An illustrated guide on the preparation of white phosphorus (P4) from red phosphorus (P)

By Pyro
16 August 2013, 3:48AM
-Introduction
White phosphorus is an extremely reactive and hard to get allotrope of phosphorus while red phosphorus is more
readily available from chemical suppliers or matchboxes.
In this article I will describe one of the ways to make the white allotrope from the red.
the reaction proceeds as follows:

So if red phosphorus is strongly heated the red phosphorus will convert to white phosphorus, but as the double
arrow indicates, this reaction is reversible so it is important to cool down the newly formed white phosphorus as
soon as possible.

This article will consist of three parts:

the first on the bending of a regular test tube to make a suitable retort, the second on the preparation of white
phosphorus from red phosphorus and the third on the purification of the crude white phosphorus to analytical
grade white phosphorus
-Reagents
H2SO4
P
K2Cr2O7
dH2O
(the amounts used here are not crucial)
-apparatus

-Hotplate

-beakers
-clamps and stands
-stirring rod
-spatula
-tweezers
-test tube (soda lime or 3.3 borosilicate)
-thermometer (ideally built into the hotplate)
-bunsen burner/teclu burner
-matches
-For the first and second part rubber gloves are not recommended as you are working with fire and in that case
rubber will make burns worse, but in the third they are highly recommended! When I was finished mine smelt
seriously like P4.
-All the appropriate safety equipment. A lab coat is essential, followed by cotton trousers, closed shoes and
goggles or a faceshield
-Part I---Bending a regular test tube to make a suitable retort
I started with a box of 16mmx160mm soda lime test tubes. I prefer soda lime as it is a lot easier to bend. Many
people prefer 3.3 borosilicate because it's less prone to cracking due to thermal stress but it's more expensive
and If you heat it properly there should be no danger at all of it cracking
you will need to light the burner and turn it to the maximum setting, then take a test tube by each end and hold the
middle in the upper part of the flame, rotate it for about 1-2mins. You should see the flame turning yellow where
it's touching the glass, now gently pull the two ends apart while bending, this will ensure a smooth bend with no
kinks that can collect P4.
the finished test tube should be bent between 90* and 100*, the closer to 90* the better. It should look something
like this:

but ideally it would be closer to 90*.

-Part II---preparation of crude white phosphorus from red phosphorus

With the spatula, put red phosphorus into the bent test tube. put enough in to get a 2-3cm deep layer on the
bottom, then place it in a clamp and suspend it above a beaker of warm water (+-50*C) so that the mouth is as far
under water as possible.

I find it unnecessary to mix SiO2 with the red phosphorus, I have never had problems with bumping.
Now start the burner, you want a gentle flame. I set it so there is a little yellow tip on it so its not too hot. Now hold
the base in your hand and tilt it towards the tube, heat the open end first and work back to the closed end (e.g.
from left to right on the above picture).

As soon as the glass gets hot enough the P will ignite. It is nothing spectacular, just a barely visible yellow green
flame which goes out quickly.

In this picture the P is on fire, it is nothing to worry about

now continue heating, the red phosphorus will turn to P4 and you will see the vapors coming up and condensing
in the curved part. The glass there is hot enough to keep it molten so once enough has built up it will run down the
glass and drip into the beaker

