and potassium nitrate together in a test tube in a one to one ratio. If it produces
much NO2 at all, the only challenge left is to bubble it through water. I haven't had the weather on my side to be able to try
this yet, but if it works well, I'll let you know.
crazynlazy January 16th, 2007, 10:16 PM

Are you quite sure of that reaction Peter? I had always read that molten sodium bisulfate acts quite similarly to sulfuric acid.
Eventually, the sodium bisulfate decomposes yielding sodium sulfate and the hydrogen cation. The hydrogen that is removed
from the sodium bisulfate replaces the potassium (and vice versa) in KNO3 thus forming nitric acid. Thus, by mixing
potassium nitrate with sodium bisulfate and heating, you get the following reaction:
NaHSO4 + KNO3 --> NaKSO4 + HNO3
Consequently, the nitric acid is obtained, albeit more directly. I am rather sure of this considering I have made hydrochloric
acid using sodium chloride and sodium bisulfate. However, I could be wrong.
As for the initial post, this seems like a rather cumbersome way of producing nitric acid. Distillation seems to be a simpler,
less toxic form of this synth. But I guess it never hurts to know.
tmp January 17th, 2007, 01:34 AM

I wouldn't be surprised that NaHSO4 and KNO3 heated in a test tube yields
NO2. The heat in the test tube should decompose the HNO3 that forms.
Decomposition of HNO3 can occur during normal distillation if the temperature

is too high. Oxides of nitrogen from decomposition is what gives the "red"
and "yellow" nitric acids their color. The highly concentrated, "fuming white"
HNO3 is usually distilled under vacuum. The result is a more concentrated
product with little or no decomposition because the vacuum lowers the
boiling point. I said "usually distilled under vacuum", because a method was
devised that could produce white nitric without distillation. Even in that
method temperature determined if the acid came out "red" or "white". At
60C the acid came out "white".
If the bisulphate is all you can get your hands on, go for it ! I was at the
hardware store yesterday. They had plenty of H2SO4 drain cleaner on the
shelf so I'll stick with vacuum distillation for now.
PeterB2 January 17th, 2007, 04:42 PM

Crazynlazy, no, I am not sure about the reaction--I only read it in the book and have never tried it myself but thought it would
be worth a shot. After if it is in a published book (albeit, a banned book), then it should be fairly legitimate.
Yes, I have some sulfuric acid drain cleaner as well and would like to try nitric acid sythesis when I get the chance. I thought
the whole argument was that NO2 and water would generate a more concentrated and purer product and thus worth some
investigation as an expedient means of sythesis.
Having just begun my journey through the fascinating world of chemistry though, I do not have a distillation apparatus (other
than the one described at http://www.hometrainingtools.com/misc/CE-DISTIL1.pdf which involves rubber stoppers which would
be corroded by nitric acid) or a vacuum pump yet. I'd like to try the method described in the "Nitric acid the easy way" thread.
Not terribly effective but easy and cheap.

"Although far off topic, I mention this because it illustrates how difficult it is to actually use microwaves as a lethal "weapon,"
since it takes many kW for many seconds to denature just a few cc of gray matter."
This is true if you use microwaves - THz in order to thermally destroy the targeted tissue. This part of the spectra, however
also has non-thermal effects especially on the nervous system. One possible way to create non-thermal microwave-THz
weapon is to adjust the radiation frequency to a peak in the absorbtion spectra of vital biomolecule in vivo.
c.Tech January 19th, 2007, 07:54 AM

I would have thought the sodium bisulfate reaction would go more like this.
2NaHSO4 -> Na2SO4 + H2SO4

As it usually does in ethanol and water.
Then the general reaction between a nitrate and sulfuric acid takes place.
crazynlazy January 20th, 2007, 12:52 AM

IIRC the decomposition reactions for sodium bisulfate is as follows:
At 315 degrees Celsius: 2NaHSO4 --> H2O + Na2S2O7

At 460 degrees Celsius: Na2S2O7 --> SO3 + Na2SO4
So I imagine that all of the water would have boiled off from the preliminary decomposition. And the latter decomposition
yielding sulfur trioxide would combine with any water that might be left in the air yielding sulfuric acid. Plus, even if 0 - 460 was
achieved quickly, sulfuric acid would protonate the sodium sulfate leaving only sodium bisulfate which would then repeat the
reaction until sodium sulfate was the only remaining substance. However I could be wrong about this as well, I am no
chemistry expert.
While I realize now that my synth. is incorrect on many levels. I do however still think that the replacement reaction happens.
It being the only logical reaction that I can see given the decomposition reactions. I would, although appreciate if anyone
could tell me why it wasn't. My basis for information was the reaction I had performed with sodium chloride and sodium
bisulfate which would give one reason to believe that the corresponding acid: nitric acid would be created, and proceed to be
decomposed as tmp pointed out.
So I'm going to have to scratch what I said earlier about the reaction and agree with PeterB2 and tmp. Thanks for pointing
that one out.
As for a contribution to the production of NO2. Use strontium nitrate as opposed to potassium nitrate. It's higher
decomposition temp. allows higher quantities to be used with more ease.
Edit: I apologize for any ambiguity, I meant degrees Celsius.
++++++++
You didn't bother to mention whether the degrees were in Celsius or Fahrenheit. In science, the importance of such details is
immeasurable.
NBK

A h e m back to the original topic: I qu ite forgot abou t this thread, so I guess it is serendipity that I ch ecked it today because I
found an interesting journal article recently. I am somewhat out of my depth with this one, but I think it has potential to be an
interesting experiment.
The article is Microwave Torch as a Plasmachemical Generator of Nitric Oxides from the last issue of Plasma Physics Reports,
2 0 0 6 , Vol. 32, No. 6, pp. 520 524.
Abstract - The possibility of using a microwave coaxial plasmatron (a microwave torch) as an efficient plasmachemical
generator of nitric oxides in an air jet has been studied experimentally. A plasmachemical model of the generator is
developed. Results of calculations by this model do not contradict experimental results. A conclusion about the mechanisms
governing NOx production in a plasma torch is drawn by comparing the experimental and calculated results.
The device seems simple enough to my untrained eye, all that is needed is a coaxial waveguide. Since I have no idea what
the hell that is, I looked it up. Fortunately the journal included a reference to an earlier publication that describes exactly how
to make one of these coaxial waveguides. Unfortunately I don t kno w precisely what they are talking abou t. I think , only my
gleaning, that the waveguide is just some wire. The earlier journal article is not exactly as clear as I would like it to be.
Perhaps a more mechanically inclined member can look over the publication.
Here is a clipping of the experimental setup. The deuterium lamp, Spectra 1600, and S2000 parts are only for this
e x p e riment s e xperimental analysis of gaseous products. These compo nents are NOT nee ded to make NOx.
http://www.roguesci.org/images/1-20-07_01.jpg
In the picture it appears as if the magnetron directs the microwaves into the waveguide. In the prior article the setup is a bit
more detailed. Here is where I am having trouble: The earlier article specifies the magnetron directs the microwaves into a
rectang ular re sonator. Maybe I slep t through that cla ss in physics , but what exactly is a rectang ular re sonator? Wh at is it
made of? can I make one? Do I even need it to make NOx?
http://www.roguesci.org/images/1-20-07_02.jpg
Lets hear from the learned members of The Forum. Any thoughts on how to build a coaxial waveguide? Is this experimental
setup as simple as I think: a consumer grade microwave magnetron direction the microwaves onto a bit of spiky wires with a
guide wire around it, and a jet of air blowing in the middle of it. Can it be that simple?
Oh, look! Someone has uploaded all three articles (there is another article that discusses the setup) to rapidshare moments
before I posted this. Thanks anonymous uploader, you are both a genius and handsome :)
Microwave Torch as a Plasmachemical Generator of Nitric Oxides . Pla sma P hysics Reports, 2006 , Vol. 32, No. 6, pp. 520 524.
(http://rapidshare.com/files/12590908/Microwave_Torch_as_a_Plasmachemical_Generator_of_N itric_Oxides.pdf.html)
A Pulse-Periodic Torch in a Coaxial Waveguide: Formation Dynamics and Spatial Structure. Plasma Physics Reports, Vol. 30,
No. 3, 2004 , pp. 255 262. Tra nsla ted from Fizika P lazm y, Vol. 30, No. 3, 2004 , pp. 283 291. (http://rapidshare.com/files/
12590909/A_Pulse-Periodic_Torch_in_a_Coaxial_Waveguide.pdf.html)
Repetitive Torch in a Coaxial Waveguide: Temperature of the Neutral Component. Plasma Physics Reports, Vol. 30, No. 6,
2 0 0 4 , pp. 531 541. Tra nsla ted from Fizika P lazm y, Vol. 30, No. 6, 2004 , pp. 575 585. (http://rapidshare.com/files/
12590910/Repetitive_Torch_in_a_Coaxial_Waveguide.pdf.html)
sparkchaser January 20th, 2007, 04:56 PM

The rectangular resonator should just be a metal box, or even fine wire mesh that has holes less than one wavelength in
diameter. The resonator basically directs the energy into the air tube, and uses the outer tube as a shielding ground. Think
coaxial cable, it's the same principle.
Meawoppl February 21st, 2007, 12:35 AM

A gf and two job changes later I am back on the project, and really want to get this rolling. I hear that making explosives is
therapeutic. I AM buying a microwave from Wal-Mart tomorrow, no more of that Craigs's list shit.

It will take more than just slapping together some free-formed (hand-bent) mesh and some improvised pipe: for example,
did you notice the temperatures that this toy can reach? Up to 7000K!! That's around 6700 Celsius, or over 12,000 Farenheit!!
And you'll be moving 5 to 10 liters/min of air at that temperature. Just for your own personal protection you will need a welding
mask, full-faced and I'm guessing at least a #12 shade lens--maybe more. A full suit and gloves.... You know, now that I
think about it, I wonder what kind of x-rays may come off of the electrons kicked around at that temperature. Not
insurmountable, but you might want to investigate that.
From what else I gleaned from between the lines, the rectangular box is not an ideal design and some waveform analysis
should be made not only for the resonator, but for the coax channel afterwards. The trick that they are using is a lot like a
pipe on a pipe organ. It needs to set up a resonance along the outer electrode, and then as the waveform reaches an
antinode, the inner electrode abruptly stops and releases the air. The microwaves are focused at that point like the sun's rays
through a magnifying glass on a poor hapless ant, initiating the plasma pulses (occuring at around 8 microseconds, or around
125,000 times per second IIRC) which, thanks to the heat capacity of the air, quickly averages out to a steady plasma torch....
But back to the issue, the electrodes will need to be tuned to catch an antinode just right, and the two electrodes will need to
be not only extremely circular (as in lens quality) but also perfectly concentric for the entire length of the z-travel.
But otherwise it sounds easy enough. :rolleyes: It would make one hell of a plasma cutter for steel or even a high-tech
initiator!
Anyway, there are some serious issues but they could either be solved through lots of calculations (enough to give you a
headache to rival a nitro-throbber) or some intuitive guesswork and some engineering methods to work around all that mess.
Good luck, I'm dyin' to see how it goes!

Al Sheik Yerbuti, you seem quite knowledgeable on the this topic. Could you perhaps recommend any engineering books that
describe the selection or creation of acceptable resonator chambers or design of microwave equipment? I have a few books
underway, but I am not sure what the proper terms are to do an effective search to find good literature.
The suggestion about the x-rays is very intriguing. Talk about unintended consequences.
It is not so difficult to get plasma in a microwave. I have seen video footage of a modified microwave producing flashes of
plasma from candle smoke. Achieving a steady flow of plasma for consistent production of nitric oxides is entirely a different
matter, and will require much experimentation.
However, if all you have to start with is wire mesh and bent tubes, those are better than a mountain of equations because
equations never actually made anything. At least you may find out what does not work and can warn others about your failures
so that they do not repeat your earlier fumblings.
jpsmith123 February 25th, 2007, 12:21 PM

Unfortunately I'm not yet in a position to do any meaningful experiments myself, but I have some ideas that might be
helpful.
I think there are several ways that microwaves could be used to make NOx; e.g., U.S. Patent #6696662 describes another
potentially useful setup that may be easier to rig up.
I have the patent in pdf format, but I'm not sure how to upload it here.
Anyway, the primary usefulness of microwaves seems to be the ability to form a uniform, high temperature plasma in air at
*atmospheric pressure*.
Moreover, I've seen several peer reviewed journal papers (mostly in the journal "The Review of Scientific Instruments", I think)
where people have constructed various plasma-producing scientific apparatus from commercial microwave ovens.
In any case, as I see it, the technical issues are: 1) to create some ions in the air, thereby creating some conductivity whereby
the microwaves can deposit energy in the air; 2) confine the plasma to a defined space, without burning up anything or
contaminating the product; 3) present a reasonable load to the magnetron to keep the efficiency reasonable and avoid
premature failure of the magnetron; and 4) avoid hurting yourself with stray microwave radiation, high voltage, or product
gasses.
It may be possible to use a microwave oven almost "as is"; i.e., with only a few modifications. In accordance with the above,
the main issues there would seem to be: getting air in and out, obviously without allowing significant microwave leakage,
confining the electric field to a volume smaller than the whole cooking chamber (to get a higher temperature plasma), and
getting some ions to start the process.
The below linked page shows plasma generation inside an oven, and thus makes me think the idea is basically feasible.
http://jlnlabs.online.fr/plasma/gmrtst/
Al Sheik Yerbuti February 25th, 2007, 09:09 PM

