Backyard Chemistry- Nitric acid

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Nitric acid
1. 2. 3. 4. 5. 6. 7. 8. 9. Background Ostwald Process Birkeland-Eyde Process Decomposition of Nitrates Drying Nitric Acid Motivation Experiment 1 Experiment 2 Experiment 3

Background
Nitric acid (HNO3) is a strong acid that attacks most metals including silver, copper, mercury, lead, and iron. There are two kinds of concentrated nitric acid. White fuming nitric acid consists of almost pure HNO3 whereas red fuming nitric acid contains a considerable amount of dissolved nitrogen oxides. Synthesizing nitric acid can be accomplished in many different ways. The most common and straightforward method is to add concentrated sulfuric acid to a nitrate salt such as ammonium, sodium, or potassium nitrate. H2SO4 + 2KNO3 --> 2HNO3 + K2SO4 It is important to slowly heat the mixture and not to achieve too high of a temperature or else you'll end up with mostly NO2 and no nitric acid. This looks all and simple, but the problem is that nitric anhydride is created, N2O5. Nitric anhydride eats practically every material alive- wood, plastic, rubber, any affordable metals, and of course, flesh. A distillation set up has to be all glass and any rubber stoppers that are involved most be throroughly covered with Teflon tape. Now that I have a glass distillation apparatus, this is how I produce my nitric acid. All other methods of producing nitric acid involve dissolving nitrogen oxide gases into water. All the chemistry behind this reaction is quite complex, but it can be summarized in two steps. Nitrogen dioxide react with water to form nitrous and nitric acids. 2NO2 + H2O --> HNO2 + HNO3 Upon heating this mixture of acids, nitrous acid will decompose into nitric acid, nitrogen monoxide, and water. 3HNO2 --> HNO3 + 2NO + H2O Now the obvious problem that arises is, how does one make nitrogen oxides? Well, there are several different paths to take, which are outlined below.

Ostwald Process
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The Ostwald Process has been the industrial method of manufacturing nitric acid ever since the Haber process for synthesizing ammonia was developed. It involves reacting ammonia with oxygen at high temperatures over a platinum-rhodium catalyst to produce nitrogen monoxide. Typically, this is done at several atmospheres of pressure and around 800C. 4NH3 + 5O2 --> 4NO + 6H2O Fortunately for the home chemist, a heated piece of copper wire can serve as a catalyst almost equally as well. In adiition, about 238 kilojoules of heat are given off for each mole of ammonia reacted. This is enough heat to keep the copper wire hot. Ammonia gas can easily be made by heating a solution of ammonia or by decomposing an ammonium salt with alkali.

Birkeland-Eyde Process
Through a high voltage plasma arc, nitrogen and oxygen from the air combine to form nitrogen monoxide. The supply of nitrogen in the air is limitless, but this process is pretty difficult for the average fellow to realize. A variation of this process involves the use of a microwave to create a plasma arc.

Decomposition of Nitrates
This is how I used to make my nitric acid. Some nitrates thermally decompose into nitrites, but the alkaline earth metals and some transition metals like copper decompose into their oxides, giving off nitrogen dioxde in the process. In my opinion, magnesium nitrate is the most useful of these because it can be synthesized easily and has a decomposition point of 330C, well within the reach of an alcohol burner. I make my magnesium nitrate by reacting ammonium nitrate from cold packs with magnesium hydroxide. In my first trial of making nitric acid, I made by own magnesium hydroxide by reacting sodium hydroxide with magnesium sulfate (Epsom salts), but this is hardly necessary as pure magnesium hydroxide can be found in laxatives. Ammonia gas is the driving force behind this reaction and is a useful by product. Mg(OH)2 + 2NH4NO3 --> Mg(NO3)2 + 2NH3 + 2H2O The magnesium nitrate is then heating and the resulting orange gas is dissolved in cold water. Mg(NO3)2 --> MgO + 2NO2 + O2 I've also made nitrogen dioxide with copper nitrate, but copper compounds are much more expensive. Oxidization of copper requires a third step. When nitric acid is made via the sulfuric acid-nitrate method, a high concentration (>98%) can be attained if desired. However, when dissolving nitrogen oxides into water, only dilute solutions of nitric acid are formed. The dilute acid must be distilled, but the acid's concentration will only increase until it reaches the azeotrope of 68% nitric acid and 32% water. At this point, both nitric acid and water will distill over at the same temperature. Thus, it is impossible to achieve greater than 68% nitric acid through simple distillation. The concentrated acid is required in many organic reactions and hence I must make it. The most common way of concentrating nitric acid is to react the dilute acid with a base to form a nitrate salt and then to distill this with concentrated sulfuric acid. This, however, is the exact process that I am trying to avoid. I am currently researching alternative methods of concentrating nitric acid.

