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Author: Subject: Nitromethane extraction
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[*] posted on 12-2-2004 at 08:10


Well, a blow with a hammer will do it (an open puddle, where part of the nitromethane will become confined, will detonate, a glass vessel, for example, will break and no confinement will be achieved, while a metal vessel will deform and do the job - I extrapolate). Drums for nitromethane are made to deform in a special way and/or break altogether to prevent confinement.
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[*] posted on 19-2-2004 at 14:36


And for goodness sake <b>DON'T USE A PROPANE BURNER!</b>

I did once, and underestimated the temperature. The glass vessel melted. Luckily it didn't contain anything combustible / explosive.




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[*] posted on 19-2-2004 at 16:18


I'm no expert but I almost find it hard to believe that nitromethane will detonate from the blow of a hammer. As soon as I get mine dried i will try with a small drop. Further more, If Nitromethane is sensitized by NH4NO3 wouldn't that make ANNM easier to detonate than Nitromethane? Hence, you can detonate ANNM with the blow of a hammer?



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[*] posted on 20-2-2004 at 04:54


Aldrich catalog says NM is flamable, doesn't say nothing about explosive. Anyway, it also doesn't say ammonium nitrate is explosive.

Merck index also says nothing about NM beeing explosive, it says it forms explosive sodium salts, flammable in contact with water. Merck says clearly ammonium nitrate is explosive.

My NM does not explode under a hammer blow.

My quick internet searches about nitromethane don't show any reliable source saying it explodes. It acts as a souce of "packed" oxigen source for fuels in race cars. It seems the extra power is not achieved by any explosive property.

Good luck again. I wish you (safely) prove me wrong.
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[*] posted on 20-2-2004 at 09:33


I'm under the impression that nitromethane is definitely an explosive. It it just much less shock sensitive than theoretic says.



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[*] posted on 20-2-2004 at 18:46


Quote:
Originally posted by tom haggen
I'm no expert but I almost find it hard to believe that nitromethane will detonate from the blow of a hammer. As soon as I get mine dried i will try with a small drop. Further more, If Nitromethane is sensitized by NH4NO3 wouldn't that make ANNM easier to detonate than Nitromethane? Hence, you can detonate ANNM with the blow of a hammer?


I believe that the NM sensitizes the ammonium nitrate, not the other way around. ANNM is sensitized to the point where it will detonate by a cap(unlike AN by itself) but not by a shock like a hammer blow.
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[*] posted on 20-2-2004 at 18:59


I could have sworn that I read somewhere that Nitromethane is sensitized by NH4NO3. I guess don't believe everything you read.

[Edited on 21-2-2004 by tom haggen]




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[*] posted on 24-12-2005 at 20:35
Nitromethane


I have some store bought nitromethane that I want to purify. I tried to create nitronates of the nitromethane using a NH4OH solution, but it failed. I measured out about 100mls of the store bought nitromethane/methanol solution and added roughly 20mls or more of a dilluated ammonium hydroxide solution to the mix. I set the mix in an ice bath. The solution after 24+ has blue oily spots (the nitromethane solution was blue to begin with) suspended in a white (assuming this is the hydroxide mixed with the nitromethane/methanol) solution.

The nitromethane/methanol solution contains 33% nitromethane.

Any ideas as to why this happened and what I can do to improve it?




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[*] posted on 25-12-2005 at 12:32


Actually, this is something I meant to test myself, precipitation of nitromethane with i.e. NaOH, to extract it from racing fuel.

Well, a) I'd use NaOH, not ammonia. It's a stronger base, and no funny reactions can occur.
b) I'd make sure to calculate that an EXCESS is present (of NaOH).
c) I'd either dilute first with at least 10x the amount of water. I should think that way you already get rid of most of the methanol, whjile insoluble NM and other oils float at the top (it roughly dissolves at 7 mole percent, so most is insoluble).

Then, extract with H2O once more (shake vigorously), let it settle, and add NaOH. The nitronate should precipitate. This then is extracted, washed more with water, and the correct amount of acid is added. NM should reappear as an insoluble oil. Beware, nitronate is very flammable.

Let us know how you get on.




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[*] posted on 25-12-2005 at 16:31


Quote:
Originally posted by chemoleo


Well, a) I'd use NaOH, not ammonia. It's a stronger base, and no funny reactions can occur.
b) I'd make sure to calculate that an EXCESS is present (of NaOH).
c) I'd either dilute first with at least 10x the amount of water. I should think that way you already get rid of most of the methanol, whjile insoluble NM and other oils float at the top (it roughly dissolves at 7 mole percent, so most is insoluble).

Then, extract with H2O once more (shake vigorously), let it settle, and add NaOH. The nitronate should precipitate. This then is extracted, washed more with water, and the correct amount of acid is added. NM should reappear as an insoluble oil.