Here the drops of P4 are condensing and dripping down

Warning!:If you overheat it bubbles of P4 vapor will come out of the test tube, catching fire the effects
range from a big bang to a gentle fizzing sound but will not occur unless you are careless
The P4 that collects in the beaker will be anything from dark red (almost black) to lemon yellow depending on how
carefully you heat.
cleanup (retort) Now that you have your P4 you need to safely remove it from the water without it catching fire.
I have two ways.
#1:wait for the retort to cool completely and then get a stopper large enough to block the mouth of the tube, then
put in between a pair of tweezers and insert it into the mouth of the retort, loosen the clamp and remove the retort.
Then place it somewhere safe (e.g. concrete, sand,...) and gently remove the stopper and let it burn, usually it just
smokes, but better safe than sorry.
#2: again wait for the retort to cool down completely, then get a pipette and gently start bubbling air into the retort,
waiting a few seconds between bubbles. the P4 will smoke a bit and sometimes catch fire. then remove the clamp
from the stand and carry the test tube to the safe spot, holding it by the end of the clamp
-Part III---Purification of the crude P4
when the P4 is freshly distilled it is usually orange with lots of other junk.
Half fill a pipette with water and then suck in the molten P4 and transfer it to a beaker of dH2O at 50*C. next add
5ml of H2SO4 and then 2 spatulas of K2Cr2O7 and stir for about 5-10 mins. then transfer the purer P4 to another
beaker of 50*C dH2O and stir for about 20 mins. by then it should be white. If it is then pipette it off to a clean
beaker of water, cool it and transfer it to a good bottle.
-results
a bottle of nice pure P4

remember to store it in the dark!

-IMPORTANT SAFETY NOTICE!!!

If you wish to try this you have to know a few things about P4:

-White phosphorus is EXTREMELY flammable and toxic

-Red phosphorus is very flammable
-high temperatures are used that can result in severe burns
-Chromium waste is hazardous for the environment
-CrVI is toxic and carcinogenic
-98% H2SO4 is extremely corrosive
-burning P and P4 creates lots of corrosive smoke
-any drops of molten P4 immediately catch fire if exposed to air
-in parts 1&2 NO gloves, molten rubber/plastic is not nice, I speak from experience (molten nylon)
-all cotton clothing, faceshield, closed shoes/boots are very important! also have a respirator nearby. a piece of
burning P4 throws smaller bits of burning P4 around and makes a lot of toxic smoke (I speak from experience
here too

you do not want to be anywhere near here

Should an accident occur, remember these things:

-put 1% CuSO4 solution on the affected area, this will give the P4 a brown/black coating, making it easier to clean
off any small bits of P4 with tweezers.
-Remove affected clothing to minimize risk of re ignition
-soak the affected area in a saline solution and keep it moist
-visit a (military) doctor is any symptoms of phosphorus poisoning occur.
from the CDC emergency response card:
Quote:

TIME COURSE: Exposure to white phosphorus may cause immediate burns that heal slowly. Systemic
toxicity from white phosphorus exposure is classically divided into 3 phases. The first phase, the
gastrointestinal phase, occurs a few minutes to 8 hours following white phosphorus exposure. Shock
during this phase may be severe enough to cause death in 24 to 48 hours. The second phase, the
asymptomatic phase, follows the first phase and lasts for 8 hours to 3 days. The third phase, the multiorgan failure and central nervous system injury phase, may begin 4 to 8 days after the second phase
begins, and may end in death.
EFFECTS OF SHORT-TERM (LESS THAN 8-HOURS) EXPOSURE: White phosphorus burns in air and
causes severe burns upon contact with skin or eyes. White phosphorus smoke will also cause eye and
respiratory tract irritation. Other initial adverse health effects are primarily due to gastrointestinal
irritation.
EYE EXPOSURE: White phosphorus fumes cause severe irritation and the sensation of a foreign body in
the eye. This leads to excessive tear production (lacrimation), spasmodic blinking (blepharospasm), and
increased sensitivity to light (photophobia). White phosphorus particles are caustic and seriously
damaging when in contact with tissues. They cause damage to the cornea, including perforation,
inflammation of the interior of the eyeball (endophthalmitis), and abnormal turning out of the eyelid
(ectropion).
INGESTION EXPOSURE: Stage 1: Feeling of warmth or burning pain in the throat and abdomen