As I said, much of the equationeering can be avoided through intuition and some engineering methods. Probably the best
workaround that an engineer could do to bypass the math is experimentation and the collection of empirical data. (Before any
other engineers get mad at me I better include that to formulate equations which describe and predict the empirical data is
good, too).
I will look to see if I can locate any books which will be helpful towards this end. I would not look into engineering books at
first for this. Conceptual matters such as this would be found more readily in physics, under electro-optics. Best bet for
beginning the quest is any undergraduate level text in general physics, in the optics section, then see where that takes you.
If you happen to be producing arcs of electricity, then depending on the voltages being generated, you are very likely to be
producing x-rays and UV. How much I can't predict at this stage, because we have no real working design yet, except what the
Russians used in their setup. They included only sufficient information about their design to demonstrate the concept and no
more--in other words they have mostly kept it secret what they designed. Depending on the amount of incidental x-rays
produced, it could be no more problematic that x-rays from your television or it could be enough to kill you from either killing
ribbons of flesh through your body (depending on where, by chance, they become spatially focused) to inducing cancers by the
ionizing disruption of your RNA etc.
Arcs of flash electricity in the microwave certainly are easy to produce but causing them to be localized and controlled will be
much more of a challenge, yes.
There is a compromise between slapping stuff together and pure equations. One is blind and the other is crippled. You will
recall that Marie Curie made great advances for the cause of science, yet paid the price of ignorance with her life. (When I use
ignorance and Mme. Curie in the same sentence I mean it with only the greatest respect; it was, however, the frontiers of
human ignorance that she was exploring. So no flames, thank you.)
I'll have to do some reading on this subject before being able to offer any more concrete information, but in the meanwhile be
aware that whoever assembles a prototype of this nature should take precautions against high-voltage, dangerous currents,
UV, x-ray, IR, loose microwaves, high-temperature plasma streams, and of course, NOx and other threats.
I'll try to brush up on some of these topics.
__________________________________________________ ___
EDIT #1
Wow, there you go. JPSmith123 snuck in right as I was posting. So imagine this: get your reactor chamber (the ball glass in
JP's link) and devise a method to create a cross-flow of gas (or air) through the vessel. I am envisioning a three-necked
reaction vessel, or distillation flask. From there, a couple hoses, drill a few strategic holes in the oven, and the rest should be
simple enough!! Good job JP!
__________________________________________________ ___
EDIT #2
I had to try it--I made a circle of cardboard and covered it with aluminum foil. I took a standard pencil and removed the eraser
end, and exposed additional lead at the bottom to make contact with the aluminum disk. I inverted a round 500ml flask and
sharpened the pencil to a length where it reached just a little into the sphere of the flask. I placed the pencil in the flask and
set the flask onto the disk in the microwave. I turned on the power for 15 seconds and noticed nothing. Upon investigation,
the pencil was hot. I hypothesized that the wood could be interfering with some effect so I carefully removed all the wood from
the lead and had a single length of the pencil lead. I retried the above experiment and noticed a couple small sparks at the
graphite-aluminum interface. The aluminum was found to be burned through, preventing further contact. In the trash I was
able to locate a lid from a can of orange juice which I cleaned and substituted for the aluminum-covered cardboard. This time,
some sparks worked their way up the lead until it reached the tip, whereupon it generated a small ball-like source of bright
light! It was steady and blue as one could see from a welder. I shut off the microwave to investigate. Inside, the lead had
broken in two. This must have occurred when I turned off the power. Where the lead was touching the flask in the sphere
portion, the borosilicate glass had melted and a set of small circular cracks had appeared. The flask was otherwise filled with a
thick, white smoke of unknown composition. It smelled waxy and i hypothesize it to be binder from the pencil lead. The OJ lid
has carbon deposits on it, signs of heat burnthrough as if it is a coated steel. The lid was cleaned of this and shows minor
damage. The lid was also extremely waxy, and I'm wondering if some wax may have remained from the cardboard sides of
the OJ can it came from, and escaped my cleaning. The pencil lead (graphite composition) shows definite burnoff at the
sharpened tip. There are whitish deposits at the other end where it touched the OJ lid. The shaft of the graphite shows an
exudate of a nearly black color, sticky and bubbly. It reminds me of burned sugar. Where the graphite broke, it shows definite
signs of a miniature explosion, and I hypothesize that a small bit of this exudate has vaporized and popped, similar to a
popcorn kernel.
Improvements: 1. Use pure graphite. 2. Do not allow graphite to contact glassware. 3. Be certain that all components are very
clean.
Further results when available
__________________________________________________ ___
EDIT #3
I've varied some parameters with little success. I've tried steel as an electrode (a nail) with little success. It did get hot which
makes me think it has too much resistance. Maybe a piece of copper? I tried the nail both sitting loose on the reflector, in
which case the nail and the reflector sparked on each other. I tried the nail welded to the reflector, and nothing observable
occurred. I made a larger reflector by using an old paint can bottom, can-opened. I did not notice any improvement. I retried
my pencil lead, once pinched into a hole on the reflector to hold it upright. There were sparks at the pinch, but no more. I put
the lead back in the original way, just sitting on the reflector and leaning on the neck of the flask. This time it worked as
originally described, and I have another burn, melt and crack in the flask. I think I'm spinning my wheels until I understand
better the information from jdsmith123's link, and now I notice Meawoppl has one, I'll read that also.
Meawoppl February 26th, 2007, 01:02 AM

I have purchased an expendable microwave, and have begun experimentation.
The best directions I have found to date come from here:
http://jnaudin.free.fr/html/oa_plsm4.htm
Which details the particulars of getting a "stable plasmoid" going. It seems like you need to create a small flame to get things
going, and they have good directions for creating something that self ignites.
Really, I am not sure if a stable plasmoid is what we need. True it would provide a large amount volume to absorb microwaves
and thusly lots of O3, But it also creates LOTS of localized heat.
I can see a similar "ashtray" sort of solution working, with lots of carbon dust, therefore arcing therefore O3. Or perhaps if the
plasmoid were unstable, (popping in and out each couple seconds, heat managment might be easier.
As for x-rays, I am not too concerned. I was under the impression that it was nearly impossible to get significant x-ray
emmissions from the lighter elements, as the outer electron shells are too tightly bound to allow the stripping of e-'s
necessary. Secondly, the difference in energy levels was low for transitions between levels to be in the energy range of x-rays.
I could be wrong, I have only ever had a class on "Experimental Microstructure Analysis" that talked about x-ray production as
more of a side note.
Please correct me if I am wrong on the above, I want to make sure I wear my lead foil underwear.
I have a good feeling on how I want to design the chamber. I plan on drawing it all out tomorrow at work to avoid a slew of
questions that will arise purely from describing a theoretical complex assembly.
One last thought, if the final HNO3 had a bunch of carbon grit in it, would cause any real problems? I suppose it would be
removed by distillation anyway, just thinking.

As for x-rays, I am not too concerned. I was under the impression that it was nearly impossible to get significant x-ray
emmissions from the lighter elements, as the outer electron shells are too tightly bound to allow the stripping of e-'s
necessary. Secondly, the difference in energy levels was low for transitions between levels to be in the energy range of x-rays.
Certainly in this new setup, with a ball and carbon thing I don't see much x-ray production. It was the other setup with a
resonance chamber and concentric electrodes that I was concerned about, epecially if there were no shielding, which might
occur by disassembling a microwave and with an open-ended waveguide. It would depend on the arcing and the voltages
generated; x-rays are most often produced by the deceleration of electrons impacting metal targets and their production is
therfore voltage dependent, not element dependent. For example, an arc welder or a plasma cutter produces copius amounts
of UV which is one to two orders of magnitude less energetic than x-rays, but with just a few thousand volts higher potential,
you are making x-rays. But still, the more I think about it the less I am worried about x-rays from these devices myself.
Still, I'd make a simple test with your prototype, though: take a disposable camera (or even just a roll of film, not digital) and
keep it about the device. make sure no metal is shielding the film, including the camera body, inside, or if you're using film,
the film canister. Of course, keep it away from all light. After running the device for some time, take the film in for developing.
black pics are negative, grey to white is positive.
nbk2000 February 26th, 2007, 03:45 AM

Go to YouTube and search for grape plasma. A simple grape will form a plasma ball in 10 seconds (sometimes), and there's
your starter. :)
Actually Al Sheik Yerbuti, I'm going to have to refute your claim that x-ray production is voltage dependent.
As I understand it, when you excite an electron out of its ground state, there are a variety of energy levels that it may jump
to, depending on what element it is. When the electron "falls" back, it will emit a photon of corrosponding energy equal to the
energy absorbed and also, of a wavelength dependant on the "distance" that it has fallen.
Otherwise, photons can be made from "knocking" electrons from the lowest shell (K shell) and then an electron falls from the
L shell to take its place.
I know most of that is right, although I'm not sure about the wavelength bit. Not all elements will produce x-rays, and my
argument is supported here (http://ie.lbl.gov/xray/mainpage.htm).
From Giancoli's "Physics" (5th Ed.) in Chapter 28, we find that we can predict the wavelength of photons given from a specific
energy level drop. The explaination says that the wavelength of an energy level transition is dependant on Z2 (Z=No. of
Electrons in an Element)
Example 28-7
Estimate the wavelength for an n=2 to n=1 transition in molybdenum (Z=42). What is the energy of such a photon?
Solution: We use the Bohr formula (Z2) with Z2 replaced by (Z-1)2=(41)2.
Wavelength propotionally = 1/((Z-1)2)
Therefore, Wavelength = (1.22x10-7m)/(41)2=0.073nm.
This is close to the measured value of 0.071nm.
If you didn't understand that, say so and I'll try an explain using Giancoli.
Anyway, it doesn't really matter. That website above says that x-rays aren't produced from elements under Calcium.

Ah, my new good friend Alexires, thank you for bringing this up. It could be clarified further. I believe we are talking about two
different issues. Yes I agree with you that elements with large Z^2 values will have characteristic x-ray spectra, most certainly.
In our present application we will be dealing most likely with iron and possibly some steel alloys with chromium. Either of these
will be able to produce x-rays by the method that you are referring to, and so will other common elements. There will be
characteristic frequencies in each element's emission spectra corresponding to the excitation energy of each electron in an
element's various orbital locations. Yes, some of these can and do attain energies in the x-ray spectra.
I, however, was referring to the production of x-rays as if in an x-ray tube, possibly produced in the waveform portion of the
microwave plasma generator. If voltages were to occur in excess of a few thousand volts it is quite possible. The effect is
referred to as bremsstrahlung which is german for "braking radiation". Through this phenomenon, the energy of the photon of
an x-ray can be precisely manipulated by the variation of the voltage in the x-ray tube. The electrons on a cathode are
accelerated by the voltage difference towards the anode. For the production of x-rays, the anode is angled outward and as the
electrons strike and abruptly stop on the anode's surface, x-rays are emitted at around 90 degrees (perpendicular) to the
electron's path. As we all know, voltage is a continuum and therefore the x-ray wavelength in this setup is tunable to whatever
frequency is desired. It is, therefore, voltage dependent.
In fact, even in the case of an element which has one of its electrons excited out of the ground state, when returning to the
ground state, as it emits an x-ray photon, its frequency and its energy is directly related to its voltage drop, and is therefore,
voltage dependent.
What you will find is that an element's characteristic spectrum is element dependent.
But more on topic, I am concerned somewhat that this bremsstrahlung effect could occur in any situation where we find
ourselves dealing with voltages in the many kV range, which is very possible with this plasma.
Say, I cannot find the tags for superscript, how are you able to format your formulae so nicely, Alexires?

The tags are sup and sub enclosed in the usual brackets. I need to stick the graphics for those back in the quick editor...
Meawoppl February 26th, 2007, 07:28 PM

It seems that this thread has evolved into two separate sub threads, one discussing the production of HNO3 in a microwave
oven, a second, discussing the use of a largish microwave assembly detailed in some literature earlier. Just wanted to let
everyone know.
As setup in the microwave oven, x-rays will not be an issue, this may not be true for the other experimental setup.

Meawoppl, did you check out the patent I mentioned? The inventive apparatus is very simple.
It's a closed rectangular waveguide with holes drilled about 1/4 wavelength from the closed end (so that the plasma occurs
where you would have a high electric field), with a quartz tube inserted through the holes through which the gas flows.
The gas is introduced into the tube through a small metal tube which also serves as an ignitor (apparently by way of corona
created by field enhancement at the edge of the tube).
My thought was to recreate this setup inside the microwave oven, for safety and ease of construction. IOW, you basically
extend the waveguide that feeds the cooking chamber, to a convenient length into the chamber. The two opposing sides of
the waveguide extension perpendicular to the quartz tube now confine the electric field (assuming TE10 mode in the guide),
thereby concentrating the field.
Of course it's hard to say without trying it, but you may get satisfactory results if you just run a quartz tube through the
cooking chamber without trying to concentrate the field. It may help to map the field somehow first to find a good
"hotspot"...maybe using an array of marshmellows or something that would give a visual indication of relative power vs.
position inside the cooking chamber.

You know, I remembered yesterday that I once discussed this same topic a few years ago. My thread is "Zapping my way to
nitric with a Marx generator" http://roguesci.org/theforum/showthread.php?t=1757
I shall merge these two threads in a few days just to let everyone know where this one will be going. The content is similar
enough to warrant their combination.
I was going to suggest you look into using a Marx generator when I remembered talking about this before. Then I found my
old thread. The original link that describes how to make a Marx generator no longer has that information, but I found many
more websites after a brief Google search.
I wanted to comment that although industry has given up on the idea of the Birkeland-Eyde Reactor, this method of producing
nitric acid is far more accommodating to the bench scale lab of the amateur experimenter or hobbiest. Quite frankly getting
ammonia and platinum is far more difficult and expensive in the short term than obtaining a HV power source and air.
The ammonia burning process needs far greater precision and optimization to get it to work. The electric arc just works every
time. It may not be the most efficient process, or economic process, but it just plain works.

Another thought I had on this was the use of a device that I have which is ready to go, almost as is. It is my plasma cutter. It
has a built-in air compressor, and pushes air through the center of the electrode (not sure if its the cathode) and heats up the
air into a conductive plasma. The current then passes into the metal, melting it, thus allowing the plasmified air to burn
through the metal. I would have to do minor fabrications to channel the air into the post-plasma stage.
866 (plasma in photo around 2 cm long)
Which brings up another topic, what EXACTLY do we do with this enriched air? I'm thinking that the simplest option would be to
bubble it into a tall PVC pipe (to increase absorption) filled with a concentrated brine of KCl. Refinement of the brine after a
certain reaction time might yield what--KNO2, KNO3, and release Cl2? Someone should verify this, I am not a chemist. (I'm
mechanical FYI). Any thoughts?

