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View Full Version : Potential new HNO3/H2SO4 method


CodeMason
September 5th, 2002, 04:05 AM
There is a potentially very cheap and easy way to produce a nitrating acid (nitric/sulfuric) mixture, involving the intermediate of nitrosylsulfuric (also known as nitrosulfonic, or nitrososulfuric) acid:
<img src="http://www.finechemicals-china.com/upphoto/NITROSYLSULFURIC%20ACID.jpg" alt=" - " />

I haven't had a chance to test it yet, but I'm going to give it a shot very soon. :)

Procedure:
Mix approx. 1 part sulfur and 2 parts ammonium nitrate, and place this mixture in an upside down glass jar above it. One may want to add ice to the top surface of the jar to aid in crystalization. The ammonium nitrate and sulfur mix is ignited, and the following chemical reaction occurs.

5S + 9NH4NO3 -&gt; 5HSO3NO2 + 9NH3 + 2H2O + 2N2

The nitrosylsulfuric acid will appear as white crystals on the side of the jar. You may want to vent the gasses because NH4OH can form from the NH3 and H2O, which could neutralize the acid. The crystals are collected and reacted with H2O2, or, by the addition of water and the bubbling through of O2 gas.

2HSO3NO2 + 2H2O + O2 -&gt; 2H2SO4 + 2HNO3
-or-
HSO3NO2 + H2O2 -&gt; H2SO4 + HNO3

(Thus this nitrating mixture would be great for reactions that require an equimolar amount of nitric and sulfuric.)
Without the present oxygen, it will make HNO2 instead of HNO3, which isn't too bad as this can be fairly easily converted to HNO3, or used on its own to make nitrosoamines.
Note: One should be careful, as ammonium nitrate/sulfur can explode, and some of the latter reactions may proceed at dangerously rapid rates if not controlled.

<small>[ September 05, 2002, 03:13 AM: Message edited by: CodeMason ]</small>

Einstein
September 7th, 2002, 05:47 PM
I don't know if that thing works, BUT: Your picture is fucked up from my point of view! How oxygen (first from the left) can connect with three "lines" (don't know that thing in english!)??? And how that nitrogen (from the left) is only connected with two "lines"???

xoo1246
September 7th, 2002, 06:06 PM
Did a fast search "NSA" as it is called is HNOSO4 and this is what it looks like.
<a href="http://myhome.cyberdreamtown.com/unichemc/nsa.jpg" target="_blank">http://myhome.cyberdreamtown.com/unichemc/nsa.jpg</a>
Since my chemistry knowledge is limited, the rest of the issues are left alone.
Merck tell us this:
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> Monograph number: Title: Nitrosylsulfuric Acid. CAS Registry number: [7782-78- CAS name(s): Sulfuric acid monoanhydride with nitrous acid; nitrosyl sulfate Additional name(s): chamber crystals; nitrososulfuric acid; nitroxylsulfuric acid; nitrosulfonic acid; nitrosyl hydrogen sulfate; nitro acid sulfite Trade name(s): Nitrose (Fort Dodge) Molecular formula: HN O 5 S Molecular weight: Percent Composition: H 0.79%, N 11.02%, O 62.95%, S Literature references: Formed as an intermediate in the lead chamber process for sulfuric acid by the reaction of sulfur dioxide, nitrogen trioxide, oxygen, and water: Cleacutement, Deacutesormes, Ann. Chim. Phys. [1] 59, 329 (1806); Lunge, J. Chem. Soc. 47, 470 (1885). Prepd from sulfur trioxide, nitrogen oxides and water: Doumlbereiner, Schweigger prime s Journ. 8, 239 (1812); de Claubry, Ann. Chim. Phys. [2] 45, 284 (1832); Kuhl mann, ibid. [3] 1, 116 (1843); from silver acid sulfate and nitrosyl bromide: Berl et al., Z. Anorg. Allgem. Chem. 209, 264 (1932). See also U.S. pats. 1,909,557 and 1,909,558. The formation of crystals of nitrosylsulfuric acid may be observed by igniting a mixture of 1 part sulfur and 2 or 3 parts potassium nitrate under a bell jar. Properties: Prisms, dec 73.5degrees. In moist air the crystals dec with the formation of sulfuric and nitric acids and above 50degrees nitric oxide and nitrogen dioxide are evolved. Sol in sulfuric acid, dec in water. USE: For bleaching cereal milling product </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">However it seems interesting!

