killswitch
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Nitromethane + hydroxide reaction
So I finally received a 5-gallon pail of 100% nitromethane the other day and was surprised to find the warning regarding its interaction with strong
alkali plastered over it in huge print.
I poured out about 10mL from the 5-gallon pail (without spillage!) and slowly added tiny prills of dry sodium hydroxide, which immediately fizzed and
turned brown with much evolution of heat.
I'm trying to understand what exactly is going on here.
From what I've read, this process forms the sodium salt of 2-nitro acetaldoxime, unless water is present, in which case sodium nitroacetate is formed.
So, when the hydroxide prills have turned brown and dried off, can they be used immediately as a shock-sensitive primary? And what of the precipitate
after an aqueous solution of sodium nitroacetate has dried?
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woelen
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The reaction with hydroxide in the presence of water (even very small amounts of water) results in formation of brown non-energetic crap. A very
violent reaction occurs if you add strong alkali to nitromethane, on my website I have a demo in which drops of nitromethane are added to solid Na2O.
This results in immediately ignition! If you pour a small beaker (e.g. 20 ml) full with prills of NaOH and then pour in nitromethane, such that the
prills are just covered (which requires roughly 10 ml of nitromethane), then you might have ignition and a roaring orange flame as well, but not
immediate, the reaction takes some time.
Look up the chemistry of nitronates, under strictly anhydrous conditions it is possible to make the white salt sodiumnitronate, which is a highly
energetic compound. You have to meticulously assure though that no water is present. Even small amounts of water cause the nitronate to turn brown and
loose its energetic properties. Acidification of a nitronate causes formation of the corresponding acid, which has a red color. You can perform all
this nitronate chemistry in alcohol, using sodium ethoxide as base. Any water, present in the alcohol will then be converted to sodium hydroxide and
ethanol and this assures that you work under perfectly dry conditions.
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Dany
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In an old review (see Chem. Rev., 1943, 32 (3), pp 373–430) the author described the reaction of aqueous alkali hydroxide
with nitromethane:
"Nitromethane, compared to other nitroparaffins, is uniquely sensitive to the action of alkali. Sodium or potassium hydroxide converts it to salts of
methazonic acid by a reaction in which two molecules condense with loss of water. This may be interpreted as an addition of nitromethane to the
carbon-nitrogen double bond of the potassium salt, followed by rearrangement and loss of water. Upon further treatment with strong alkali, methazonic
acid is converted to nitroacetic acid (384). The crystalline sodium salt of nitroacetic acid can be obtained directly in a single operation by
dropping nitromethane into a 50 per cent aqueous solution of sodium hydroxide maintained at 50°C., heating the solution to boiling for 10 min., and
cooling. The free acid is obtained by acidification with hydrogen chloride of the finely divided salt suspended in ether.
Unfortunately, i cannot upload the original review (the size is 3Mb) but you will find an attach file (.JPEG) of the reaction scheme involved in the
conversion of nitromethane to methazoic acid and to nitroacetic acid.
P.S: this review (Chem. Rev., 1943, 32 (3), pp 373–430) has been mentioned in Encyclopedia of explosive and related items
volume 8, page M-72, but the authors made a mistake in the reference by putting the year 1938 while the true year of publication is 1943.
Dany.
Attachment: Reaction of nitromethane with alkali hydroxide.zip (83kB)
This file has been downloaded 539 times
[Edited on 26-8-2013 by Dany]
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AndersHoveland
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Nitromethane quickly reacts with a concentrated aqueous solution of sodium hydroxide to form the sodium salt of methazonic acid (alternatively named
sodium 2-nitroethanaloximate),
(2) CH3NO2 + NaOH --> HON=CHCH=NO2Na + (2) H2O
The dry sodium methazonate salt is highly shock-sensitive and can explode violently.
In the absence of water, nitromethane reacts with sodium hydroxide dissolved in alcohol to form the sodium salt of nitromethane. If water is added,
the solution immediately turns reddish brown, and the reaction is the same as if aqueous alkali had been added to the nitromethane to begin with. If
hydrogen chloride is passed into an alcoholic solution of the sodium salt of nitromethane, the nitromethane may be recovered. However, the reaction
with water to form methazonate salts is not reversible.
[Edited on 27-8-2013 by AndersHoveland]
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franklyn
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Research on Nitromethane
www.dtic.mil/dtic/tr/fulltext/u2/497917.pdf
Activating & Directing Effects of the Nitro Group in Aliphatic Systems
www.uni.illinois.edu/~vaughen1/ChemMobile//fulltext
http://chemland-group.itrademarket.com/1445565/nitromethane....