I wrote this last night, but as the forum went down JUST as I tried to post it, I'll post it now.
Al Sheik Yerbuti - Ahhh, ofcourse. Forgot about that one, it has been 2 years since I did physics. E=hf, where E is energy, h is
planks constant (about 6.63x10-34) and f is frequency.
Sorry all, looks like an electron with changing velocity will throw off energy of frequency E/h.
Then question now becomes, do the electrons that are ionized inside a microwave oven have the energy to give off x-rays?
Forgive me if I am incorrect, but 1 microwave photon (of 2.45x109Hz) has about 1.62x10-24J of energy (using E=hf), which
means the MAXIMUM amount of energy (Ek) that an electron could have is the same.
The minimum energy for x-rays are several orders of magnitude above this energy (x-rays have energys from 1.98x10-17
upwards). So, unless my maths suck ass (which it does, but still), that means that one electron would need to be hit with
1.2247537x106 microwaves before it has the energy to give off 1 x-ray (and come to a complete stop).
What are the chances of that happening?
Al Sheik Yerbuti - Are you sure about how the plasma cutter works?
Have a look here (http://science.howstuffworks.com/plasma-cutter4.htm).
I think you may be fantasizing a little by using a plasma cutter. A mig welder might be adapted to create your plasma easily,
but I'm not too sure about the plasma cutter. Then again, I have no practical knowledge of how either work, just what I have
gleaned off the internet, so feel free to argue.
Actually, a mig would work, if you could work out how to replace the feed wire with something that won't melt and the inert gas
with atmospheric air. Buy a cheap mig and pull it apart...
Al Sheik Yerbuti February 28th, 2007, 10:37 PM

Hi Alexires. Interesting calculations. Try it this way: Large numbers of microwave photons attack the surface of the electrode/
waveguide. Many electrons are stripped away and removed in an ionized stream, leaving behind an increasing voltage
potential. It only would take a couple thousand volts for theoretical UV production, and as a ballpark number, ten thousand
volts to have the velocity for x-ray production. In that case, energy is proportional to the square of the velocity BTW.
Your number of 1.2x106 is an impressive size, but remember that one Coulomb contains the charge of 6.2x1018 electrons (or
protons, for that matter) and your number is a mere 1.9x10-13 the size, or about two - ten-billionth of a coulomb. How does
that relate to our understanding? One Ampere passes one Coulomb of charge every second. As an example, a microwave of
800 Watts (by American voltage of 120V) will pass around 7 Amps per second, which is 35 billion times 1.2x106. Every second.
Frankly, I don't see this as being fruitful. I can go from direct experience, that my welder (which happens to be a small MIG
welder) will quickly burn my skin from its UV emissions, as my arms will attest. It is supplied by a household current of 120V,
20A. It's output is 90A, which gives a maximum theoretical output voltage of 27 Volts. This 27 volts is sufficient to produce all
the UV needed to blister my skin in just a few minutes of welding. I have a very small homeowner-sized unit. Imagine what an
industrial unit can produce.
As far as using the MIG for this job, it is completely unfeasible. As stated earlier, it only produces around 27V and requires a
current sink (the workpiece) to maintain the spark. As a matter of fact, the wire is repeatedly submerged into the weld puddle,
hunderds of times a second, and the resistance of the heated wire at the puddle focuses the power at that point, causing the
wire to explode (vaporize) and to break the circuit. The wire is advanced, resubmerged in the puddle, and the process
repeated.
One may hook up a range of shield gasses, I prefer C-25 for general use, which is 75% CO2 and 25% Argon. One could use
no gas at all, using a special wire with a flux core, in which case the MIG welder is now properly called a FCAW welder. My
cheapie home unit can do both, but the FCAW method, while slightly more portable, stinks and splatters and IMHO, produces
a vastly inferior weld.
Now on to the plasma cutter: I can promise you I know more about its operation than a tiny article in "HowStuffWorks" could
convey. That borders on insulting, Alexires. (But you're still my buddy) I am assuming that everyone is able to see the photo
that I posted in post #40? The image shows the hot gasses being ejected into the atmosphere, quite clearly in a plasma
state. The particular unit that I own has, as I said, an internal air pump and shoots this stream of air up the hose, and
through the electrode where it is heated and charged and ejected in a plasma stream. This is in fact the device most likely to
produce results for us. I believe this device WILL work. The welders are too low of voltage and infeasible to modify to our end.
IOW they will NOT work.
If you are curious, my welder is a Lincoln Electric SP125 Plus and my plasma cutter is a Hypertherm PowerMax 190C. Readily
viewable on the WWW.
I seriously advise against pulling apart a welder and screwing around with that, unless you are a very experienced electrician!
It is deadly inside. Although I agree that any hands-on types like us should have welders.... So get one, use it, but don't ruin
it!

U.S. patent #5692495 (assignee: BOC Group) claims that passing "air, oxygen-enriched air, or air containing a small amount
of ammonia over a noble metal catalyst at an elevated temperature (500 to 1200 degrees C)" will make NOx.
I was aware of the use of platinum to make NOx from ammonia, but I'd never heard of it used just with air.
Also, I have a paper describing a classroom demonstration of "acid rain", wherein NOx is made from an oxyhydrogen flame.
I have both the patent and the paper in pdf format. Is there any way to upload them here?
++++++++++
No need. Anyone here for some time knows how to find patents. NBK
Meawoppl February 28th, 2007, 11:21 PM

I started playing around with my microwave today some small results:
I setup two pieces of graphite mechanical pencil lead in a cork separated by a small amount and got some pretty impressive
arcs/plasma going.
Curiously, when covered with a glass mug it no longer sparks. I think that the glass is soaking up too much energy (it get
rather warm), so I am going to seek out a thinner vessel tomorrow.
Ideally, I would want to do it all in a modified test tube with light negative pressure pulling through a condenser with some
steam. That sounds like it could work well.
I will update again tomorrow.
Alexires March 1st, 2007, 06:22 AM

Al Sheik Yerbuti - I'm sorry if I offended you. I was simply asking if you knew about plasma cutters and mig welding. I know
barely anything about either of them, so anyone would be better qualified than I in regards to them.
As much as I have enjoyed talking with you about this, we haven't really resolved anything. Personally, I doubt that you will be
in danger of x-rays when trying to produce NOx in a microwave, but, if Al Sheik or any other forum members think that there is
a danger, I would recommend lead sheilding around the microwave. At least a few mm thick. Think about it. Personally, I'd
rather die from some SHERPA (thanks NBK) than from cancer.
If there is the case of dislodging electrons, we might think about using that to our advantage. Electromagnets aren't hard to
make, and something that acts like a SEM (Scanning Electron Microscope), just without the viewer might be useful in
generating high temperatures. Ofcourse, this idea isn't overly feasable, and I would try the microwave idea before trying to
concentrate a beam of e-.
Also, in response to Meawoppl's latest post in this thread, why do we need to have a glass bulb around the plasma? If we
could focus the microwaves in some way, or create a stable(ish) plasma, why bother with the glass. It simply causes problems
(cooling, air supply, etc.). Then again, from what I have read, it is necessary, but why, I am not sure.
Still, I think the other thread regarding passing air through a jacobs ladder, or arc of some kind is alot more feasable than
making a NOx producer from an old microwave.
RTPB principal, KISS. Lets go back to the basics. We are looking at a different approach than the arc way of making NOx
(although making an arc in a microwave certainly would be useful, but probably in the other thread).
I think I have an old microwave at home. I'll have a little look over the weekend, see if I can find it and turn it into an
experimental apparatus.
Al Sheik Yerbuti March 1st, 2007, 07:05 AM
No offense taken my good friend Alexires! I've been on forums before, it's a form of communication rife with
misinterpretation. I am proud of your commitment to factuality. I am also happy to be investigating this topic with you. Keep
us on our toes!
I agree we could spend more time now in constructing functional models and less in academic masturbation. As a practical
solution to the fear of x-ray, a roll of film may work well as a detector. Also, I saw recently that there were inexpensive x-ray
detector tags at http://www.sciplus.com/ , get them while they're hot! For UV fears, a bit of SPF works wonders.
As for my spare time to follow, since my current nitric acid generator has a phenomenal rate of maybe 20 ml/day running full
blast, I believe I'm ready to assist in this project in a more hands-on experimental fashion. I still think that we can attain
better yields with the improvement of NOx capture after its production in a Microwave Generator (MG). Towards that end, I
intend to "pretend" that the plasma arc cutter approximates the output of your MG, and experiment with improving the NOx
capture. I will certainly report results. The way I see it, I am ahead of many people in the sense that I have a device capable
of doing what the MG will be intended to do, which both relieves me of the need to test, construct and optimise an MG, but
also gives me an opportunity to get a head-start on the reclaimation portion of our project.
But anyway, I'll get onto it ASAP. I have some reading on nitrogen compounds to do, as I still think there might be a way to
cause the nitrogen to precipitate out; Then I intend to show that distilled water can become acidified when the plasma-cutter
gas is passed through.
NBK: I can't think of anything better! (Yet) :(

//Roses are red; Banannas are fruity//
//If I get a bomb; Al Sheik Yerbuti!!!//:D
____________________
EDIT: to add this info:
Radiac Detector
Poloroid No. DT-60/PD, gov't #16-D-19884-1031 dosimeter for measuring cumulative exposure to X- and Gamma- Rays. Still
in use today on some older ships according to a naval officer friend of ours, the badge/detector is nonself-reading with a
range of 0 to 600 roentgens. They are meant to be scanned by a machine called the "Radiac Computer Indicator CP-95A/PD",
which we do not have. Still, a cool bit of cold war history in original military packaging with instructions dated 1951. 1-1/2" dia x
7/16" thick with a 3/4" sq radiophotoluminescent glass inside.
21517 RADIAC DETECTOR $2.00 / PKG(4)
You may not be able to get quantitative measurements of exposure without the reader, but if it gets dark, it's bad!

Al Sheik - Is that 20ml of 100% nitric acid a day? Because if it is, that wouldn't be so bad.
I will be awaiting your research regarding NOx uptake. It is certainly a part of the project that needs thinking about.

I'm not sure how pure it is, that's debateable. it is fuming, it is orange-red, clear, and yes, 20 ml a day. I should draw out how
I do it, but it is a well-documented procedure. Basically, I found two ball-shaped bottles and put KNO3 and sulphuric in one
ball, no more than what will not spill out when tipped over (neck horizontal). I tape the empty one on top, starting with teflon
pipe thread tape, then electrical tape, then duct tape. Each is important: Teflon resists acid, The electrical seals the teflon, the
duct tape holds the rest in place and stops the two bottles from blowing apart from the pressure. The saltpeter/acid side is
placed in a sand-filled bowl, on an adjustable heat source. the other bottle is supported horizontally off to the side. I usually
have it sitting on an open jar, the mouth suports it well. The two bottles are thermally separated with a piece of cardboard with
aluminum foil taped to the hot side. A slit allows the barrier to go around the taped necks. I have three cold packs that I
alternate on top of the collection side, two in the freezer and one on the bottle. I cover this with towels to keep that side cold.
Never put a cold pack on a bottle that got hot. So keep it cold or turn it off and let it cool if it gets away from you. The heat
side, I adjust the heat to maximize the density of the red fumes. There is an ideal temperature range, and above that or
below that, the red fumes are not as thick. As long as the cold bottle stays cold, the fumes pass over and condense.
Eventually the generation side solidifies and stops making fumes, that's all you'll get. Collect the red fuming nitric after the
system cools (the cooler the better), place in airtight glass jar with glass stopper. I didn't have a stopper the right size, so I
wrapped some teflon tape around a test tube, held it in place with electrical tape and used that as a stopper. Lather, rinse,
repeat. Image below clicks to enlarge.
http://img443.imageshack.us/img443/4982/hno3generatoric6.th.gif (http://img443.imageshack.us/my.php?
image=hno3generatoric6.gif)
I guess eveything is relative, 20 ml is excruciatingly time consuming, and I never have enough.
No progress yet on Plasma cutter thing, but I'll go do that here in a few minutes.

This thread and the "Nitric Acid from Air and Water (http://roguesci.org/theforum/showthread.php?p=88445#post88445)"
thread are so similar I am getting confused on what to post in which. Both involve the use of plasma to generate NOx gasses,
but produce the plasma in different ways.
The other thread is focused on electric arcs, this thread on other types of plasma generation.
There are two types of plasma that produce NOx gas, high temperature and low temperature. The high temperature plasmas
break the molecular bonds of nitrogen and oxygen gas over 3000 oC whereupon the highly reactive free ions quickly
recombine with anything they happen to collide be it nitrogen or oxygen. Thus NO is formed, along with original nitrogen and
oxygen molecules.
A low temperature plasma like a glow discharge plasma does not use a high temperature flame. Instead it relies on ionizing
oxygen and nitrogen between high voltage electrodes. I know what glow discharge is in theory, but I lack practical knowledge
of how to use or build such a device. If anyone happens to know of a source of information, I would like to hear it. These
should be simple to build, but I can't find any plans or commercial products.
I found plenty of physics articles and alternative energy scammers talking about sketchy info from the 1930's, a very nice
website with a decent how-to on making your own telescope mirrors (complete with homemade glow discharge cleaner using a
propane tank, but no mention of the glow discharge technology itself), and lots of stuff on sputtering, but no devices.
A plasma torch is a nice idea since it is a commercial package available OTC, but, and this is a big but for many, they are
damned expensive. I try to limit my research on materials that are available to the widest possible audience. This is not to
say the plasma cutter direction of research is not invalid, the devices are attainable after all, but that only a few will bother
spending $400-$1000 for one of these (the cheapest I could find on froogle was $400).
I should qualify that and say few people would be willing to buy a plasma cutter *unless* there was a very clearly worked out
method of producing decent quantities of nitric acid resplendent with plans, schematics, pictures, pictures, more pictures, and
video.
Anyhoo, I am getting sidetracked from my main line of research, the tungsten catalyzed electric arc process. I admit I have a
LOT to learn about high voltage electronics, plasmas, ion generators, and the like. I can see why people enjoy building Tesla
coils and Jacob's ladders. I have enough trouble with chemistry to be learning evil physics :)
EDIT: Oops, I forgot to mention the reason for my talking about glow discharge in the first place. US patent 4,287,040
Production of nitric oxides. The invention relates to a process for the production of nitric oxides by passing through the
discharge a mixture comprising air and nitric oxide as seeding material, and recovering the produced nitric oxides.
Lets get to the heart of it, the rest is fluff: A flow of air was maintained through a tube of 6 cm length and 2 cm diameter with
a constriction of 30 mm length and 3.5 mm diameter at the middle of the tube, the pressure of air entering the tube being
100 torr. A glow discharge was maintained at a current of 0.2 A. The limiting energy yield for nitric oxide formed by the total
discharge power was less than 0.55 mole/KWhr. The steady state concentration of the nitric oxide (NO) produced by the
discharge was about 6 percent.
About 5 percent of the mixture leaving the discharge tube was reintroduced into the discharge tube at its entrance, and thus
this passed again through the discharge plasma with air introduced. An increase of about 10-20 percent of yield was obtained
by this seeding with nitric oxide.
Ahh, there is the rub, a glow discharge plasma is used. The point of this patent is to inject NO gas into the discharge zone to
act as a non-ionizing gas that increases the efficiency of the unit. I don't know how they expect to keep the NO from reacting
with oxygen and forming NO2 before it is injected back into the plasma.
If I was doing this I think I would recycle the NO gas given off by the reaction of NO2 with water which forms NO and nitric acid.
Of course that assumes I can figure out how to continually add more air and draw off the NO without creating a closed system.
Hmmm...

Al Sheik - While your method is dubious (its found in the Anarchists Crapbook afterall), you could always work out the % using
the density...
Edit: Mega got a post in before I clicked the button.
http://jnaudin.free.fr/html/s_gdp1.htm
This is a website on making a Glow Discharge Plasma Panel.
As I understand, glow discharge plasma is simple where there is such a high voltage difference that the air is ionised. This can
sometimes be observed on transformer boxes outside your house. A blue haze sometimes hangs around them.
Interestingly enough, I found this (http://www.iop.org/EJ/abstract/0022-3727/27/4/018).
It states that NO2 decomposes when passed through a low pressure glow discharge plasma.
Mega, Here (http://science-education.pppl.gov/SummerInst/SGershman/Structure_of_Glow_Discharge.pdf) is an interesting

PDF on glow discharge phenomenon.