accompanied by feelings of intense thirst; nausea, vomiting (emesis), diarrhea, and severe abdominal
pain; garlic odor to the breath, vomitus, and feces; vomitus and feces may glow (luminesce) and are
capable of causing burns on contact with skin; death may occur within 24 to 48 hours due to complete
cardiovascular collapse.
INHALATION EXPOSURE: Eye and upper respiratory tract irritation are expected. Delayed onset of
accumulation of fluid in the lungs (pulmonary edema) is possible. Whole-body (systemic) effects may
also occur. See Ingestion Exposure.
SKIN EXPOSURE: White phosphorus causes severely painful, partial (second degree) to full thickness
(third degree) burns, which have a characteristic yellow color and garlic-like odor. Smoke may be
released from the burn site from the continued burning of white phosphorus or the formation of
phosphoric acid. White phosphorus is highly fat soluble, and easily absorbed through the skin, possibly
causing whole-body (systemic) effects. See Ingestion Exposure

here are other ways to perform step II:

http://www.versuchschemie.de/topic,5774,-Wei%DFer+Phosphor.h...
http://woelen.homescience.net/science/chem/exps/RedP2WhiteP/...

Conversion of phosphorus, red to white

This webpage describes how red phosphorus can be converted to white
phosphorus fairly easily. Red phosphorus, although not available
everywhere, still can be purchased in many countries, while white
phosphorus is much harder to find. For that reason, it may be interesting to
convert some red phosphorus into white phosphorus. The purity of the
white phosphorus, obtained in this way is fairly good, although it certainly
cannot reach the quality of commercial samples. The material, obtained in
this way, however, is perfectly suitable for all kinds of spectacular
experiment with white phosphorus.
This experiment is one of the most risky
experiments from the chemistry section of this
website, due to the large risk of fire. White
phosphorus is EXTREMELY flammable and very
poisonous. It also is corrosive and can give rise to nasty wounds, which are
only healing very slowly. This experiment MUST be conducted outside, with
nothing flammable and valuable nearby, or in a very good fume hood, with
glass protection wall. Some vapor of white phosphorus may be emitted.
These vapors are intensely poisonous. That is another reason why this
experiment must be conducted outside.

The main principle behind this experiment is that red phosphorus, when
heated strongly, decomposes and sublimes in the form of P4 molecules.
The P4 can be condensed on a cooler place to white phosphorus. A special
distillation setup, capable of handling very high temperatures, combined
with the use of an inert atmosphere, would be required to perform such a
sublimation of red phosphorus. On a small scale, it can be done with a
simple test tube, which is prepared in a special way.

Required chemicals:

red phosphorus
marble chips (calcium carbonate)
hydrochloric acid (needed for "safe" cleanup)
bleach or calcium hypochlorite (needed for "safe" cleanup)

Required equipment:

test tube, made of Duran glass

hot propane torch
clamp for test tube
glass wool

Safety:

See warnings above, this experiment MUST be conducted

outside!

Disposal:

Any white phosphorus waste (e.g. on test tube walls, in a tub, in

glass wool, in tissues) must be destroyed. Nothing may remain
behind, due to the extreme risk of fire. A special section of this
webpage is devoted to the cleanup after performing the experiment.
The cleanup itself also is a rather nasty job, but the final result is a
safe situation, without risk of fire.

Preparation of special "distillation device"

A test tube must be bent in a special way, such that it contains the part
where the red phosphorus can be heated and at the same time it contains
the part where the white phosphorus can condense and can be collected.
The test tube must be one of high quality Duran glass. Ordinary glass
certainly will crack in this experiment, with possibly disastrous
consequences. Duran glass is not easily melted, but with a hot propane
torch this is possible, when the test tube is kept in the tip of a narrow
roaring flame. The test tube is slowly rotated and the place which must be
bent is kept in the roaring flame. At a certain point, the glass starts glowing.
At that point, the test tube can be bent carefully and slowly. If the bending
angle is sufficiently large, then take it out of the flame and let it cool down.
After cooling down, a similar thing is done with the second bend. Use
plastic clamps for manipulating the test tube. Although the glass becomes
amazingly hot at the place where it is bent, near the bottom and the top of
the test tube it only becomes warm, one can even touch it without getting
burnt. But for convenience and safety it is better to use a clamp for
manipulating the test tube.
The final result is shown in the picture at the start of the webpage. The red
phosphorus is put in the bottom part of the test tube, the
- shaped part
of the bent test tube collects the condensed and liquid white phosphorus.