Drying Nitric Acid

Magnesium nitrate can be used to dry nitric acid to the concentrated form. Although anhydrous nitric acid cannot be synthesized easily because it decomposes upon heating, magnesium nitrate trihydrate may be used. The trihydrate can be formed by heating magnesium nitrate hexahydrate to around 150C. Unfortunately, this method would require at least 1.5g of magnesium nitrate per millilter of dilute acid. The salt would then be filtered from the solution and the redried for further use.

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Motivation
Why do I want nitric acid so badly, you ask? Well, several reasons. React it with silver and you get silver nitrate, an important tool used in the qualitative analysis of chloride ions. Mix it with three parts concentrated hydrochloric acid and you get aqua regia- "royal water". This mixture of acids can dissolve gold and platinum! A mixture of concentrated sulfuric and nitric acids can nitrate many organic compounds like benzene and cellulose. Not only is it a strong acid, it is an oxidizing strong acid!

Experiment 1
A slight excess of 25 millilers of a suspension containing about 2 grams of magnesium hydroxide was added to a solution that contained 5.4 grams of ammonium nitrate. The solution was boiled down until it was partially dry. A strong odor of ammonia was detected during this process. The approximently 5 grams of magnesium nitrate thus formed was then heated in a flask with an isopropyl alcohol fueled flame. A plastic tube connected to the flask and was led into water. The flask was heated five times in this manner and yet there probably was still more magnesium nitrate left that remained undecomposed. The top of the flask was colored orange due to a high concentration of nitrogen dioxide throughout the experiment. Rapid bubbling ensued as the gas passed through the water. The 130 milliters of water had a final pH of 1.13. The next day, the solution was boiled down to 2.5 millilters yielding a theoretical concentration of 24% nitric acid. The nitric acid was then added to a wide variety of metals on a dropwise scale. The results strongly support the presence of nitric acid and are shown below. Zinc*- bubbled vigorously Cadmium*- bubbled vigorously Magnesium*- bubbled vigorously Copper- bubbled a bit Manganese- bubbled a bit Iron**- bubbled a bit and turned light yellow Nickel- no visible reaction *A significant amount of oxide may have been present. **The iron used came from teh steel of a paper clip. Since these reactions were done on a minuscule scale, I could not see if any nitrogen dioxide was evolved although its formation relies heavily upon the initial concentration of nitric acid and the metal in question.

Experiment 2
I managed to synthesize concentrated nitric acid in this experiment, and after more than two years of brainstorming and research, it is ironic, although probably predictable, that I would utilize the simplest method of production. The reality is that distillation of sulfuric acid and a metal nitrate is the only efficient way to obtain concentrated nitric acid in an amateur laboratory setting. I used my new 19/22 glass distillation apparatus and filled a 100mL round bottom flask with 29.5g of crushed KNO3, 15.3mL H2SO4 (of uncertain concentration), and 5mL H2O. I wrapped the thermometer adapter as much as I could with Teflon tape, and used an oil bath to heat the flask. I connected the vacuum adapter, which led into an Erlenmeyer receiving flask chilled in an ice-water bath, to the Liebig condenser. The canola oil bath reached temperatures up to 320F with no visible smoking. It did bubble and bump a little bit due to water which was boiling out of the beaker. Orange nitrogen oxides escaped for some time even when the temperature of the head was still below 20C. The head temperature did not increase significantly until I stopped the flow of water around the distillation column. A clear fraction of nitric acid started to come over at around 115C. The water that surrounded the distillation column boiled as the glass became hot.