<small>[ September 07, 2002, 05:11 PM: Message edited by: xoo1246 ]</small>

Pu239 Stuchtiger
September 7th, 2002, 11:13 PM
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">The formation of crystals of nitrosylsulfuric acid may be observed by igniting a mixture of 1 part sulfur and 2 or 3 parts potassium nitrate under a bell jar.</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Where does the hydrogen come from?

xoo1246
September 8th, 2002, 03:32 AM
Remove

<small>[ December 11, 2002, 01:04 PM: Message edited by: xoo1246 ]</small>

CodeMason
September 8th, 2002, 06:50 AM
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">BUT: Your picture is fucked up from my point of view! How oxygen (first from the left) can connect with three "lines" (don't know that thing in english!)??? And how that nitrogen (from the left) is only connected with two "lines"???</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">It is a poor diagram, because the N=O represents a nitroso group, where that other oxygen is connected to the nitrogen and not the oxygen. This satisfies all valencies.

CodeMason
September 8th, 2002, 06:56 AM
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">Where does the hydrogen come from?</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">My guess is along the same lines as xoo1246's, if nitrosylsulfuric acid is actually formed, the hydrogen is probably donated from H2O in the atmosphere or locked up in the crystal structure of the KNO3. Perhaps, however, potassium nitrylsulfate (KSO4NO) is formed instead. Merck is not infalliable, and small mistakes such as this are pretty common.

Madog555
September 8th, 2002, 10:17 AM
this is very interesting, i wonder if it will be better than KNO3/H2SO4 or the like.

i will probaly give this a shot soon.

rikkitikkitavi
September 11th, 2002, 03:15 PM
nitrosylsulfuric acid hydrolyses according to:

2NOHSO4+H2O=&gt; 2 H2SO4 + NO

2NOHSO4 + SO2 + 2H2O =&gt; 2 NO + 3 H2SO4 is also a possible hydrolysisreaction

it is formed by unwanted sidreaction in the lead-chamber process when to little water is present for :

NO2+ SO2 + H2O =&gt; H2SO4 + NO (main reaction)

I doubt that NH4NO3 kan replace KNO3 since NH4NO3 doesnt decompose into NO or NO2 upon heating. But it is worth a try.

/rickard

Marvin
September 28th, 2002, 12:10 AM
5S + 9NH4NO3 -&gt; 5HSO3NO2 + 9NH3 + 2H2O + 2N2 is not a primary reaction. The burning mixture produces a mess of oxides of sulphur, oxides of nitrogen, nitrogen, ammonia and water and results in varying amounts of nitrosyl hydrogen sulphate and nitrosyl sulphuric anhydride, (NOSO3)2O which also explains the lack of hydrogen in the saltpeter/sulphur chamber crystals, and for which that is one example of a balenced reaction. The saltpeter/sulphur result is important and arises from this being part of an old method for making sulphuric acid. A ladle containing sulphur and saltpeter is inflamed in a large glass balloon with a small amount of water in the base. The sulphur trioxide produced dissolves on the water, The process is then repeated to obtain more concentrated acid. If only a tiny amount of water is present, chamber crystals form, the less water the more nitrosyl sulphuric anhydride relative to nitrosyl hydrogen sulphate being present. This is the forunner of the lead chamber process for nitric acid. While it may seem long winded it neer completely replaced the nordhausen process which worked by distilling iron sulphate.

It was found that the bigger the balloon the less saltpeter was needed and the process gradually evolved. Nitrogen dioxide oxidises sulphur dioxide into sulphur trioxide, ending up as nitric oxide. The nitric oxide reacts with oxygen in the air to form nitrogen dioxide and the process repeats. The maximum concentration of acid this process can produce is about 70%. Higher than 70% the acid starts to absorb nitrogen oxides and so the catalytic reaction grinds to a halt, and secondly the resulting acid mix starts to attack the lead from which the chambers in the industrial process were made. Incidently chamber crystals form on surfaces not in contact with the acid solution, hense the name. Ok, it might seem like the above is irrelavent but I am getting neer something vaguly resembling a point. Becuase of the above I have grave doubts you can oxidise the chamber crystals without diluting them well beyond useful for nitrating mixtures, and then when you do you will get difficult to contain and highly unwelcome clouds of NO/NO2. Remeber also that acidified nitrites produce NO/NO2 by decomposition of HNO2 (Very unstable in strong acid solution, particulaly when concentrated and in the presence of dehydrating agents, all of which potentially apply) and you have to pass through this stage to get to the nitration mixture. Yet another reason the mixture might liberate large volumes of NO2 during the dilution/oxidation.

NO2 has been called quite justly "One of the most insidious poisons". Dont let the fact you see it regulaly trick you into thinking its safe to be around. Fear it, make all efforts to avoid breathing it in.