Adding one more step to this... First, add a lot of H2O and remove any oil you can--either with an eye dropper, separatory funnel, or whatever. If you don't, the oil will saponify when you add NaOH and just make things very messy (it's hard to clean off, too); not to mention, it will be very hard to collect your precipitate.




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[*] posted on 25-12-2005 at 19:01


How would you separate the oil and NM? They are both insoluble and will be in the same layer at the start.
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[*] posted on 25-12-2005 at 19:04


by reacting the emulsion in water with NaOH......



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[*] posted on 25-12-2005 at 20:10


The way I read it, he was describing some physical means of separation, not a chemical one. I may be wrong, though.
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[*] posted on 25-12-2005 at 20:38


I see what you mean now.
Samosa worries about saponification with NaOH of oils OTHER than NM. Those other oils are obviously not seperable from NM by dilution in water, as both will form an insoluble layer. So you take that layer, make an emulsion with H2O and add NaOH (correct amount, this can be calculated as the conc of NM is usually given), and the NM will react to form nitronate, while hte remaining oil will not react (saponification is not an issue really as saponification requires higher temperatures, long reaction times and so on, while the nitronate reaction is instantaneous).




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[*] posted on 26-12-2005 at 02:16


"...Beware, nitronate is very flammable..."

I seem to remember that the reaction between nitromethane and lye was quite violent, but I haven't tried it out. Can you think of any other precautions, chemoleo? I have quite the overabundance of racing fuel at my resthouse... ;)

Alternatively, can anything other than a base extraction be used?

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[*] posted on 26-12-2005 at 14:35


Yeah, you could esterfy the methanol, but I think that way is harder.



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[*] posted on 26-12-2005 at 15:07


Quote:
Originally posted by chemoleo
...(saponification is not an issue really as saponification requires higher temperatures, long reaction times and so on, while the nitronate reaction is instantaneous).


I think it's experiment time :P. But I tried something similar to this a year or two ago and got a caustic gunk all over my beaker shortly after I added NaOH to the RC fuel, and I couldn't find anything that would dissolve it.

Anyhow, as was stated already, there would be an oil and an aqueous layer on dilution with water... But Nitromethane is also 'significantly' (quoting an MSDS) soluble in water. So the acid/base route might be a way to recover the NM from methanol/water that would otherwise be disposed of.




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[*] posted on 26-12-2005 at 15:33


Perhaps impractical but....
React the mix with bleach to get chloropicrin, separate chloropicrin, react chloropicrin with Fe/HAc, to get methylamine, then oxidize methylamine to nitromethane again.
:P

EDIT: Thanks Samosa, I changed the above to HAc.

[Edited on 27-12-2005 by rogue chemist]




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[*] posted on 27-12-2005 at 01:11


Quote:
Originally posted by rogue chemist
Perhaps impractical but....
React the mix with bleach to get chloropicrin, separate chloropicrin, react chloropicrin with Fe/acid (either HCl or HAc I forget which), to get methylamine, then oxidize methylamine to nitromethane again.
:P


Wouldn't reacting Chloropicrin with a reducing agent and HCl lead to Phosgene Oxime!? I'm game for that.

But there is a way to get methylamine from chloropicrin...there are a lot of neat, potentially useful reactions that can be done on it.

However, if chloropicrin can be converted back into Nitromethane, this is a very viable answer. I tell you from experience that Chloropicrin is very easy to isolate from this mixture with a simple separatory funnel.

EDIT: here we are, from War Gases:

Quote:
Geisse, with iron filings and acetic acid, obtained methylamine:

CCl3NO2 + 6 H2 --> CH3NH2 + 3 HCl + 2 H2O


Phosgene Oxime is obtained if one uses Tin powder and Hydrochloric Acid; although I remember Zinc powder being mentioned also.

[Edited on 12-27-05 by Samosa]




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[*] posted on 27-12-2005 at 12:02


Quote:
Originally posted by Samosa


But there is a way to get methylamine from chloropicrin...there are a lot of neat, potentially useful reactions that can be done on it.



You do have that file that was on the FTP entitled 'chloropicrin'? It goes into much more detail than The War Gasses about the chemistry of chloropicrin. A lot of cool things can be made starting from it, CI4, C(OC2H5)4, KNO2, etc.

Now to oxidize the methylamine HCl formed, what would be the best oxidizer here, something commonly available like permanganate or persulfate would be nice, although whether they would work I do not know.




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[*] posted on 28-12-2005 at 11:02


Quote:
Originally posted by chemoleo
Actually, this is something I meant to test myself, precipitation of nitromethane with i.e. NaOH, to extract it from racing fuel.