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I then realized that, although no water flow around the distillation column was beneficial, the absence of water circulating around the condenser was detrimental to the yield because I saw nitric acid vapors escaping from the vacuum adapter. I unplugged the T unit of the tubing system and plugged the hose line directly into what I thought was the condenser. Unfortunately, I was mistaken and the line led to the hot column. Therefore, when I turned the water valve on, water immediately reached the distillation column and flash boiled. The steam produced from this incident must have blown the line and water poured into the searing oil bath and all over the red-hot buffet range. A raging eruption of steam ensued and I was forced to abort the experiment. In the short period of time that effective distillation did occur, I collected less than 5mL of yellow liquid. The distillate reacts vigorously with copper as expected and gives off lots of brown nitrogen dioxide gas and eventually turns into a blue solution of copper nitrate. I saved the distilling flask in hopes that I can continue distillation at a future time. The thermometer adapter did survive, but it had visibly shrunken in size. I would like to distill another batch of nitric acid using a 500mL flask although my current ring stand and clamp arrangement do not allow for such a structural adjustment. I took a horribly inaccurate measurement of the distillate and all I can say for sure is that its density is greater than 1g/mL. The measurement I did get was 0.4g/0.3mL, a density of 1.33g/mL, which corresponds to a concentration of 54%. About 3 weeks after performing the above experiment, I reacted some of the distilled nitric acid with copper so that I could video tape it. To my surprise, the reaction was not very vigorous and no brown nitrogen dioxide gas was evolved. I later realized this was due to the extreme hygroscopic nature of concentrated nitric acid. The nitric acid had absorbed water from the atmosphere and hence became less concentrated. With dilute nitric acid: 3Cu + 8HNO3 --> 3Cu(NO3)2 + 2NO + 4H2O With concentrated nitric acid: Cu + 4HNO3 --> Cu(NO3)2 + 2NO2 + 2H2O I definitely want to run this experiment again so that I get better yields. I look forward to properly titrating a batch of nitric acid with sodium hydroxide or possibly ammonia. Perhaps, I could then further make 99% nitric acid by drying it with magnesium nitrate.

Experiment 3
I performed nearly the same experiment as the one previously described, but this time I finally achieved good results. The set-up was a little more secure and featured a few major improvements. First off, I used a pond pump to power the water circulation system. Another major improvement was that I thoroughly wrapped the thermometer adapter in Teflon tape after I had inserted the thermometer in it and measured how far I should push it through. This way, I was able to wrap the tape on the adapter and to the thermometer glass, which ensured a much better seal. Also, the entire set-up seemed to be a lot sturdier because I was more patient in putting the distillation apparatus together. I used a 250mL round-bottomed flask as my distillation flask which is two and half times the size of the one I used in the previous experiment. I placed the flask in an old large soup can. I was just barely able to fit this larger can on the edge of the hot plate burner because I took the time to make sure that the ring stand clamps were perpendicular to the edge of the hot plate. More significantly, however, I decided to use the medium hot plate burner because using the high power hot plate burner would have meant having the hot plate situated in a way in which its control knob would have been facing towards the ring stand base. This would have increased the distance between the ring stand and the hot plate just enough to make it impossible for the metal can to be placed flat on the hot plate burner. After situating the clamps on the ring stand in their proper positions, I filled the can with canola oil up the neck of the round bottomed flask. I then connected the receiving flask to the Liebig condenser via a 19/22 vacuum adapter, which fit perfectly unlike in the previous experiment when I mistakenly used a 14/20 vacuum adapter instead. I used another old soup can to put the 100mL round bottomed receiving flask in and filled it with ice water. Since the distillation flask was greater than the size of the one previously used, I simply doubled the amount of chemicals used, yielding a mixture of 59.0g potassium nitrate, 30.6mL of sulfuric acid, and 10mL of distilled water. Upon adding the sulfuric acid, the mixture began to emit a small amount of white nitrogen oxides fumes. The mixture was let to