Look at the chart here under pH and composition of carbonic acid solutions
http://en.wikipedia.org/wiki/Carbonic_acid
Notice that pH of CO2 in water , increases until near neutral ~ 7 at
high vacuum. Given that the pH of nitromethane is just over 6 , it looks like
it can displace CO2 from sodium carbonate when subjected to a vacuum.
Sodium carbonate has a pH of 11.6 so it can readily acidify nitromethane.
It looks like dry sodium nitronate can be easily made in this way with just
Soda ash and a vacuum pump. Soda ash is ( the industrial name of
anhydrous sodium carbonate ). Washing soda is typically the monohydrate.
2 CH3NO2 + 2 NaCO3 => 2 NaCH2NO2 + Na2CO3•H2O + CO2
an alternative result could be
CH3NO2 + Na2CO3 => NaCH2NO2 + NaHCO3
The risk is that as the sodium salt accumulates , the remaining nitromethane
becomes increasingly sensitized and prone to detonation. The vacuum will
need to be allowed to bleed back to air pressure very slowly to avoid shock.
A solution in methanol as the non participating solvent could act as a buffer.
.
[Edited on 27-8-2013 by franklyn]
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Marvin
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Existing thread, http://www.sciencemadness.org/talk/viewthread.php?tid=1089
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killswitch
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Quote: Originally posted by woelen  | The reaction with hydroxide in the presence of water (even very small amounts of water) results in formation of brown non-energetic crap. A very
violent reaction occurs if you add strong alkali to nitromethane, on my website I have a demo in which drops of nitromethane are added to solid Na2O.
This results in immediately ignition! If you pour a small beaker (e.g. 20 ml) full with prills of NaOH and then pour in nitromethane, such that the
prills are just covered (which requires roughly 10 ml of nitromethane), then you might have ignition and a roaring orange flame as well, but not
immediate, the reaction takes some time.
Look up the chemistry of nitronates, under strictly anhydrous conditions it is possible to make the white salt sodiumnitronate, which is a highly
energetic compound. You have to meticulously assure though that no water is present. Even small amounts of water cause the nitronate to turn brown and
loose its energetic properties. Acidification of a nitronate causes formation of the corresponding acid, which has a red color. You can perform all
this nitronate chemistry in alcohol, using sodium ethoxide as base. Any water, present in the alcohol will then be converted to sodium hydroxide and
ethanol and this assures that you work under perfectly dry conditions. |
I performed the nitromethane-hydroxide reaction under conditions pretty much guaranteed to contain water (the air was humid as all hell, and by the
end of the addition the last prills of hydroxide had wetted the weigh paper considerably).
However, the brown crap left over was not useless. I found that it burned with incredible vigor, splitting a hole in the Reynolds wrap nearly as large
as the pile itself. The bright yellow sodium flame leaped at least 15 centimeters into the air. The burning was complete in a fraction of a second.
This was with no attempt at grinding or granulation.
However, when pressed into a straw, it became utterly nonflammable, to the point that perchlorate matches were incapable of igniting it and would even
go out if pressed firmly against it.
My conclusion is that it is extremely easy to dead-press. It might be capable of making DDT under confinement or in larger quantities.
I will be away from my lab for a considerable period, so I won't be able to test how well it might make DDT under confinement.
[Edited on 29-8-2013 by killswitch]
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woelen
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Could you please describe precisely what you did. Give each step in your experiment, quantities used (approximate if not measured exactly), form of
chemicals used (e.g. powder, prills, purity) and if you had drying steps in the process, these also should be mentioned. With that kind of information
I certainly am willing to repeat your experiment.
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killswitch
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Roughly 20 ml of purportedly 100% NM (direct from a racing fuel supplier) and 5 grams sodium hydroxide (very small prills, >95% purity). The
hydroxide was added to the NM over roughly 30 minutes
If the prills are being dispensed from a coffee filter, the last few should adamantly refuse to separate upon shaking, having wetted the paper for
several millimeters in every direction with absorbed moisture.
The contents of the beaker are then added to roughly 15mL of water, resulting in a reddish-black color and a partially-immiscible clear layer on top.
This was then allowed to dry for several days. A black, crystalline material formed along the edges, consistent with the behavior of a substance
precipitated by evaporation. This black substance was flammable and burned extremely well. A brown-red substance with no discernible structure and
almost clay-like consistency was also formed. This burned well when unconfined, but became completely useless when compressed.
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