1) I will certainly do my best to verify my findings and use rigorous scientific methods to conduct my experiments.
2) YIKES! I had no idea that my method was in the AC. I don't believe I have even read it, although I have certainly heard of
it. Do you happen to have a link to it lying around conveniently? I would be interested in that take on this method.
----------------------------------
EDIT: Oh, you mean the two-bottle and the sulfuric and saltpeter method? I thought you meant the plasma cutter thing. Hell
yea, this method is certainly effective. I got my initial information on this method from a US Army Field Manual, FM-31-210. I
have been playing wit it for a while and have improved it for my convenience and efficiency. As a matter of fact I now have
reason to believe that the purity is so high that you might have to ADD water to get HNO3. That is discussed in the other
thread.
4)The efficiency of this double-bottle method is why I am interested in capturing our enriched NOX emissions from plasma
discharge methods in a chemical manner, such as KNOX as opposed to in a solution of water. I took the bypassing of
distillation and drying stages of HNO3 to be obvious, if we could make pure saltpeter from Potassium Cloride and electrified
air. My mistake, so I'll mention this explicitly: If we can capture our NOX (which is produced by some type of electrical burning
of air) by making chemically pure SOLIDS such as KNO3, there are proven methods for the production of NO2, which I take to
be anhydrous Nitric acid. NO2 can be condensed at ~20 Celsius and reacted with H2O to make HNO3 of a purity and
concentration exceeding the requirements of our needs.
EDIT 2: I added a drawing to my post above (#48) which visualizes the description contained therein. END EDIT #2
5) I agree that these threads are blurring. Some of that is my fault, I apologise. OTOH, maybe it could be straightened out,
but it might not matter so much, in the long run.
END EDIT
----------------------------------
3) My main interest in using a plasma cutter in this manner is because I happen to have one. For me, it is a shortcut to the
end result of verifying the efficacy of the method. I can, basically, cut to the chase and verify the theoretical, saving time and
money for some to build a device only to find that the theory is in error.
3b) As I have posted in the other thread, I have had some encouraging results and will pursue improvements in efficiency.
nbk2000 March 5th, 2007, 05:44 PM
The 2-bottle distilling setup is one of the few things they didn't fuck up in the AC, probably because they got it from the first
Black Book.
It's crude, but it works.
jpsmith123 March 5th, 2007, 07:07 PM

It seems that the question of whether a glow discharge tends to make NOx, or to get rid of it, depends on the so-called
"electron temperature" of the plasma which I guess is a measure of the power density of the plasma.
It seems humidity is a factor also...at least in a dielectric barrier discharge plasma.
A dielectric barrier discharge might be another way to go. Here is a paper that talks about it a little bit.
http://www.alexchirokov.narod.ru/Presentations/France_ISPC_Oral_FrOral_AUG_2001.pdf
Chris The Great March 7th, 2007, 02:51 AM

You'll need to use a potassium base, such as hydroxide, carbonate or bicarbonate, to get KNO3. KCl will not form KNO3 when
exposed to NO2. However, the base might also form nitrite (KNO2) by reacting with NO and NO2 before the NO can be oxidized
by the air... I couldn't say for certain at all how much of a problem this would be.

I think that the go for removing NO2- ions from HNO3 is to add H2O2 to the acid, hopefully oxidising the xNO2 to xNO3.
Interestingly enough, I found this.
http://www.rsc.org/publishing/journals/CC/article.asp?doi=b609005b
It describes catalysing NO2 + water into Nitrous Acid via irradiation from illuminated titanium dioxide.
Also, found this (http://pages.towson.edu/ladon/orgrxs/reagent/oxidizer.htm). From my understanding, it alludes that Nitrous

Acid can be used to oxidise amines and amides into N-nitroso compounds, as opposed to nitric acid, which cannot. So possibly
the addition of an amine or amide could remove Nitrous Acid impurities in Nitric Acid. I don't really know about that, someone
with more knowledge than me might be able to verify it.
Ahhh, just read Chris the Great's post on the other thread.
Mega, maybe we could join these two threads in the Special Project Section under Nitric Acid? Maybe under Plasma production
method of HNO3 or the like?
Meawoppl March 8th, 2007, 08:55 PM

I can now make BIG sparks in the microwave, with relative ease. After an hour or so of playing with the setup myself and a
friend were informed my my room mates that it was making a terrible smell? We had no idea that there was a smell, does NO/
NO2 do that?
knowledgehungry March 9th, 2007, 01:23 AM

Yes. NO2 certainly makes an unpleasant smell.
nbk2000 March 9th, 2007, 01:56 AM

Could also be ozone.
But, regardless of what it is. it's not healthy for you to be breathing it in.
During experiments in the production of toxic gases (NOx or O3), you MUST have adequate ventilation to prevent any
exposure, as damage is cumulative and irreversible.
FUTI March 9th, 2007, 12:09 PM

If the smell was of the kind you sense near photocopying machine...that should be ozone.
Some of those bioionizator gadgets make small quantities of ions (and maybe little ozone too). Is it a "far cry" to expect that
this device can provide some kind of "priming mixture" for microwave to ignite the plasma more reliable?
Guys these two threads that we have about the HNO3 production by other means are so close in my mind that if by chance I
posted in wrong thread I do apologize but in my mind they start to look like Matrix clones.
Meawoppl March 9th, 2007, 07:20 PM

The trickier question that I was getting at was why would we not smell anything? Did we possibly saturate some chemical smell
receptors? Is that a known behavior of O3 or NOx etc?
chemdude1999 March 9th, 2007, 07:56 PM

Meawoppl, after using an ionizing air cleaner for a few years (before I realized they have some drawbacks), I would say ozone
can dull your olfactory senses.
For example, after coming into my old apartment with the cleaner running full tilt all day, the ozone was very apparent. Distinct
smell/feeling. However, after as little as an half hour, the smell/feeling would be much weaker. Like I would get use to it or
something.
Visitors would vouch for this as well. Now, I'm not sure on NOx. Just something to ponder.
NBK's advice to always have adequate ventilation is the safest approach. Take care of the lungs and open a window at least,
do it outside, or make a fume hood.
mr.pyro March 9th, 2007, 08:44 PM

I do believe it was ozone we were creating. I noticed that the smell in the beginning of the arc process was similar to smells I
have previously smelt while arc welding. It makes sense that we are going to produce the same gas with a similar electric arc.
A wikipedia/google search on gas produced while welding returns mostly ozone and small quantities of NOx and other trace
gases. I did not smell any kind of NO2 during this experiment like NO2 produced during a nitration reaction so I think we
hardly produced any of this at all.
It seems there is a simple test for ozone concentration that might be worthwhile.
http://www.achooallergy.com/acc-ozonewatch.asp
nbk2000 March 9th, 2007, 09:47 PM

Many toxic chemicals can be smelt at first, but then olfactory fatigue kicks in, and you keep breathing the toxic gas because
you no longer smell it, thinking it somehow magically disappeared.
If you smell it when you first get exposed to it CLEAR OUT! Assume the gas is strong enough to kill you, and take appropriate
measures to ventilate the area.
This same situtation of olfactory fatigue happened to me with H2S. I was using it in a synthesis and smelled a sulfurous smell,
but it 'magically disappeared', and I continued on. An associate came in and complained about the nauseating stench, telling
me it was building up!

As far as using the MIG for this job, it is completely unfeasible. As stated earlier, it only produces around 27V and requires a
current sink (the workpiece) to maintain the spark. snip
Now on to the plasma cutter: I can promise you I know more about its operation than a tiny article in "HowStuffWorks" could
convey. That borders on insulting, Alexires. (But you're still my buddy) I am assuming that everyone is able to see the photo
that I posted in post #40? The image shows the hot gasses being ejected into the atmosphere, quite clearly in a plasma
state. The particular unit that I own has, as I said, an internal air pump and shoots this stream of air up the hose, and
through the electrode where it is heated and charged and ejected in a plasma stream. This is in fact the device most likely to
produce results for us. I believe this device WILL work. The welders are too low of voltage and infeasible to modify to our end.
IOW they will NOT work.
snip
Until now, I have avoided posting in the Nitric Acid threads, despite a 'burning' desire :D to do so, because I have not yet done
the experiments.
However, having a 30-year background in power-electronics, including arcs and plasmas for industrial processing, the arc/
plasma method for Nitric is something I've studied in some depth over the years.
The above-quoted post requires a response, and I've been wanting to add some suggestions to the project anyway; so I am
going to go ahead and post, despite not yet having done the trials myself...
First, the above info on Plasma-cutters is incorrect. What he is seeing is the "pilot arc". In fact, in terms of current-path, the
plasma-cutter ISN'T any different than the MIG. The MAIN current does in fact go -through- the plasma stream into the
workpiece (the plasma stream is a good conductor).
Sheik, if you think about the fact that you must connect the 2nd lead of the plasma-cutter TO the workpiece with heavy-gauge
wire and ground-clamp, you will understand that this connection is for closing a high-current circuit which is THROUGH the
workpiece.
Again, when you hold the torch in the air, away from the workpiece, and see that hot jet coming out, that is the PILOT arc; not
the 'main' arc.
For anyone interested in plasma-cutters, I suggest studying one of the seminal patents in the field, from way back in 1955:
WELD-pat2806124- ARC TORCH AND PROCESS - RM GAGE.pdf
Nicely, it also happens to be one of those few patents which are REALLY well-written; and with lots of specific "real data" given.
Gage was with Union-Carbide, i.e. Linde....the firm which also came up with TIG-welding originally.
In fact, one of the interesting things you'll note upon careful examination is that, for this seminal work on plasma-cutting, he
is USING a regular TIG power-supply!
In other words, the voltage is NOT critical; and in fact a MIG power-supply could be made to work. It is not optimum though;
for two reasons.
First, higher voltage does help; in that it gives you more freedom to increase plasma-stream/arc length between electrode and
workpiece.
But far more important is that a MIG supply is a constant-VOLTAGE supply; and it is difficult to produce STABLE plasmas with a
voltage-source. You want a constant-CURRENT power supply; i.e. a supply which varies its own voltage as needed
automatically; in order to maintain a constant current.
Note; A MIG supply can easily be changed to a current-source by insertion of an impedance in series with it; i.e. a resistance
(wasteful) or an inductance.
FYI, a typical modern plasma-cutter runs around 250-300vdc OPEN circuit; falling to 50-150vdc (depending on conditions) when
the arc is struck. My ESAB PCM-750i runs about 120v when it's set to 50 amps.
Typical constant-voltage (i.e. MIG) welding supplies run about 20-30vdc during arc; without much increase at open-circuit;
perhaps to 30-50vdc OC.
Constant-CURRENT arc-welding supplies (i.e. for TIG and stick) also run 20-40vdc under full load; but rise to 60-100vdc open
circuit.
Note that a plasma-cutter and a regular (i.e. stick/tig) power-supply are both constant-CURRENT type supplies. I.e., current-
source vs. voltage-source.
Note also that the voltage during arc is highly dependent on the arc-LENGTH; among other variables/conditions.
fwiw, I designed such PWM inverters (and motor-drivers, switching power-supplies, etc) for a living for many years. I currently
have two ESAB plasma-cutters, a Miller Dialarc-HF 300 TIG welder, a Lincoln Weldanpower-225 engine-driven stick/MIG in the
yard-truck, an engine-driven Miller Trailblazer 450 amp MIG/stick for "the big stuff" :D , and a couple others sitting in the
storage-trailer that I can't even remember right now... :rolleyes:
I did not like to read of Sheik's failure to detect pH change with his plasma-cutter experiment; because I have expected this
machine to be PERFECT for a high-production Nitric-acid plant for us.
I am not sure why his experiments didn't work out yet; but I do plan to continue fabricating and testing such a plant here. I
still believe a plasma unit to be an excellent foundation for such a plant.
(also any old DC stick-welding supply; so there shouldn't be a need to drop big bucks on a plasma-cutter if you don't have
one; although they are DAMN handy to have around... :D )
Part-2: Supersonic Expansion
Last night, I did a forum-search for "supersonic" and "nozzle"; expecting those to have been discussed here already.
Surprisingly, I've found no mention of them in regards to Nitric; so I'll go ahead and introduce this concept; because it was a
key aspect of the later Nitric patents which were concerned with -efficiency- of the process.
As noted elsewhere in these nitric threads, the nitrogen oxides at very high temps want to go back to being oxygen and
nitrogen. One of the best ways to prevent this is to chill the arc-output gas. The faster you cool it, the more NO2 is retained as
product.
The best way to chill a gas quickly is not by refrigeration, but via expansion.
I believe it has also been shown/mentioned that the best way to improve production of the oxides is by raising the pressure.
These may sound conflicting, but they can actually be -complementary-.
An excellent way to achieve both desirable conditions in the same apparatus, is to use a supersonic, or DeLaval, nozzle at the
heart of the process. This type of nozzle, by design, is fed with high-pressure, produces a supersonic zone/shockwave in the
throat, and then rapidly expands the gases at the exit; thus achieving exactly what we want, to wit:
- high pressures in the hot reaction-zone
- extremely high cooling-rate within microseconds/centimeters of the oxidation reaction occurrence/zone.
My (still unbuilt/untested) design replaces the 'standard' plasma-torch with a machined copper Delaval nozzle which, unlike in
a regular plasma-cutting setup, WILL take the entire arc-current. The power-supply will have to be run at a minimum current-
setting to avoid rapid overheating and erosion of this nozzle. Even so, this setup is likely to only work for short runs; but that
should suffice for testing the viability of the process.
If the process works properly, I will then fabricate a double-walled version, to provide for water-cooling.
Note that a typical "plasma cutter" gives us a base to work with which is both constant-current, and designed to process gas at
about 4-10 atm. So it's indeed a good place to start, in my opinion.
Further on Arc Control and Nozzles:
Also, many designs of arc/plasma electrodes in various applications provide for turning the gas-flow into a vortex as it passes
through; which spreads the arc around the entire surface area of the nozzle/electrode; which prevents melting/erosion of the
surface at any one spot.
(normally, an arc WANTS to stay at the spot it first strikes, as that area instantly becomes surrounded with vaporized metal
ions which makes it the easiest place for the arc to jump to / continue at.)
One can also use EM forces to continuously move an arc along an electrode. I found this patent particularly interesting and
relevant...
PLA-pat2964679-ARC PLASMA GENERATOR - Moving Arc Saves Electrodes - SCHNEIDER.pdf
(these guys crack me up....the performance graph in that patent runs from 2,000 to 20,000 amps of line-current! those guys
don't fuck around... :D )
This one is also worth looking at:

DIR-pat3400070-HIGH EFFICIENCY PLASMA PROCESSING HEAD with DIFFUSER with EXPANDING DIAMETER - Naff.pdf
Now that I think about it, it may be helpful to add a list of relevant and semi-relevant patents to the end of this. These are all
patents that I have read and found worth saving and annotating. (Mods: if including the patent-list is inappropriate here,
please edit/delete, and let me know for future ref.)
In summary:
1) ANY power-supply will work; including MIG if that's all you have; but a constant-CURRENT source is much preferred; and a
higher-voltage supply gives you more options. While a plasma-cutter supply is likely best, and will indeed be the basis of my
first experiments; an old DC stick-welder is also constant-current, has a reasonably high open-circuit voltage, and should be
workable for a production plant. However, I can't verify this as known-fact until having done the experiment myself.
2) Superfast cooling of the reaction-products preserves more of the hard-won oxides. Supersonic expansion is one of the best/
easiest/cheapest/simplest ways to achieve this super-fast cooling.
3) The generation of plasma via RF fields (e.g., microwaves; but actually you can use other freqs too) is also a viable route.
The patent-list below was selected via "plasma", so will include some patents of relevance to the RF route as well.
4) Arc and glow-discharge are two different things; but both types of plasma are very "hot", in the energy-level sense. For
those interested in the non-arc routes, I suggest research into ICP or "inductively coupled plasma", and "electrodeless
discharge". Note that virtually all "glow discharge" situations require pressures BELOW atmospheric. This does not sound
optimum for NO's production; although such a plant may involve other factors which make the low-pressure unobjectionable.
ps; there areways to make a "glow discharge" stable at 1-atm, in somewhat limited situations. Again, the list below contains a
few items relevant to this.
I hope this post clarifies the situation somewhat regarding power-supplies for "plasma processing"; and also introduces some
additional concepts which are ripe for further discussion and experimenting.
ps; Mega, I was going to address your questions about resonant-cavity design too; but this post has gotten so long already;
that I'll leave it for another time. Suffice it to say that ALL cavities have "antinodes"; and that cavity design/construction can
be a relatively easy thing. I have made numerous cavities from 1/2"-3" copper water pipe. This material is also very easy to
work with, fabrication-wise; e.g. for water-jacketing, gas plumbing, etc. etc.. fyi, a few of the patents in the list below deal with
cavities.
List of A Few Relevant Patents:
CH-pat5397961-Apparatus for generating a pulsed plasma in a liquid medium.pdf

