Sciencemadness Discussion Board

Distilling methyl nitrate

Yorty2040 - 5-4-2024 at 15:52

I know it's an extremely dangerous procedure, but I would like to know more about it, and see if anyone's done it.

If I understand correctly, the formation of methyl nitrate in aqueous nitric acid is an equilibrium reaction, and distilling off the methyl nitrate as it forms can force the reaction to completion via Le Chatelier's principle even if the nitric acid concentration is low and no dehydrating agent is present.

Of course, I wouldn't do it at standard pressure, as the boiling point of MeNO3 would be higher than the runaway temperature, but I can't find the data for the b.p at decreasing pressure for the various components. What pressure and temperature point would be ideal for boiling off the MeNO3 (and condensing it in a receiving flask cooled with a dry ice/acetone bath)?

I suppose purging the setup with nitrogen before reducing the pressure would be another helpful safety measure, but I'm not sure if it would be worth the effort, since the vapor concentration in ppm air would be the controlling factor in propagating a fire or explosion.

dettoo456 - 6-4-2024 at 06:56

A nomograph (https://www.sigmaaldrich.com/US/en/support/calculators-and-a...) can give you an idea of BP’s at different vacuum pressures.

As for actual synth, apparently alkyl nitrates can be decanted according to this orgsyn article (http://www.orgsyn.org/Content/pdfs/procedures/CV2P0412.pdf) and the patent I linked below, but they use mixed acid for the nitration, not WFNA or azeotopic HNO3.

I’d definitely advise against distilling energetics, especially close-to-OB%-balanced ones, and Methyl Nitrate is a brisant one at that. The ppm/O2 concentration might not matter in this case, a bit of metal somewhere in the apparatus or outside of the vessel could be all it needs to rapidly decomp.

Is there any reason you don’t want to use a dehydrating component in the rxn? If you can’t get H2SO4, polyphosphoric acid is comparable in dehydrating strength and only requires heating phosphoric acid up to like 400C for a while and cooling the resulting sludge down for later use - Magpie wrote a good little thread on it. It’s totally recyclable too.

[Edited on 6-4-2024 by dettoo456]

Attachment: Alkyl Nitrate Prep.pdf (660kB)
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[Edited on 6-4-2024 by dettoo456]

DennyDevHE77 - 6-4-2024 at 08:04

As far as I know it is not distilled in the usual sense, compressed air is bubbled through it, and coupled with its strong volatility it is distilled.
Quote: Originally posted by dettoo456  
Is there any reason you don’t want to use a dehydrating component in the rxn?


The question wasn't asked of me, but if they had asked me, I would have said that buying large quantities of H2SO4 can be suspicious, while nitric acid is completely legal. Well that's exactly my case. Following from that, and considering that for me for example 70-75% nitric acid is completely legal and available in large quantities, then I could make large quantities of explosives if possible. Methyl nitrate is one such substance. But I have the desire to blow down a tree by blowing up a few liters of nitroether, for example. Some people make do with ammonium nitrate explosives, and some people basically make a few grams of each.

Yorty2040 - 6-4-2024 at 11:41

It's way cheaper and easier to make aqueous nitric acid by distilling NaHSO4:H2O + KNO3 or using a Birkland-Eyde reactor than by constantly buying H2SO4 or reconcentrating it by boiling it down.

4-Stroke - 6-5-2024 at 22:40

Bad things are bound to happen at the worst time possible. Now what if one of your flasks implodes under vacuum? I don't know the quantity that you are planning to distill, but it could cost you your life. Yes, the risk is minuscule, but life is expensive.

j_sum1 - 7-5-2024 at 00:10

Good questions and I wish I could help.
I am going to recommend reading the thread, "life after detonation". This is the k8nd of thing that should be done with a healthy amount of neevousness.

ManyInterests - 1-6-2024 at 18:14

I plan on making methyl nitrate in the future. But I do NOT recommend doing it through distillation. It is simply too dangerous and any advantages are simply not worth it. Just use the regular nitration mixture method and keep a dump bucket with plenty of water ready in case a runaway starts to happen. The Improvised Munitions Handbook even mentions that if any spike in temperature or sudden darkening of the color means you got only a few seconds to drop it in a large quantity of water before disaster strikes.

bnull - 2-6-2024 at 08:31

Do you really need methyl nitrate? Volatile, toxic, explodes at 64 °C or so (which funnily enough is its boiling point at standard pressure). I usually stay away from chemicals that even the nazis were somewhat reluctant to handle.

If, and only if, you really need that thing, see the paper below. Methyl nitrate from methyl iodide and silver nitrate.

Marco Reichel et al., "Solid‐State and Gas‐Phase Structures and Energetic Properties of the Dangerous Methyl and Fluoromethyl Nitrates"

Edit: I was reading some old posts in Detritus (I must admit it can be quite funny sometimes) and, after following the "crapping spree" of a thankfully banned member, ended up in a 20-year-old thread (not in Detritus) about methyl nitrate which goes on for 6 pages.
Quote: Originally posted by vulture  
Methylnitrate, CH3NO3, is the nitric acid ester of methanol.

Volatile liquid, D 1,2075, boiling point: 64,6C.
Deflagrates at 150C.

I was wondering if anybody ever prepared this compound and/or knew a good synthesis.

Safety warnings and more data are also welcome as usual.


https://www.sciencemadness.org/whisper/viewthread.php?tid=74...

[Edited on 3-6-2024 by bnull]