Filling the "distillation device" and preparing for heating

The bent test tube first must be filled with some red phosphorus, and after
that, it must be flooded with carbon dioxide. The carbon dioxide can be
prepared by putting some marble chips in dilute hydrochloric acid and the
gas must be delivered into the bent test tube with a thin flexible tube, which
is pushed into the powdered red phosphorus. Be sure to make a lot of
carbon dioxide, such that really all air in the bent tube is displaced by the
gas. Production of carbon dioxide must not be too fast, otherwise the red
phosphorus may be blown out of the test tube.
Immediately after that, put some glass wool in the upper part of the test
tube, such that the carbon dioxide does not quickly escape from the tube.
Immediately after that, attach the test tube to a clamp in a position as
shown in the picture below.

At the left, one can see the glass wool (most of it is covered by the clamp),
at the right, one can see the red phosphorus, which will be heated.

The test tube must be loosely closed with a piece of glass wool. Do not use
a rubber stopper or a tightly fitting cork. Such a stopper might pop out of the
test tube during heating (pressure buildup, due to expanding gas) and that
will result in instant fire.

Heating the red phosphorus, making white phosphorus

With the setup as described in the section above, the experiment can be
performed relatively safely. One does not have to fear ignition of the
phosphorus inside the test tube. The only real risk is cracking of the test
tube, while the red phosphorus is heated. If that occurs, then there will be
instant violent fire and burning drops of phosphorus will be sprayed
around. Be prepared for such an event, and assure that you can quickly
step away if this occurs. Also wear adequate eye protection and leather
gloves during the heating part of this experiment. If the test tube cracks,
then quickly step aside and let the phosphorus burn. Do not try to
extinguish the fire, this is nearly impossible. For this reason, this experiment
MUST be performed outside, at a place where a phosphorus fire cannot do

any harm. White phosphorus burns are particularly nasty, because burning
droplets are sprayed around all over the place.
In order to reduce the chance of cracking of the test tube, first heat the
entire part, where the red phosphorus is up to the bend (the right part of the
test tube in the previous picture, the left part in the picture below). This
heating must be done evenly. After this initial heating, the flame of the
propane torch must be pointed below the red phosphorus and it must be
kept at that place for a while. When this is done, one quickly sees formation
of yellow/white fumes.

At a certain point, the flame of the torch must be put to full blast, but the test
tube may not become so hot that it melts. Slowly, the red phosphorus
sublimes and impure white phosphorus condenses in the cooler part of the
test tube, which is the
- shaped part of the test tube. The result is
shown in the picture below.

The picture shows the remains of the red phosphorus, which is a black solid
(impurity of the red phosphorus, this most likely is another allotrope of
phosphorus, which is much less reactive than red phosphorus) and a liquid
blob of white phosphorus, which appears red due to contamination with
small particles of red phosphorus. Also, drops of white phosphorus appear
on the upper side of the test tube. These can be heated a little as well, in
order to have all the phosphorus collected into a single blob.
At the end of the experiment, all red phosphorus has sublimed, only some
black crud remains, as shown in the picture below, which was taken from
above.

The resulting white phosphorus is shown in more detail in the following

picture:

When this situation is reached, then let the test tube cool down, with the
glass wool still in its opening.Never remove the glass wool, as long as the
test tube is not completely under water! Opening of the test tube will result
in instant fire!

Working up the white phosphorus, purifying to some extent

When the test tube has cooled down, then take it out of the clamp and
immerse it in a tub, full of cold water. When it is completely under water,
then the glass wool can be removed and the water flows into the test tube
and air/carbon dioxide bubbles to the surface of the water. When cold water
is used, then the white phosphorus solidifies. Once the test tube is full of
cold water, it can be taken inside, and further workup can be done inside.
The picture below shows the test tube, full of cold water, with the solidified
blob of white phosphorus and the glass wool also inserted again.