CH-pat6471932-Plasma-Catalytic production of Ammonia from N2 and H2O.pdf
CH-pat7037484-Plasma reactor for cracking ammonia and hydrogen-rich gases to hydrogen.pdf
DIR-pat3248446- PLASMA STREAMS AND METHOD FOR UTILIZING SAME - Applied Physics.pdf
DIR-pat3400070- HIGH EFFICIENCY PLASMA PROCESSING HEAD with DIFFUSER with EXPANDING DIAMETER - Naff.pdf
DIR-pat3429691- PLASMA REDUCTION OF TITANIUM DIOXIDE - Mclaughlin.pdf
DIR-pat3694618- HIGH PRESSURE THERMAL PLASMA SYSTEM - Poole.pdf
DIR-pat3862393- LOW FREQUENCY INDUCTION PLASMA SYSTEM - Dundas.pdf
DIR-pat4361441- Treatment of Matter in Plasma-Rotating 60hz Arc - Tylko.pdf
DIR-pat4680096- Plasma smelting process for silicon - Dosaj-DOW.pdf
DIR-pat4745338- Electromagnetically sustained plasma reactor - Hollis.pdf
DIR-pat5039312- Gas Separation with Rotating Plasma Arc Reactor - Hollis.pdf
DIR-pat5147998- High Enthalpy Plasma Torch - Tsantrizos-Noranda.pdf
DIR-pat5200595- Induction Plasma Torch Water-Cooled Ceramic Confinement Tube - Boulos.pdf
DIR-pat5288969- Electrodeless Plasma Torch for Dissociation - Wong.pdf
DIR-pat5630880- Large Volume Plasma Processor for Any Feedstock - Eastlund.pdf
EB-pat2902614- ACCELERATED PLASMA SOURCE.pdf
EB-pat3648015-Fairbairn-RF GENERATED ELECTRON BEAM TORCH.pdf
PCB-pat4618477-Uniform plasma for drill smear removal reactor.pdf
PLA-belljar.net_plasma.htm.pdf
PLA-ESAB-pat6346685-Plasma arc torch - Improved Sealing.pdf
PLA-pat2964679-ARC PLASMA GENERATOR - Moving Arc Saves Electrodes - SCHNEIDER.pdf
PLA-pat3004137-Producing High Gas Temp by Flowing Flame through Plasma.pdf
PLA-pat3278796-MAGNETICALLY CONTROLLABLE PLASMA FLAME GENERATOR.pdf
PLA-pat3577207- Microwave Plasmatron.pdf
PLA-pat3619403-GAS REACTION APPARATUS-Oxygen Plasma- Gorin-LFE.pdf
PLA-pat3641389-HIGH-POWER MICROWAVE PLASMA DISCHARGE LAMP - Leidigh-Varian.pdf
PLA-pat3790742-Plasma Torch Head - Auer.pdf
PLA-pat3903891-GENERATING PLASMA 1-atm - maybe Torch - Brayshaw.pdf
PLA-pat3911318-High Power UV-Vis from Plasma- Spero.pdf
PLA-pat4129772-Electrode structures for high energy high temperature plasmas.pdf
PLA-pat4883570-Reentrant Cavity for 10x Lower Freq - Chemical Processing in Atmospheric Plasmas - Efthimion.pdf
PLA-pat5069546-Atmos pressure capacitively coupled plasma spectral lamp- for AA.pdf
PLA-pat5122713-Atmospheric pressure capacitively coupled plasma excitation source- for AA.pdf
PLA-pat5131992-Microwave induced plasma process for producing tungsten carbide - Church.pdf
PLA-pat5274306-Capacitively coupled radiofrequency plasma source - Kaufman.pdf
PLA-pat5414235-Gas plasma generator with resonant cavity - Lucas.pdf
PLA-pat5414324-One atmosphere, uniform glow discharge plasma- 1-100khz.pdf
PLA-pat5534232-Apparatus for reactions in dense-medium plasmas.pdf
PLA-pat6232723-DC Plasma discharge via Liquid-loaded Porous Nonconductive Electrodes.pdf
PLA-pat6416633-One-Atm-Resonant excitation for generating plasmas - Spence.pdf
PLA-pat6686558-Atmospheric pressure inductive plasma apparatus.pdf
PLA-pat6771026-Plasma generation by mode-conversion of RF-electromagnetic wave to electron cyclotron wave.pdf
PLA-pat6982395-Plasma Welding with low jet angle divergence - Bayer MTU.pdf
PLA-The Brush Cathode Plasma--A Well-Behaved Plasma-NIST966.pdf
PLAS-pat3597650-ARC RADIATION SOURCES-like Plasma Torch.pdf
PLAS-pat5977715-Handheld atmospheric pressure glow discharge plasma source.pdf
PLAS-pat6217776-Centrifugal filter for multi-species plasma.pdf
PLAS-pat6923890-Chemical processing using non-thermal discharge plasma.pdf
PLAS-pat6936144-High frequency Plasma Source.pdf
SF-Co-Gen of C2 HCs and SynGas from CH4 and CO2 using Dielectric-Barrier Discharge Plasma Reactor without Catalyst at Low
Temp.pdf
SF-Is tadi-CoGen of SynGa s and C2+ HCs fro m Methane CO2 in A Hybrid Catalytic Plasma R eactor-Fue l2006 .pdf
SF-Istadi-CoGeneration of C2+ Hydrocarbons and SynGas from Methane and CO2 using Dielectric-Barrier Discharge Plasma
Reactor without Catalyst at Low Temp.pdf
SF-MIT-pat6322757-Low power compact plasma fuel converter- Cohn.pdf
SF-pat5626726-Cracking Hydrocarbon Liquids w Submerged Reactive Plasma - Lockheed.pdf
SF-pat6159432-Plasma Conversion of gas streams containing hydrocarbons.pdf
SF-Plasma Quench Process for Natural Gas-10119388.pdf
VAC-Ion-pat6824363-Linear inductive plasma pump for process reactors.pdf
VAC-pat4641060-Electron cyclotron heated plasma for vacuum pumping - Dandl.pdf
WELD-pat2806124- ARC TORCH AND PROCESS - RM GAGE.pdf
WELD-pat3555234- PLASMA ARC METAL MACHINING - Ilya Shapiro.pdf
WELD-pat3567898- PLASMA ARC CUTTING TORCH - Irwin.pdf
WELD-pat3641308- PLASMA ARC TORCH HAVING LIQUID LAMINAR FLOW JET FOR ARC CONSTRICTION.pdf
WELD-pat3809850- Plasma Arc Power System w Separate Pilot Arc Control - Carbide.pdf
WELD-pat4943699- Power Supply for Both Arc and Plasma -Thommes ITW.pdf
WELD-pat4977305- Low Voltage Plasma arc cutting - Severance-Ltec.pdf
WELD-pat5086205- Using Welding power supply for Plasma Cutting - Thommes-PowCon.pdf
WELD-pat5558786- High quality Plasma cutting of Stainless and Aluminum - Couch-Hypertherm.pdf
WELD-pat6037566- Reduced Cost Arc and Plasma Power Supply - Yasuhara - Panasonic.pdf
WELD-pat6313431- Plasma cutter for auxiliary power output - Schneider ITW.pdf
megalomania April 23rd, 2007, 01:44 AM

Now that is what I call a quality post :) You are indeed spot on about the need to rapidly cool the resulting NOx gasses after
formation. The reaction is in equilibrium at high temperatures, so cooling them will increase yields. I am not familiar with the
technology of supersonic nozzles, but I understand the principle, and they sound like the perfect solution.
Increasing the pressure will not only force more reactant into the finite space of the plasma, but it should also shift the
equilibrium away from free nitrogen and oxygen ions and towards ozone and nitrogen dioxides. There would be no equilibrium
benefit to be gained in forming NO from nitrogen and oxygen diatomic molecules because it is still forming an atom per atom
molecule, but ozone and NO2 are favored because they have 3 atoms per molecule. In theory, a rather large percentage of
NO should form because the percentage of nitrogen is so much higher than oxygen that it cant help but recombine to form
nitrogen oxides and nitrogen. The faster the products can be cooled, the higher this yield should be thus avoiding the inherent
instability of NO at high temperatures. I suspect the thermal decomposition of nitrogen dioxide is the reason why yields of
only a few percent are obtained.
This is certainly turning into a serious project, but with all of the equipment available to the consumer, and all of the
technology being off the shelf I can see this becoming a formidable tool for the home, farm, and small business production
of nitric acid or nitrogenous fertilizers.
A patent list is perfectly acceptable. Please, keep them coming.
Nitric-producer April 23rd, 2007, 05:21 PM

Hydra, do you have a drawing or something of the expansion nozzles you described, after reading through all the "plasma"
threads, I realised it could improve yields a good bit on all our "plasma reactors"!
Just want to say well done to everyone slaving away on projects like this. I feel we are starting to make a lot of progress now.
After reading this thread with great interest - I really want to go buy an old microwave! :D

mega, thanks.
Nitric: Here are a couple of excellent DeLaval design pages:
http://members.aol.com/ricnakk/th_nozz.html
http://www.engapplets.vt.edu/fluids/CDnozzle/cdinfo.html
That 2nd one even includes a design-program applet.
Considering the mass-rate and input pressure we're likely talking about (i.e. both pretty small), I'd guess that a nozzle for our
app will be quite small; and with a tiny throat.
It should be easily machineable on any small lathe. Not that gooey copper is all that much fun to machine... :D
Another alternative would be to grind a drill to profile; and simply drilling the part to shape.
Note: in our app of course, there's no need to machine the -outside- to profile. That's only done in aerospace apps to reduce
weight. Instead, one might look at drilling holes around the periphery as cooling-water channels; and in fact including nozzles
at the outlet-end; where the spray/steam would exit and be entrained with the rapidly-expanding NO flow.
As I understand the process, the sooner the NO's are in contact with water, the better. Can't get any sooner than this. :D
Drilling deep small-diam holes in copper will not be fun; but an alternative would be to go ahead and turn down the outside
(does not have to be to any particular profile though), then machine a shell and braze that on, to form a double-wall structure.
Add the tiny exit-spray nozzles in the end-plate.
Note; there are a number of copper -alloys- available; which may be much preferred for this application. The one I have in
mind right now is a copper-tungsten alloy intended for machining spot-welding electrodes from.
As I recall, it's about 7-8% tungsten; and is considerably harder and stronger than pure copper; while giving up about 20-30%
of conductivity.
Worth looking into.
By the way, the MSC catalog (which is HUUGE) lists all sorts of interesting materials for sale...including this alloy...and including
things like screen (mesh) in many different materials, including stainless. They also have graphite, as I recall. Anyway, that's
a catalog that's well worth having on the shelf.
This nozzle assy will be somewhat of a project, no doubt. But it has the potential to perform virtually every important and
desirable HNO3-gen function, in an optimal way; all in one part. So I intend to pursue it at least to the proof-of-concept stage.
webuyhouses May 7th, 2007, 12:14 AM

Regarding the price of microwave ovens, I have had great success obtaining used ovens by searching the trash.Try apartment
buildings, or trash collection night in neighborhoods. This is in the USA, and I assume it is true anywhere.
Most if not all of the ovens I found this way have worked (I must have sold 20+ for scrap metal) If they don't, check the fuse,
or just energize the primary side of the big transformer. I have never seen a magnetron go bad.(from cooking food;) ) Worst
case is the timer control burns out.
Also, the magnetron is powered through a half-wave rectifier. Tne post had mentioned hard-wiring the magnetron to operate
continuously. I haven't tried this, but the way to do it would be replace the single HV rectifier diode with a 4-diode full wave
rectifier (from 4 ovens). This will still have a power dip at 120Hz, but possibly adding a much larger capacitor will be able to
smooth it out. (I figure it would have to be around 4kv, 100millifarad compared to the oven's .68-ish millifarad one.) Keep in
mind that this will more than double the average power input to the magnetron. From what I've read, reflected power tends to
be more destructive than absorbing all the available power, so careful design of the rest of the device will be important to
keep it cool.
I just tried an experiment to reliably ignite a plasma ball. I whacked out a spot in the door frame so I could stick in the leads
from a 5kv NST, taped so that the arc would switch itself on. Switching on the transformer and the oven resulted in some
unstable plasma, and the wires melting VERY fast.
Thermiteisfun October 5th, 2007, 01:46 PM

http://www.emanator.demon.co.uk/bigclive/ozone.htm
This makes quite a bit of ozone, a few of the other things on his site are pretty interesting

I get a 404 error visiting that link... They have a homepage, but no links to anything else at all.
EDIT: There it is, ozone.htm
It's .htm NOT .html
Nitric-producer November 30th, 2007, 09:35 PM

Been doing some research on this lately. With regard to Mega's post on page 3 (post 24), the diagram of a plasma torch, I
believe that most of the workings are overly complicated for the average home user. Most of the eccentricities of the design
are used for ignition of the plasma ball :confused: .
A simple torch would consist of a magnetron coupled to a waveguide, (basically a rectangular metal tube) and the waveguide
attaching to a glass tube (pointing upwards) with air blown through it. To ignite the plasma inside the glass tube, would
however require a high voltage discharge across the airflow.
I would assume that (with my limited knowledge on waves and plasma), a plasma would form inside the tube and remain
there after the high voltage discharge stopped?
I have a neon sign transformer which would be perfect for the high voltage discharge. However I have no idea if this would
work at all :p
gaussincarnate December 6th, 2007, 11:55 PM

Unfortunately, my experience with plasma is much more theoretical than I would like. I can tell you, however, that the exact
configuration detailed in Mega's patent is not exactly experimenter friendly. Microwave resonance cavities are made out of
niobium-Yb alloys in a clean room. They are rolled on CNC lathes (spinning, not cutting lathes) and welded with electon
welding beams. The smallest sharp protrusion (dust, a burr, etc.) causes a catastrophic meltdown due to arcing and
instantaneous generation of very, very high currents. One of the largest manufacturers of MRCs (fnal) makes, on average,
one a month. In other words, I would not suggest this method.
I would however, suggest trying to form the plasma out of pure nitrogen and accelerating it towards a tank of water at the
other end. Naturally, unless you feel like making a superconducting accelerator, the majority of your velocity will come from the
nitrogen imput nozel. Luckily, N has a rather favorable charge to mass ratio in plasmas, meaning that an electric field will do a
great deal to accelerate it. Although it may sound rather complicated, I believe (more accurately, hope) that a simple N
plasma in a tube directed downwards into a tank of water with a very positively charged electrode at the end should suffice.
That is, of course, assuming that a very high velocity nitrogen ion will rip the hydrogen off and form nitrogen oxides that would
be instantly converted into nitric acid. It may be a long shot, but if it doesn't work, it could still be used to silence neighbors.
That would be a unique threat; "If you don't get your dog off of my lawn, I will shoot it...with high-velocity nitrogen ions. HAHA
I will give yor dog cancer. In eight years."