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Backyard Chemistry- Nitric acid

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stand for no more than ten minutes, and then I turned the medium burner on the hot plate to high. Heating in this manner continued for more than two and a half hours. At first, a large amount of orange and yellow nitrogen oxides were given off. During this time, the mixture inside the distillation flask was a bright red-orange. Later, clear nitric acid began to condense on the walls of the distillation flask, but since the head temperature never exceeded 70C and hovered around 60C most of the time, no product distilled over and hence the mixture was essentially refluxing. I then decided to carefully flip around the hot plate burner and use the hotter burner. In order to keep the metal can flat on the burner I had to prop it up with a wrench because the hot plate control knob now took up space. This was somewhat of a precarious situation, but I was careful enough and all proceeded well. Heating continued with the high power burner for approximately an hour. A clear liquid slowly distilled over and the head temperature stayed very steady in the range of 114-118C. This occurred when the temperature of the oil bath was 370F. As distillation continued, the temperature of the oil bath slowly increased to 430F and the head temperature slowly decreased to 105C. This decrease in head temperature along with the fact that the receiving flask was no longer receiving any condensate and that the mixture in the distilling flask had noticeably decreased in volume signaled to me that distillation had finished. I assume the canola oil used is rather refined because it reached such high temperatures without smoking. One site mentions that refined canola oil smokes below 450F, but other sites mention much lower smoke point temperatures. The distillate is a pure yellow liquid that does not noticeably fume. I think that if I had connected the receiving flask after the initial proliferation of nitrogen oxides has ceased, say when the head temperature is at 60C, that then I would obtain a clear liquid. I do not think that the absence of the dissolved nitrogen oxides would affect the yield of the reaction very much. I was elated the volume of the distillate was slightly more than 25mL. This allowed me to pour the nitric acid in my 25mL volumetric flask. The weight of this 25.0mL was 35.1g, giving a density of 1.404g/mL, which corresponds to a 68% w/w or 15.1 molar concentration. This is very exciting because 68% nitric acid and 32% water is the azeotropical composition of nitric acid which boils at 120.5C. The distillate may have actually boiled off at this point and the thermometer recorded a lower value because it was slightly misplaced. Even if this was not the case, the head temperature I recorded still strongly testifies the presence of azeotropical nitric acid. It also makes sense that I did not attain a concentration higher than 68% because the concentration of the initial sulfuric acid used was no higher 13.6 M, that being the figured derived from the assumption that the drain cleaner sulfuric acid has a concentration of 18 M. I should really measure the density of this sulfuric acid so that I can figure out its approximate concentration. Since azeotropical nitric acid has a concentration of 15.1 M, this means that the concentration of the acid actually increased during distillation which is exactly what should happen. I am not sure if this logic is necessarily accurate, however, because if the reaction goes all the way to completion, two moles of nitric acid are produced for every one mole of sulfuric acid. I estimated that there was approximately one milliliter of nitric acid in excess of the quantity that was massed out, giving a total of 26mL or 67% yield. I stored the nitric acid in a glass bottle after thoroughly wrapping its rubber seal in Teflon tape. I then wrapped the bottle in aluminum foil because I know that light increases the rate at which nitric acid decomposes into nitrogen oxides. The nitre salt cake in the distilling flask was yellow and thoroughly solidified. I washed the cake with water several times and it turned white. I then broke up the mass with a stirring rod and emptied the wet pieces of salt into a beaker where I left it to dry. Hopefully, I successfully washed most of the acid residue away and I can use what presumably is a mixture of potassium sulfate and potassium bisulfate in other experiments. Overall, I am quite satisfied with the results of this experiment. Now that I have 25mL of 68% nitric acid, I am not sure what I want to do with it. Three ideas that immediately spring to mind right now are to synthesize silver nitrate, oxalic acid, or nitrocellulose. Back to the Backyard

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