Further working up can be done in a tub, filled with a layer of 10 cm of warm

water. Take water, which is quite warm, but not so hot that you can't stand
working in it with your bare hands.
Keep the test tube still full of water (with the glass wool plugged in and the
test tube kept in the same orientation as when it was heated with the
propane torch!) under a tap with hot running water, e.g. while filling the tub,
in which further work up is done. The phosphorus will melt again.

Next, take a small glass beaker and put this in the tub with warm water. The
beaker must be completely under the warm water, and a few cm of water
must be above the beaker. Keep the test tube with the molten phosphorus
under water, above the beaker, and then remove the glass wool and
carefully pour the white phosphorus into the beaker. All of this must be
done under the warm water, otherwise instant fire will be sprayed around!
Try to avoid pouring in some of the black crud as well. For this reason, it is
important that during the melting of the white phosphorus, the test tube is
kept in horizontal position, such that no white phosphorus by accident flows
to the bottom of the test tube and is contaminated with the black crud.
Once all phosphorus is in a beaker, the beaker can be taken out of the tub.
The raw liquid material at the bottom of the beaker looks as follows:

A small video shows the material in the beaker under a layer of warm water.
It is a fairly mobile liquid, which does not stick to the glass. The video can
be downloaded by clicking here, its download size is approximately 2
MByte.

Further purification by filtering

The white phosphorus, as prepared according to the procedure given
above, already is suitable for many experiments, but one can fairly easily
purify the liquid phosphorus by means of filtering through glass wool under
water.
Again, all work must be done completely under warm water. Never allow air
to come in contact with the liquid white phosphorus!
The white phosphorus does not stick to glass. One can easily suck the
phosphorus into a glass pipette with 5 to 10 ml volume. In order to do so,
the beaker with the phosphorus must be put under warm water again, and
the pipette also must be put under water, assuring that most air is out of it.
Under water, first suck in some water, and then suck in all crude white
phosphorus. Next, while keeping all of the material and the pipette under
water, take a piece of glass wool and keep this in front of the opening of the
pipette and then carefully press out the phosphorus above the beaker. If
this is done, a lot of solid crud remains behind in the glass wool and the
white phosphorus goes through the glass wool. Only use a thin layer of
glass wool, otherwise you will have to press too strongly, with the risk of
pressing all of the white phosphorus out of the pipette at once, resulting in
many small globules under the water, which need to be collected again.
After this purification step, the phosphorus still is not white. It has a
brown/yellow color after this purification step, but better results cannot
easily be obtained with the simple equipment, used in this experiment. The
yellow phosphorus, obtained in this way, however, is perfectly suitable for
synthesis work, and also for all kinds of experiments, which require white
phosphorus.
The beaker with the purified white phosphorus can be taken out of the tub
and the warm water can be replaced by cold water. With this replacement
of water, again assure, that the phosphorus does not come in contact with
air.

Once the phosphorus has solidified and cooled down to 15 C or so (the

temperature of the cold water), it can be transferred to a petri dish, filled
with water. Brief contact with air now does not lead to instant fire anymore.
With a sharp knife it can be cut into smaller pieces, while it is under a thin
layer of water in the petri dish. After cutting, the smaller pieces have to be
put in a little vial, filled with cold water. Do not take pieces of white
phosphorus in your hands. The pieces may ignite and cause severe
burns. Use a pair of tweezers for transferring the small pieces from the petri
dish to the vial.
The final result is the following, which is approximately 3 grams of white
phosphorus:

The solid is soft and waxy. A rounded glass stick can easily be pressed into
the solid. A sharp knife fairly easily cuts the solid.

Cleaning up of all tools, glassware and tub

All items, which have been in contact with the white phosphorus, may have
solidified droplets or globules of white phosphorus on them or in them. It is
very important to thoroughly cleanup any remains of white phosphorus.