Improvised Manufacture of Nitric Acid > HNO3 with g r a h a m c o n d e n s e r
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GTOzoom Novem ber 13th, 2006, 07:06 PM

I n o n e o f m y d r e a m s , I p u r c h a s e d a g r a h a m condenser ('http://www.unitednuclear.com/other.htm )', and some NaNO3. I was
look ing into how to m ake white fuming nitric acid, but their really isnt any clear instructions. I am still looking for a source for
sulphuric acid, but that should n't be a problem (I'll probably end up using a car battery.)
I was wondering if using this method would work and an y possible ways to im prove upon it:
Set up a boiling flask with a tube attached to the top which goes to the condenser. Run water through it, an d b o i l t h e m i x o f
H2SO 4 and NaNO3. I beleive that 'pure' nitric acid should come out of the other e nd of the condenser and then I can just
refine it with urea and boil it u ntil it becom es white fum ing. It just sounds a little to easy thats all. :cool:
I a m a n a m ateur chem ist and I just want to m a k e s u r e t h a t I a m n o t o v e r l o o k i n g a n y d e t a i l s .
I will post pictures once the expirim ent is set up.
wymanthescienceman Novem ber 16th, 2006, 01:51 AM

W hat kind of connection are you going to use for the top of the condensor to the boiling flask? It obviously can't be rubber,
and since it isn't a ground glass joint, you'll have a hard tim e finding something to use that isn't eaten by hot HNO 3 vapor.
The only thing I would recom mend is teflon, as it is one of the few things that isn 't affected by HNO3. If you can't get a hold of
t h a t I g u e s s c h e m ical resistan t PVC tubing could work, if you can get the right size to fit that thing.
You'll also probably n eed a distillation adapter that has a thermom oter port so you can read vapor temperature. But my guess
is, u nless you can find suitable materials, it won't work with that condensor. You should probably get a one piece retort or a all
glass jointed distillation rig for nitric.
I was lucky e nough to have come across a one piece distillation rig with ground glass joints and a therm o m eter port that is
also ground glass:
http://www.roguesci.org/theforum/attachment.php?attachmentid=845&d=1163653308
It is rather self contained usin g only 2 or 3 joints. Just hook up two flasks, water cooling, and a vacuum adapter (Fo r HNO3),
a n d o f f y o u g o . P r o b l e m is I don't have a doub l e e n d e d 2 4 / 4 0 v a c u u m a dapter yet, or a vacuum pump for that m atter, so I
can't do pure HNO 3 anytim e s o o n .
You could try the m ethod used in the thread "HNO3 the easy way", although it takes a lon g tim e and it runs the risk of excess
NOx vapors if done improperly. I've tried it with lim ited success, but it evolved too m uch NO x (Even at 60c) and took way too
long that I gave up and decided to just do it the right way next tim e. So now I'm s a v i n g u p f o r a v a c u u m p u m p or a spirator
and an adaptor, then I'll be in business.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Cheap
Vacuum Pump
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wymanthescienceman January 31st, 2007, 11:09 PM

OK, first off I w anna let you know that since I want to use this for HNO3, that I think it belongs in this section. I've used the search engine but couldn't find anything about using
one of these.
I recently bought myself a Foodsaver vaccum preservation system for vacuum sealing foods, and I dont really have any more use for it so I was wondering if I could use it as a
vacuum pump for distilling HNO3. I cracked that baby open and found it was surprisingly simply built. (See pic # 1) Low and behold it uses a very simple pump for removing air
from the bags. I have a few questions about maybe using it as a possible vacuum pump for the distillation of HNO3.
First, do you think it can pull enough of a vacuum to distill? It looks as though it has a sw itch (The round red thing, See pic #2) that automatically kicks in the heat strip for
sealing the bag at a certain vacuum. The switch reads -500mbar and the only reason it is there is for activating the strip when it reaches its max vacuum, it can easily be
removed from the system if need be as I doubt the pump will create enough vacuum to implode a flask. The pump itself can create enough vacuum to crush a soda can, and
thats about the only way I have to tell the vacuum it pulls because I dont have a vacuum gauge.
Second, the pump and piston is made of some type of plastic (See pic # 3), I'm not exactly sure what kind, but the piston has a rubber gasket which is obviously a no no for hot
HNO3 vapor, so if I were to use this, any vapors or NOx gases w ould have to be removed or greatly reduced. So what would be my best bet for this? I thought about having a
sodium bicarbonate solution to filter out these gases, or some other type of substance in-line to remove the vapor before it reaches the pump and destroys it.
If anyone has gotten one of these to work for distilling, please let me know how it worked out. I'm up for any suggestions to get this to work because I can't spend over $200
for a vacuum pump. If you need more info about it I can try to answ er your questions.
Pic #1 http://www .roguesci.org/theforum/attachment.php?attachmentid=858&d= 1170298211
UPDATE: While doing a bit of browsing after looking at the vacuum sw itch I came across a vacuum table. I found out that if that sw itch indeed works w hen the pressure drops
by 500 mbar, then the vacuum pump must pull close to a 400mm Hg vacuum, but NOx are usually removed from HNO3 at around 200mm Hg for 10-30 min according to Wiki.
After seeing this I decided to check out boiling points for HNO3 at reduced pressures and came across a boiling point calculator. At 400mm Hg HNO3 will boil at approximately
66-68C, down 15-17C from its atmospheric BP of 83C. Would this reduced BP allow me to distill good HNO3 without excess NOx, or would I need a higher vacuum to do it
correctly? I've tried to distill HNO3 at atmospheric pressure but it doesnt work well. It's very slow and I can't do it in cold weather. I'm thinking that even though the vacuum I
may be able to create isn't enough, it will give me a somewhat decent HNO3, compared to w hat I got before. All I want is clear HNO3 at a concentration of 70% or higher.
What do you guys think? Am I way off?
Alexires February 1st, 2007, 04:35 AM

Good one wyman, I understand your pain of not being able to buy a vaccum pump.
First off, there isn't "enough of a vaccum to distil" per'se for HNO3. ANY vaccum is a good vaccum in this case. Since people have been known to distil clean nitric at STP, the
reduction of 15*C in bp will w ork w ell for HNO3. If you don't know how far exactly your pump draws down to, a suggestion is to attach it to a flask and put some DISTILLED
(important) w ater in there and see at what temperature that boils. That will tell you what kind of reduced pressure is in there. This w ill let you calculate the bp of HNO3 at that
pressure.
Nextly, hot HNO3 vapors + anything is bad. Glass works, but things like plastic, PVC, workbenches, hotplates, skin, etc aren't good things to mix with it. To make sure you don't
get that in your vaccum pump, you will w ant a vaccum trap or 3 hooked up betw een your vaccum adaptor (attached to your receiving flask ofcourse) and your pump. Fill 'em
with Bicarbonate solution and you should be pretty ok.
On the matter of if your flasks can take the pressure. As I understand it, if a flask is rated for vaccum operation it shouldn't matter how low the reduced pressure gets (even to a
"total" vaccum) the flask w ill keep together.
If you are unsure w hether your flask can take the pressure you can
1) Ring the maker and ask them. Make sure you get the right model, etc.
2) Buy some stuff you know is capable of operating at reduced pressure, or
3) Hook the flasks up to the vaccum pump, hide behind a wall where you can turn the vaccum pump off without getting inline for shapnel and turn the sucker on.
Remember, glass shrapnel is bad for your happiness.
A couple of other tips, when you are distilling nitric under vaccum, don't use a bunsen burner to heat it, don't use a water bath (a w hole bunch of hot nitric + w ater = pain). Use
an oil bath, keep the temperature as low as possible while still getting some distillate and that will keep it nice and free from NO2.
Can't think of anything else, so other than that, good luck and tell us how it goes!
aikon February 1st, 2007, 07:58 AM

w w w.frogfot.com
You'll find a DIY vacuum pump there made totally out of hardware stuff.
wymanthescienceman February 1st, 2007, 08:45 PM

OK, the main reason I started this thread was that I have yet to get a vacuum take off and 2 RBF's for my distillation rig. I have a water cooled Liebig that has a distillation
head on it, its a one piece thing, but I wanted to know if this would w ork before I spend $75 on the 3 more parts. If anyone thinks that this has a snowball's chance in hell of
working, then let me know so I can snap up a vacuum take-off, a 1000ml RBF, and a 500ml RBF.
Another thing is I KNOW that it's NOT necessarily safe to distill HNO3 indoors without a fume hood, but it's extremely cold outside so I can't distill outdoors. How bad of a risk
would I take if I did it indoors? All my equipment w ill have 24/40 joints and is totally sealed, but would there still be a huge risk of leakage and poisoning if the only outlet to
outside was the other end of the vacuum line? That was the only plan I had for now. My thought was the vacuum w ould remove any fumes and drown them in the vacuum
trap, I just can't see fumes escaping the joints when it's under negative pressure.
If it's too risky I'm not going to do it, so just tell me how I stand.
knowledgehungry February 2nd, 2007, 12:08 AM

IMHO it is not too risky to do it indoors if you can quickly exit the area and ventilate it. Maybe if you put the other end of the vacuum line into a bucket of w ater(I am assuming
the end of the vacuum line you are referring too is the exhaust end) it would provide one more layer of safety. It is not a good idea to try this if you live in an apartment.
If pssible use an electric heating source so that if things head south all you have to do is pull the cord and run, allow ing things to settle down on their ow n. I would not
recommend you do this indoors using a flame heat source.
wymanthescienceman February 2nd, 2007, 12:49 AM

I understand w hat you mean, I was thinking of just running the exhaust outside but doing it into a bucket of water will also help, though the water may freeze out there :)
And yes, I'm obviously going to use electric heat, the flask in a bath of w ater or sand. I'm still trying to figure out why Alexires says to use oil rather than water, it seems as
though hot HNO3 + Oil = FIREBALL/EXPLOSION. After reading a few other threads I see that water is the only sane liquid to use, but I figure that I'll use sand instead since it is
inert. That way I w on't have anything but hot acidy sand to w orry about in case of implosion, rather than a giant bath of hot dilute acid that will most likely sputter everywhere.
The bath I was going to use is a Teflon coated aluminum deepfryer that has variable temperature settings. I figured it w ould be my best bet since its nice and easy, plus Teflon
is always good.
As soon as I get a good deal on some flasks I'll try and get them so I can do a vacuum test w ith my setup, I really don't want an implosion when distilling ANYTHING. I figure I'll
try distilling water under vacuum a couple times first, then if all seems w ell I'll go for it. I would still like to hear from anyone that can help or has any more tips.
FU TI February 2nd, 2007, 11:05 AM

This is of course sick joke...but w hy not a glycerine bath? Little crack and you just made two things for the price of one. :P ...only question that remains will it also do the
ignition part? You are right NO2 and kerosine combo is used as rocket fuel (and also nitric acid) but I'm not sure will it explode on contact...need to check it.
This raise one OT question for forumities...I know a little about binary CW...but did anyone made reliable binary explosives. I know that black powder is complex mixture but it
is intimately mixed prior use. Has anyone made binary explosive of that kind like CWs are made?
I hope that maybe AN based solution as oxidiser and petrol/emulsifier as fuel can make "reliable" mixture. Imagine bomb/shell that mix the components in flight to target -
there is a couple technical hurdles in that (I know that) but it is posible to achieve. That would be some kind of safety mechanism/redundant arming sequence. AN based
mixtures are very safe already so this isn't best choice for testing the main goal/principle but can be used for developing purposes.
I know also for the Murphy's law : "It is not posible to make device foolproof as fools are so inventive"....so this is maybe overengeenering with little effect...also AN based
explosive w on't have the same bite like the "old faithfull ones" :).
As for vacuum issue...man if I could distill near 200Celsius boiling liquid (at 760mmHg) with use of a water vacuum pump your NA distilation will go just fine if you don't mess
something.
wymanthescienceman February 2nd, 2007, 02:17 PM

I'm just curious, what the hell are you talking about? What does any of w hat you said have to do with this thread other than the last bit you said? I'm guessing he must have
had to be joking about the oil bath to test me or something but what does NO2 and kerosene have to do with anything? And why are you rambling about CW? Honestly, some
people around here that talk about making CW are just plain messed up, what kind of crazy person would w ant to fuck with that other than a terrorist.
For mine and everyone elses sake on this earth, I hope you guys only joke of this CW stuff.
knowledgehungry February 2nd, 2007, 03:05 PM

He wasn't talking about CW he w as talking about binary explosives similar to binary CW. As to the glycerine bath, yes he was joking as he says "This is of course a sick joke".
Sand bath is good, however a problem I see w ith it(same problem w ith an oil bath) is that even if you pull the plug because you have a leak, the sand/oil is not going to lose its
temperature for quite some time.
If there is a large leak it is far too risky to go near the source unless you are wearing a protective suit and face mask as hot HNO3 vapor will oxidize just about anything.
Make sure the room you are doing this in is fuel(most things are a potential fuel, I am referring to solvents etc.) free, make sure there are no nice things made of metal that
you don't w ant to corrode. Make sure you have access to the outside, and a shower if you get it on you.
A homemade "fume hood" is not too hard to create if you only w ant to vent products to the outside not "scrub" them. Most large hardware store have the things needed, I have
one in my basement although my dad made it for drying the basement out rather than for chemical purposes.

"As to the glycerine bath, yes he was joking as he says "This is of course a sick joke".
When I was referring to the joke I meant the oil bath that Alexires was referring to. But anyw ays, using either a water, oil, or sand bath is almost the same when you talk about
heat loss. Yes water will lose heat faster than oil or sand but not a whole lot faster to be alot safer. The main reason I want to use sand is that if the flask does indeed implode,
it will just absorb the acid and it w on't splatter everyw here, but now that I think about it, it w ill just increase the surface area and all the acid will evaporate really fast causing
the room to fill with vapors, w hich can't be good. Now I'm stuck.
The flasks I w as planning on getting are heavy walled RBF's, the same ones this company sells w ith thier vacuum distillation kit, so I'm guessing that they run a very low risk of
collapse, almost none when I consider that my vacuum is nowhere near what a commecial vacuum can pull. The only thing I would have to worry about is my condensor
collapsing, which in that case wouldn't be so bad because it wouldn't be dumping a flask full of hot acid everywhere. I think if I test it and it holds up I should be fine, but I was
going to use some thick plastic sheeting underneath everything just in case of a spill, that way acid woun't touch antything but the acid resistant plastic. Is this a bad idea? Alot
of others use this plastic to make cone funnels for the jar in a jar method like in "HNO3 the easy way".
nbk2000 February 2nd, 2007, 10:13 PM

What about using a saturated solution of a mild base, like sodium carbonate, to neutralize the acid in case of a cracked flask?
Yes, there'll be a lot of foaming created by the resulting CO2, but hopefully not enough to cause any greater problem than that created by hot nitric acid splattering everyw here.
You could also hang a large sheet of thick polyethylene sheeting as a tent over the whole assembly so that the acid is contained in case of breakage.