Well, a) I'd use NaOH, not ammonia. It's a stronger base, and no funny reactions can occur.
b) I'd make sure to calculate that an EXCESS is present (of NaOH).
c) I'd either dilute first with at least 10x the amount of water. I should think that way you already get rid of most of the methanol, whjile insoluble NM and other oils float at the top (it roughly dissolves at 7 mole percent, so most is insoluble).

Then, extract with H2O once more (shake vigorously), let it settle, and add NaOH. The nitronate should precipitate. This then is extracted, washed more with water, and the correct amount of acid is added. NM should reappear as an insoluble oil. Beware, nitronate is very flammable.

Let us know how you get on.


I tried that just a little while ago using Devil Lye (100% NaOH). Using the 33% NM solution I had, I measured out 33gs of the NaOH and added it to the diluted nitromethane solution (I used 10X the amount of water like you suggested) and a few seconds later it boiled and began to bubble out of my beaker! I discarded the solution (all over my garage floor. I missed the waste bucket -_-) immediately. Was it because I added too much NaOH too fast? Or maybe because it was 100%?


BTW, the NaOH was solid, not liquid, hence the use of grams :P Perhaps that was a factor?

[Edited on 28-12-2005 by Dream of the iris]

[Edited on 28-12-2005 by Dream of the iris]
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[*] posted on 28-12-2005 at 11:12


If the amount of NaOH was correct, its form won't matter much. The problem is that you added too much too fast without adequate cooling. Try precooling the NM and putting the beaker in an ice bath when you do the reaction next time. Also, try dissolving the proper amount of NaOH in water first and cooling that. This should eliminate that pesky heat of hydration from the reaction.
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[*] posted on 28-12-2005 at 11:37


You need roughly 61 grams nitromethane per 40 grams of NaOH. In other words, you had an excess of NaOH which is not good.

Cooling is essential, and I'd FIRST dissolve the NaOH in water, cool it, and THEN add it very slowly at 0 deg C to the diluted cool NM. The reaction of nitronate formation is known to be exothermic, so beware.

Also, at no time to you need to dry the salt (it's dangerous), just filter the precipitate, wash it with water for a fair bit, and then take the precipitate and add a slight stoichiometric excess of dilute acid - SLOWLY! The acid excess is needed to drive the equilibrium to the left, i.e. where NM is insoluble in water.

Here some quotes from E&W.

By Philou:
Quote:
*saturated ammonia solution gives heat and a dark brown solution of NH4CH2NO2 but :-( I was not able to isolate the salt by evaporation (even in the cold)-I suspect the compound to be very unstable it decompose into its elements maybe due to an equilibrium in solution:
NH4OH + CH3-NO2 <==> NH4CH2-NO2 + H2O.
*saturated solution of NaOH (solid prills) gives a lot of heat (you might expect an explosion or a fire!!!) but the isolated salt don't give interesting results (except if confined and dry).
The NaCH2NO2 is difficult to dry because it picks up water from air. It burns with puffing flammes. I guess it would explode if confined in an enclosed metal pipe and heated by a surrounding heat source like Black powder or Na chlorate/suggar or a fire.
*KOH gives a precipitate with a lot of heat also (fire or explosion to expect without water cooling or if big quantities are made).
Less difficult to dry than the Na salt. Burn fiercely like NC outside and once confined surely it will go boom.
*Ca salt I made has the advantage of being dry, precipitate, burn fiercely and explode when confined (very easy to use).


By Vorion
Quote:

i made Ca(CH2NO2)2 by mixing pure NM with Ca(OH)2 and a few drops of water while stirring. As i didnt want to make big quantities i have now about 0,5g Calcium nitronate. It looks like Cinnamon powder when dry (and pulverized). It was easier to make than NaCh2NO2, which i made about a month ago and dropped because of a strong smell of Ammonia after half a day stored dry, because the temperature is easier to control.
Zaibatsu had some impurities in his product because he used Calciumcarbide. I used pure Calciumhydroxide + CH3NO2 and i do have some bigger crystals in my product, i tried to separate them and they look a bit darker than the other product.




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[*] posted on 28-12-2005 at 19:08


How big are the nitronates supposed to be?

Edit by Chemoleo: Clarify. HOw big, what, molecular mass? ionic radius?

[Edited on 29-12-2005 by chemoleo]




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[*] posted on 29-12-2005 at 12:12


Molecular mass. Well, compare nitronates to, say, table salt or something.

Also, I did everything you said, but nothing really happened (no crystals formed) so I let it sit overnight and when I returned there was black liquid in the beaker with no crystals. Maybe I should heat it to speed the process?

[Edited on 29-12-2005 by Dream of the iris]

[Edited on 29-12-2005 by Dream of the iris]




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