Simply wiping off with a tissue and then throwing away of this tissue
introduces an unacceptable risk of fire, especially on warm summer days.
White phosphorus can easily ignite when in contact with air, even at room
temperature.
As a demonstration of the danger, the glass wool, which was in the test
tube during heating, is kept in air for a while. The picture below shows how
much smoke is produced from this piece of glass wool. Knowing that this
piece of glass wool is completely soaked with cold water makes it even
more scary. A video also shows this smoking of the wet glass wool.
Download size is appr. 1.25 MByte.

Throwing such smoking material in the trash bin, introduces a serious risk
of fire. Such a fire may occur, hours later, when most of the adhering water
has evaporated. All white phosphorus hence must be destroyed.
A sure method of destruction is the use of a bleach solution, to which a
slight excess of hydrochloric acid is added. One can also use calcium
hypochlorite (swimming pool tablets or granules), which is added to 10
times its volume of water, and then some hydrochloric acid is added until
the liquid becomes clear and green/yellow. Bubbles of chlorine will be
produced in the liquid, as if it were a soda drink. Immerse the glass wool in
this liquid for a while. Also pour this liquid into the bent test tube. The tub
also must be treated with this liquid. Any tissues, brushes or whatever is
used for cleaning also must be treated with the chlorine-water. Avoid
contact of the chlorine-water with the skin.
Let the chlorine-water do its work for 5 minutes and then replace it with
fresh liquid. During the cleaning up, quite some white smoke may be
produced from specks of white phosphorus, which are exposed to air. This
is not dangerous, but it looks weird and somewhat scary.
Perform the cleaning action outside, or in a very well ventilated room.
Chlorine gas is very poisonous and has an extremely choking odor.
Fortunately, its warning properties are good. Even at low concentration,
chlorine gas is unbearable. Do not make too much of the chlorine-water at
once, use multiple small batches.
After cleaning, all materials must be rinsed with water, and then the
materials which are thrown away can go in the trash bin. The cleaning fluid
can be flushed down the drain and after this, a tub full of water can be used
to rinse away all chlorine-water.
After one minute of standing in the acidic chlorine water, the bent test tube
almost is free of white phosphorus. Only two spots of white phosphorus
remain in this particular situation as shown in the picture. After three more
minutes of standing in fresh chlorine water, all orange/brown spots are
gone, and only the black material remains. This is not a problem, the black
material is inert.

The white phosphorus in action

After all this effort it is nice to see how the white phosphorus burns. It is
exceptionally easily ignited, and it burns with a heavily smoking flame. It
also burns while spraying around many small droplets, due to boiling of the
very hot droplet of molten phosphorus. This makes white phosphorus fires
exceptionally dangerous.

The spraying around is nicely demonstrated by the following picture (which I

did not make myself) of burning a much larger amount of white phosphorus.

A video also demonstrates the burning of white phosphorus. Only a very

small piece of phosphorus (just a few mm) was put on the tip of the screw
driver, shown in the video, and ignited. Download size is approximately 3.5
MByte.

Discussion of results
Red phosphorus and white phosphorus are different allotropes of the same
element. Red phosphorus consists of phosphorus atoms, arranged in an
irregular pattern of atoms. It is an amorphous solid of irregular
macromolecules. In this arrangement, the atoms of phosphorus are fairly
tightly bound to the macromolecules structure and this makes the solid
quite stable and inert at room temperature. It also makes red phosphorus
(like carbon, silicon, and boron) insoluble in any known solvent. If red
phosphorus does dissolve in some solvent, then it is part of a chemical
reaction and it is converted to another compound.
White phosphorus consists of P4 molecules with a particular structure, in
which there is considerable strain in the molecule.

When red phosphorus is strongly heated (400 to 500 C) then the large
macromolecular structures are broken down and atoms of phosphorus

escape from the solid. These combine to molecules of P4 and at colder

places, this condenses on the glass.
The strain in the P4 molecules makes them so reactive. White phosphorus
can ignite at a temperature as low as 30 C. Red phosphorus must be
heated to at least 240 C before it ignites