I had thought about using a basic solution, but I had thought it would be a bad thing because of the foam but it sounds like it will be alot better to have alot of neutral foam
than acid. I think I might try it, depending on how much foam is actually produced. The other thing I had thought was using a base mixed in with sand in a sand bath, but that
might not be as good. I'll see when I figure out exactly w here I'm going to do this.
The tent idea sounds good, I'll probably try it. But depending on w here I do this I'll have to see how much room I have to work with.
FU TI February 3rd, 2007, 03:29 PM

Wow! Sorry man if I insulted you in some way...didn't mean to do that. Joke is a joke. On CW issue...you w ill notice more that one thread mentioning that subject so better
learn to accept it. I had to use that term since I couldn't find any other example to explain idea that sparked reading this thread. Anyway I do appologise to you since that was
(as I stated) - OT(off topic).
Anyway sand bath is something I have on my "to do" list. I need to do little book showelling to find a good blueprint for that, and I have seen also some improvisation jobs that
use small pearls of zeolites instead of sand. I'm still bumping that idea in my head...like is it safe and ussefull, it is a costly anyway so I wouldn't waste my money if it won't
work.
wymanthescienceman February 3rd, 2007, 03:48 PM

No problem w ith the OT thing, I was just w ondering w hy you decided to put that here, no biggie. And yeah, since there's alot of people that talk about CW, that's fine but I just
don't really understand why people talk of such things, and the fact that you put it in my thread kinda put in my head that people might think I was into them, which I'm not.
And as for the sand bath, I was figuring on using regular cleaned silica sand, its cheap and easy to get, 20lb will probably fill my bath and then some. I at first thought it was
safer because ther would be no sputtering, but as I already mentioned, it will make the acid evaporate into a death cloud in no time. I'm still mulling the idea of a base in the
sand to neutralize the acid, but I don't know how it will w ork. Another thing I had though of w as some kind of container under the bath to catch excess foam in case of worse
case scenario. I think I should be fine, I just have to make sure I have no leaks in the system when it's all hooked up. After I get my flasks I'll set up the system and take pics
so you all can see what I have planned.

Improvised Manufacture of Nitric Acid > Nitric acid physical properties - just the facts
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View Full Version : Nitric acid physical properties - just the facts
Al Sheik Yerbuti March 2nd, 2 007, 01:03 PM

Data for nitric acid. Feel free to copy this inform ation. This thread is for p hysical p roperties only.

S a m e graphs but larger. Alternate source for th o s e h a v i n g d o w n l o a d i s s u e s . R e d f u m i n g n itric pic, also. Clickable for larger
im a g e .
http://img33 7.imageshack.us/img337/6559/nitricaciddensityiy4.th.gif (http://img 3 3 7 . i m a g e s h a c k . u s / m y.php?
im age=nitricaciddensityiy4.gif) http://im g99.im a g e s h a c k . u s / i m g 99/6627/nitricacidboilingp ointpi7.th.gif (http://
im g99.im a g e s h a c k . u s / m y . p h p ? i m age=nitricacidboilingpointpi7.g if) http://img111.im a g e s h a c k . u s / i m g 1 1 1 / 9 1 1 8 /
nitricacidm eltingpointqm 9.th.gif (http://img111 . i m a g e s h a c k . u s / m y.php?image=nitricacidm eltingpo intqm9.gif) http://
im g338.im a g e s h a c k . u s / i m g338/7773/redfumingnitricay0.th.gif (http://im g338.im a g e s h a c k . u s / m y . p h p ?
im a g e = r e d f u mingnitricay0.gif)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > HNO3
Purification with CO2
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Shalashaska June 24th, 2007, 12:39 AM

This method of purification of HNO3 struck me as one of the more simple and less dangerous ways out there, since there is no distillation, and thus, no NOx. But
since this method has been but vaguely mentioned by NBK2000 about five years ago, in 2002, I have a couple questions.
1. First of all, I'm guessing that for this to work, the HNO3 must be impure with NOx, and not water, since water would freeze right along with the nitric. Or
would there be fractional crystallization, and the HNO3 would precipitate out as the water is frozen?
2. Should the dry ice be plopped right into the nitric acid, or put around the container it's in, kind of like a CO2 bath.
3. Should the HNO3 be a minimum concentration, or theoretically could you do this with 20% if you had such a horrible concentration.
4. In NBK's posts about it, he mentioned use of methylene chloride; is this a necessary component of this process?
Note: I know that the HNO3 should be as cold as possible, to prevent sublimation on contact, but that's about all I know for sure about this procedure.
Please excuse my complete lack of knowledge about this, but its only mentions have been rather obscure.
Edit: After finding the actual "Methylene Chloride" thread, I realize there was much more information on this subject than I previously believed. When I read it earlier, it was
the archive version and there was only one page.
Enkidu June 24th, 2007, 01:23 AM

The usefulness of the dry ice (frozen CO2) comes not from any chemical composition but its temperature. The temperature of dry ice is below the freezing point of anhydrous
nitric acid. The use of dry ice has nothing to do, AFAIK, with removing NOx.
The idea is to freeze the nitric acid and thus precipitate it from the DCM (or other extraction solvent). So yes, DCM is necessary.
If you were to subject 20% nitric acid to the temperature of dry ice, you would not be able to freeze out anhydrous nitric acid.
Look up the 'Preparation of Anhydrous Nitric Acid with Methylene Chloride' patent and carefully read the threads on this board about this process. You will learn all you need to
know.
Edit in response to your post below: I believe raffinate means that the DCM/HNO3 will be a separate layer than the sulfuric acid, in which case a simple medicine dropper
extraction could be used; is this correct?
Yes, that's correct, but to obtain any significant amount of nitric acid, you'll need the volume of quite a few medicine droppers.
Shalashaska June 24th, 2007, 01:38 AM

The usefulness of the dry ice (frozen CO2) comes not from any chemical composition but its temperature.
Well I knew that at least, so don't think I'm completely retarded. : /
Edit/Addition (as to not be a post whore)
Okay, so once the nitric acid is dissolved in the methylene chloride, how do you separate the DCM/HNO3 from the Sulfuric? It says:
The methylene chloride raffinate is then separated from the aqueous acid solution by any conventional liquid separation techniques.
I believe raffinate means that the DCM/HNO3 will be a separate layer than the sulfuric acid, in which case a simple medicine dropper extraction could be used; is
this correct?
s-lab June 24th, 2007, 04:28 AM

Where do you get your nitric anyway? all i can find is rubbish 10% stuff from my supplier. Is there a way you can make it more conc?
Rbick June 24th, 2007, 11:52 AM

s-lab-
Search the internet for reagent grade HNO3, there are countless chemical supplier sites that will sell you 70-90 + percent nitric acid. 90% will cost you quite a bit, we're talking
100 USD or more. You're better off in the long run making your own, but if you're lazy and have lots of money, it is easy to get. And of course you will probably be put on a
government watch list unless you have a damn good reason to have high conc. nitric acid. 70 percent can be bought for as low as 35 USD for 500ml. I think it is looked down
upon to list specific websites, but if you take 5 minutes to google search it, you'll find it.
Shalashaska June 24th, 2007, 03:49 PM

Oh, trust me, I have looked for nitric online. However, it was about at the 3rd chemical website that I discovered prices for 500mL 70% didn't get below $30-50 US. That's
about when I decided to just stick with ANFO and various synths that can substitute a nitration bath (H2SO4+xNO3) for nitric acid.
But then I found this wonderful nitric synth for *anhydrous* nitric, which caught my attention greatly due to relative ease, and the fact that I really wanted to make RDX, and
clearly, nigger-rigged bottle nitric wasn't gonna cut it.
Note: I noticed nigger-rig wasn't underlined red with spell check XD

Improvised Manufacture of Nitric Acid > Found 2 liters of 70% nitric acid. W hat to do with it?
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WEsailedfromPeru July 27th, 20 07, 02:1 5 AM

I j u s t h a p p e n e d t o f i n d T W O LITER S of 70% Nitric acid sitting in a bottle on a shelf in m y garage. The bottle is clear glass, b ut
it was encased in opa que styrofoam. I have no idea how old it is. What worries me is that the cap seem s to be plastic and it's
wrapped in electrical tape. :ee k:
I'm new with chem istry and I don't have the equipment to handle this stuff, though I'd like to be sure it's stored safely so that
I can use it when I acquire the tools and knowledge to. How do I store th is stuff properly? What do I need to buy in order to
handle and keep it safely?
This is sort o f an insane story so thanks for sticking with me here. Hopefully, I'll find more rare chem icals stashed away in m y
garage!
The_Duke July 27th, 20 07, 05:4 4 AM

Answers beyond your wildest dream await you, just follow the link...;)
Answers (http://www.roguesci.org/theforum / s e a rch.php)
Also note that we have a dedicated section here for nitric acid discussion, you have therefore broken several of our rules
(n00bs starting new topics is also against the rules in m ost cases). These are only just a few reasons why we discourage most
n00bs from starting new threa ds.
Shalashaska July 27th, 20 07, 01:0 9 PM

As for using it, if you're not fam iliar with nitric a cid at all, read up a lot (using link mention e d a b o v e ; ) ) a b o ut precautions and
syntheses.
If you wanted to get into some serious stuff, you're going to need to distill it to get upwards of 90%, but what you've got now
s h o u l d d o y o u for nitroglycerin, E/PGDN, and va rious m ono, di, a nd tri nitrations, depending on the specific com p o u n d .

I'll give you the sam e answer I give to anyone who tells m e t h e y f o u n d a c h e m ical and wa nts to know what to do with it: Give it
to m e...
Hm m , I m u s t b e c o n f u s e d b e c a u s e I t h o u g h t t h i s w a s c h e m istryquestion.com for a second. That's the place you want to ask a

l o a d ed question about what you can "do" with one of the top 20 most important industrial and laboratory chem icals of all
tim e . . . H o w a b o u t a s k i n g s o m ething easy like solving the unified field theory?
The answer your safety concerns in a manner u nderstandable to the non chemically trained: Treat the nitric acid like it was a
bottle of som e strangers urine. That is don't sniff it, don't spill it, don't get any on you, wash it up right away should any leak,
and handle the bottle in such a way to prevent any of the aforementioned dont's. Don't do anythin g with a strong acid that you
would not do with som e guys rancid pu rified stinky urine.
WEsailedfromPeru A ugus t 9t h, 2007, 06: 36 PM

It even looks like urine! But after reading what I have, I've got so m uch m ore respect for it. I'm definitely going to keep it a n d
work on planning a process to up the concentra tion.
I'm sorry I m issed the entire nitric acid section here. Thanks for moving the topic.
209 August 16th, 2007, 04:36 PM

No sense sta rting a new thread for this, but have a question about some acid I recently aquired. I aquired about 34 0 m L of
Nitric acid, the bottle was labeled nitric acid, and has all the prop erties and characteristics, yet the label had n o m a r k i n g s a b o u t
how old or th e concentration.
W h e n t h e b o ttle is opened, white fum es can easily be seen coming of the nitric acid. I am assuming that this nitric has a
high er concentraion than 75% but can anyone estim ate the range?? (I also know for a fact that it is infact nitric acid).
The_Duke August 16th, 2007, 06:29 PM

209, how ma ny tim e s m ust we tell you to UTFSE before it finally sinks in through your thick skull? Its really no wonder why your
rep is in the negative.
Try m easuring the de nsity for starters... :rolleyes:

Improvised Manufacture of Nitric Acid > Distillation of HNO3 with O TC products
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totenkov Novem ber 25th, 2007, 07:03 PM

A few days ago I was trying to distill some more nitric with purified KNO 3 s t u m p r e m o v e r .
Here is the p ic:
http://i215.p hotobucket.com/albums/cc6/totenkov/nitricacidstill.jpg
Nothing cam e o v e r . T h e t e m p was held at 85C for over an hour a nd a half and absolutely no HNO3 was reco vered. You can
clearly see NO 2 buildup in the flask, however nothing was distilled. I used the correct amount of reactants, taken from Jarrods
post, used a water bath for the heat and didn't have any clum ps of nitrate. The H2SO4 wa s d r a i n o p e n e r a t a b o u t a 9 3 %
concentration. This is the first time I have done it with drain opener and stump re mover, and it clearly isn't working very well.
I know m y setup is quite limited and d o e s n ' t h a v e a v a c u u m b u t m a n y d o n ' t h a v e s u p e r a d v a n c e d g l a s s w a r e ( n o n e o f m y

glass is ground except for my organic chem s e t b u t t h e c o n d e n s e r g o t s m a s h e d : ( ) T h e i d e a o f t h i s t h r e a d i s s o p e o p l e w h o
are really lim ited can find som ething that will work to make HNO3.
If you can spot a problem, let's here it! :)
Enkidu Novem ber 25th, 2007, 08:08 PM

It needs to be hotter. Your solution will boil at a higher tem perature than pure nitric acid.
Masonjar Chemist Novem ber 26th, 2007, 01:52 AM

I agree with Enkidu, also what ratio of nitrate to acid did you use? In m y first attem pts at nitric I always had too little nitrate
and yeilds were very poor.
High Density Novem ber 26th, 2007, 12:54 PM

Maybe you got a lot of reflux in the bo iling flask, Try to isolate it, Or use a higher water bath.
Blowing dry air trough the flask will drive the HNO3 through the condenser, And reduce NOX evolution, This requires som e m o r e
heating to compensate, And spills a little HNO3 .
W ith this me t h o d y o u don t e v e n h a v e to boil it, With ro u g h l y t h e s a m e tim e .

No vacuum p u m p n e e d e d .
I have used this method for sulfuric acid & nitric 68% 1:1 And works grea t, Density 1.5+ slightly yellow NA.

Improvised Manufacture of Nitric Acid > Proper/Safest Heat Source Q u e s t i o n
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TORCHed February 28th, 2008, 05:36 AM

I have navigated this forum for about a year now, and have never asked a question, but rather used the search to find some
kind of explanation to any questions I've had. However, I seem to find conflicting informa tion on the question below...
I a m wondering what is the proper/safest way to heat the the KNO3 and sulfuric acid m i x . I h a v e a 2 5 0 m l d istillation retort
setu p I'm p l a n n i n g o n u s i n g .
I have 99.9% KNO3 powdered, and m ore than likely will be experimenting with over the counter drain clearing products of 93%
purity. The process is not foreign to me, but the heat source is what I want to address.
I have read tutorials on this site as well as others all varying on the heat source to properly and safely heat in order to distill
the nitric acid. I have read of an open heat source such as a Bunsen burner, heating plate, using an oil bath, glass fiber
insulation, etc.
W hich is the most com m o n l y u s e d s e t u p d o y o u u s e a n d / o r r e c o m m e n d ?
Also, related to the use of an oil bath idea.... I can see using an oil such as olive oil or related cooking oils to be a possibly a
flam e risk if in contact with a flam e. However, I wonder if synthetic (autom otive) motor oil can be used as a substitute. That is
just an idea com i n g f r o m s o m e o n e w h o i s a g e a r h e a d .
T h i s m ay be a stupid question that probably was answered m any times, but any help would be gracious! Thanks guys!
Masonjar Chemist March 2nd, 2 008, 01:48 AM

I always use oil baths for distillation. U sually, I use a "cooking h ot plate" with a sm all aluminum pot filled with vegetable oil. At
the bottom of the pot, I put a small piece of a paper towel so th at the distillation flask never actually touch e s t h e a l u m i n u m
p o t . I h a v e u s e d a c a mping stove in place of the hot plate before; however I prefer the hot plate as tempe rature control is
m uch easier with it.
I'm not sure about synthetic motor oil, but I have heard that using conventional is a bad idea, and a quick way to stink up
your whole neighbor hood. I h ave used antifreeze in place of vegetable oil, but at the tem peratures that are required to distill
nitric, you will end up boiling most of it away. Another m e d i u m to consider are sand baths, I hear they are the easiest to use in
term s of tem perature control, I im agin e clean up is MUCH easier, and as an added bonus it totally inert! W orst case senario, if
your flask breaks in an oil bath, the hot nitric a cid will likely ignite the oil. W here as with a sand ba th, the worst thing that could
happen is that you loose your sand container.
JouMasep March 2nd, 2 008, 05:00 PM

You did not state if you distil under vacuum .
For lower tem p e r a t u r e s s u n f l o w e r o i l i s g o o d e n o u g h . I n t i m e it will polym erise a n d b e c o m e s t i c k y t h o u g h giving off rancid
alde hyde like fum e s o n h e a t i n g .
For t e m peratures hig her than c . a . 1 8 0 C i t s be s t t o u s e s a n d .
Much better than either for lower than about 22 0 degrees C, is silicone oil.
Its ex pensive though.
In truth, I have used the classical Bunsen burner plus asbestos / steel gauze mat as well.
Especially for sm aller quantities, it s c l e a n .
First prize for anything but very high temperatu res is a heating mantle. Big disadvantage is that besides the high price tag,
one needs a different m antle for each size of flask
O n e m ay t h i n k a b o u t D I Y c o n s truction here, I t s no t hugely com p l i c a t e d . O n e o f t h e c h a l l e n g e s lies in neatly sewing up the

woven glass fibre mats for the lining.
I h a v e n e v e r t a k e n o n e a p a r t , b u t I m quite sure that b e n e a t h t h e l i n i n g I would find a nichrom e t y p e o f resistive elem e n t

wire running within a f l e x i b l e e n c a s i n g of interlocking porcelain s e g m e n t s . T h a t s t u f f can b e f ound . I ve s een it of t e n e n o u g h
in electrical appliances.
H e a t i n g m a n tles rock!
Emil March 11th, 2008, 03:09 PM

P e r s o n a l l y I d o n o t s e e t h e n e e d o f s e tting up an oil ba th for nitric acid distillation. Reguardless of a vacuum distillation or n ot,
a n o p e n f l a m e will do quite sufficiently. Start with a m e d i u m flam e, and then regulate as necessary when you com e n e a r t o a
boil.
I u s e a c a m ping style gas burner with a steel gauze ma t. Hot plates are ok, but I am n o t a h u g e f a n o f t h e m . I f i n d t h e y t a k e
a long time to heat up your liquid, and I find an open flame is much easier to regulate beings as you can completely stop the
flam e in less than a second. A heating plate will stay hot for a long while.
T h e r e a s o n I u s e a c a m ping stove ove r a bunsen burne r is because the flam e is alot wider on the stove. It's basically a cooker
ring. This allows a wider heating area as I don't want to ever crack one of m y beautiful flasks just from b a d h e a t i n g .
I f y o u a r e a b l e t o d o s o , I d o r e c o m m e n d a v a c u u m distillation. This allo ws for a wider "zone" when it com e s t o h e a t i n g . I ' m

not sure of the tem p I distill at, as I do not have a therm o m eter incorperated in m y rig. At a guess I would say around the 50
d e g r e e s C m ark, as it does ta ke a fair am m o u n t o f h e a t i n g b e f o r e b o i l i n g. It doesn't really m a k e t o o m u c h o f a d i f f e r e n c e
though in this instance. You'll know when your acid is about to boil so that is all that m atters. This results in som e very nice
ever so slighty yellow fum ing Nitric, with not one sign of a NO x fume anywhere during the whole lab.
Judging from your post, you m e n t i o n e d a 2 5 0 m l retort, so I assum e you will be d oing at a norm al atm ospheric pressure. I
personally have never tried without a vacuum , but let us know how it goes. All I would suggest is to be a great deal more picky
with the heating at atm ospheric.
JouMasep March 15th, 2008, 07:04 AM

Vacuum distillation is tops for nitric acid the lo wer the temperature the less decom position and yellowing oxides.
W hat will also aid in reducing the dissolving of said nitrous oxides into your product, is the introduction of a fine, fine stream of
air.
Usual practice to achieve this is to take a thin glass tube and pu t this into the pla ce where normally your therm ometer would
be.
This tube is drawn out over a flam e to a very fine capillary and the broke n o f f e n d i s s u b m erged into the liquid. Not much
vacuum will be lost as a result of this as the am ount of introduced air is m inimal.
Apart from getting a cleaner p roduct, this type of set-up also elim i n a t e s b u m ping. (Even i f b u m p i n g i s l e s s o f a p r o b l e m d u e
the presence of solid KNO3 / K2SO4 crystals. Generally, the m o r e s m o o t h a n d e v e n a d i s t i l l a t i o n g o e s , t h e m o r e p u r e y o u r
product.
W hen using a retort, this set-up would not be possible. I have not used retorts since a very long tim e; it is what the alchem ists
used but better than nothing . If you only wish to do incidental experim entation, on a smaller scale it is a decent and cost
effective way to go. O therwise get to ground glass joints A.S.A.P. Should this be too costly, subsequently to discarding
(breaking!) my retort a very long tim e a g o , I p r o g r e s s e d t o m a k i n g s i l i c o n e s t o p pers (fro m s e a l a n t ) a n d t h e n c o v e red them in
m ile s of PTFE tape. It was laborious and eventually the vapours got through anyway. Just m a k e s u re that if youd decide to go
this route, you use pure PTFE plum bers tape, n ot something cheaper tha t contain s PVC or what have you.
W hatever glassware you use, Em il is right: a spread out heat source such as a ring burner- is better than a single point
burner.
R e m ember: the less concentration of heat on any point of your m ixture -and therefore least am ount of localized heating- the
less decomposition will take place, and the better your product! (The chance of glass breaking is also m inimized of course.)
Charles Owlen Picket March 15th, 2008, 10:27 AM

From a n e m p i r i c a l s t a n d p o i n t t h e a b o v e h a s b e e n m y experience as well. Howeve r the strength level of vacuum d i d n o t a p p e a r
to affect the product as much as the temp. (80 C)
A friend had left me with his e x p e n s i v e p u m p u n t i l h e c o u l d p u t a l o c k o n h i s s h e d a n d s a i d I c o u l d u s e s a m e to m y heart's

content. I ha d a h a l f - a s s p u m p and did several distillations. My pum p su c k e d . H i s p u m p s u c k e d m uch better! But both
a p p e a r e d t o a c h i e v e t h e s a m e results in the final produ ct.
I was careful with m y tem p and received the sam e very light lem on clear bright nearly anh ydrous a cid from both. Th e virtually
clear bright acid looked sweet and pure and the m orning dew. The tiny touch of lemon yellow could be brought to total clarity
with less than a gram of Urea.
However, tha t level of temp control could be m aintained best (IMO) with a hot plate of fair quality as anything else could not
m e e t t h e s a m e levels of standardization. O ne thing I have found is that when working with HNO3 / nitrations outdoors (the
s a f e st method for lack of fume hood); I work at 0400hrs as that tim e ha s the least UV an d yet enough light to see well (false
dawn). Setting up at "zero dark hundred" is worth the hassle as it's free from disturbances and intrusions as well.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > Special Project 1: Improvised Manufacture of Nitric Acid > Uses of
Non-Anhydrous Nitric Acid
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3287 November 29th, 2008, 03:10 AM

While there seems to be a small degree of conflict on the matter, I'm gathering that RDX production is impossible without anhydrous nitric acid, and that producing anhydrous
nitric acid is time- and equipment-intensive. So, my questions are:
What is the reasonable concentration limit with regards to home-made nitric acid (via the substitution reaction occurring when sulfuric acid and a nitrate are mixed)?
What high explosives can be produced with nitric acid in the 50-90% range, if it is impossible to home-produce anhydrous nitric acid?
Emil November 29th, 2008, 07:28 AM

I'm not sure if your post really needed an entirely new thread, but we'll let the mods decide that.
I'm not to sure about the concentration of the Sulfuric and nitrate mix, but it has to be relativley high. It mainly depends on your grade of sulfuric acid.
RDX is the most awkward really. I would only recommend making it if you really have some decent equipment, for the simple reason it is so picky on your nitric acid. For the
hassle it is worth, I would be more inclined to make something like PETN. The good thing about PETN is you can use 98% Sulfuric acid and 60-70% Nitric acid. The latter being
much easier to get hold of than fuming Nitric. I think there is even a method which involves Sulfuric and a nitrate, however I wouldn't use that route unless it was the last
option. Of course Pentaerythritol can be a real pain to get hold of, where as hexamine is dead easy. You just have to weigh the situation up.
If your only planning on making a smallish amount just to experiment with, then RDX could be worth the hassle. The damn problem with it on a bigger scale, is that the
synthesis drinks Nitric acid like it is going out of fashion. PETN's yields are FAR superior, which for the ametuer home chemist, makes it much cheaper to make.
UTFSE and you will find so many more explosives that can be synthesised using lesser grade nitric. After all, you are on the best explosives site on the entire internet, the
answers are only a few clicks and letters away...
3287 November 29th, 2008, 08:04 PM

PETN would be great if there were a ready source of pentaerythritol, but the difficulty of acquisition makes it unappealing for me.
I've read books that call for only 90% nitric for the nitration of hexamine, but given that the publisher of the books is usually Paladin Press I'll have to assume that they're
wrong when both mega and the folks at Sciencemadness call for 100%.
I'm only making a thread because of the particular situation - obviously there are many explosives that will employ nitric acid of various concentrations, but rather than seeking
out whatever I can find I wonder what people here think best balances cost and ease of material acquisition.
Alexires November 30th, 2008, 01:09 AM

but rather than seeking out whatever I can find I wonder what people here think best balances cost and ease of material acquisition.
Which reads to me:
but rather than UTFSE I wonder if other people will spoonfeed me the answers.
Enjoy your 2 week vacation.
megalomania December 2nd, 2008, 11:23 PM

You can use a lower concentration of nitric acid, but your yield will drop sharply. This is the general result of nitrating a large variety of organic compounds. You would not get
similar yields using double the volume of 50% acid either, it does not work like that. Lower acid strength means a higher pH, reduced chances of molecular interaction, different
solvent effects, take your pick.
If you increased the time of the reaction, say days or weeks instead of hours, you may eventually get the kinds of yields a concentrated acid would give. May, not will.
I provide many specifics of acid concentrations in the procedures on my website at roguesci.org. Invariably the vast majority of explosive preparations use 98% or greater nitric
acid. This is not a coincidence, it is not something I made up, it is something emphasized in many scientific journals. Typically the presence of water interferes with the reaction
to the extent that yields drop with decreasing acid concentration.
All you had to do was use the search engine I set up just for the Chem Lab procedures, looking for nitric acid. You would easily have found a list of every explosive using nitric
acid, and a quick scan of the pages would have shown you what the percentages are. A whole 15 minutes to answer that question. You could instead have made a post with
actual examples of what explosives you found through your own research, and then asked your question. This is the proper way to do it and it would have made for a far more
interesting and useful new thread. Doing this would have increased your standing, now you are flushed down the toilet for wasting everyone's time.

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1. Uses of Non-Anhydrous Nitric Acid (4 replies)

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rikkitikkitavi August 23rd, 2002, 12:14 PM

So what mea ns of dehydrating do we have? Im refering to conce ntrating

There is also the possibility of using solid dehydrating agents like

Industrially, Mg(NO 3)2 is used in parallell to the H2SO4 m e t h o d .

Is this feasible to do in a labscale?

vulture August 23rd, 2002, 02:53 PM

xoo1246 August 23rd, 2002, 05:32 PM

<sm a l l > [ A u g u s t 2 3 , 2 0 0 2 , 0 4 : 4 4 P M : M e s s a g e e d i t e d b y : x o o 1 2 4 6 ] < / s m a l l >

kingspaz August 24th, 2002, 09:38 PM

Pu239 Stuchtiger August 24th, 2002, 10:55 PM

MgSO 4 + HNO 3 ----&gt; MgHSO4(NO3)

Polverone August 25th, 2002, 02:17 AM

rikkitikkitavi August 25th, 2002, 05:44 AM

However, it is a solution of 72 % m /m that is used in the extractive distillation.

B e s t i s P 2 O 5 , H 2 S O 4 , C a S O 4 e t c. This lead m e to believe that

Madog555 August 29th, 2002, 04:54 PM

rikkitikkitavi August 29th, 2002, 05:36 PM

jimwig S e p t e m b e r 3 0th, 2002, 10:23 PM

s o u n d s r e a s o n a b l e . m i x t u r e o f "HNO a nd HSO " and distill. should be som e pretty strong

rikkitikkitavi October 1st, 2002, 02:51 AM

simply RED October 18th , 2002, 08:15 AM

Marvin October 19th , 2 0 0 2 , 0 9 : 2 1 P M

Polverone October 20th , 2002, 06:07 AM

vulture October 20th , 2002, 11:56 AM

simply RED October 21st, 2002, 10:37 AM

Ca(NO3)2 - 1dolar per kilo

Marvin October 22nd, 2002, 01:33 AM

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stanfield July 20th, 2001, 05:17 PM

Anthony July 20th, 2001, 08:12 PM

So you should need tw ice as many molecules of NaNO3 to H2SO4.

RAM of NaNO3 = 1x23 1x14 3x16 = 85

Lagen July 20th, 2001, 08:39 PM

stanfield July 21st, 2001, 03:41 AM

more seriously, i found 405g like anthony...

Any reply is more than appreciated

Lagen July 21st, 2001, 08:25 AM

Somebody with greater experience, please give us your comments...

Anthony July 22nd, 2001, 03:20 PM

Lagen July 22nd, 2001, 04:08 PM

stanfield July 22nd, 2001, 06:05 PM

Lagen July 22nd, 2001, 06:29 PM

Anthony July 22nd, 2001, 08:43 PM

stanfield July 23rd, 2001, 05:31 AM

Lagen July 23rd, 2001, 08:11 AM

stanfield July 25th, 2001, 05:46 AM

and could you send me your density table ?

thanx for all !

Demolition July 25th, 2001, 05:59 AM

stanfield July 25th, 2001, 09:24 AM

John456 July 25th, 2001, 02:05 PM

stanfield July 25th, 2001, 05:55 PM

here is my distillation apparatus :

stanfield July 25th, 2001, 05:58 PM

Lagen July 25th, 2001, 07:52 PM

MgSO 4 + HNO 3 ----> MgHSO4(NO3)