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Author: Subject: Hydroxylamine via HCL, Nitromethane, and H2O?
Khemi
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[*] posted on 20-9-2016 at 17:10
Hydroxylamine via HCL, Nitromethane, and H2O?


Can you arrive at (H3NO) Hydroxylamine hydrochloride by refluxing
(6mol)

648g HCL
450g H2O
366g Nitromethane

and if so, how long should the reflux take at 100c? How much distillate should be removed before crystallization will take place?

What is the anticipated yield of H3NO.hcl?

I truly appreciate the help/advice.
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Texium (zts16)
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madcedar
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[*] posted on 20-9-2016 at 20:30


Sure, I didn't check your ratios but Axo did it here (with pictures):

https://www.sciencemadness.org/whisper/viewthread.php?tid=58...
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nitro-genes
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[*] posted on 21-9-2016 at 00:58




Attachment: Action of mineral acids on primary nitroparafins.pdf (433kB)
This file has been downloaded 174 times
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zed
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[*] posted on 21-9-2016 at 16:31


Ahhh. Something I hadn't suspected.

Nitromethane seems to produce Hydroxylamine PLUS Carbon Monoxide under these conditions. Gotta do something about that CO gas.

Perhaps this experiment is best performed, as an outdoor experiment.
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nitro-genes
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[*] posted on 22-9-2016 at 03:15


IIRC, only using highly concentrated sulfuric (>85%) carbon moonoxide is formed in large quantities, it's still best to perform this reaction outside though. Not only due to any potential CO formed, but a layer (good stirring) of nitromethane saturated with HCl at >100 deg C. may also be potentially explosive (although I couldn't find any examples were this was the case). The reaction with concentrated sulfuric is more dangerous, as this produces some exotherm upon mixing/heating, and heating should be performed cautiously in the beginning. Also not sure if even very concentrated HCl would produce any CO at all, as Axt's pressure bottle would have exploded if this was the case.

[Edited on 22-9-2016 by nitro-genes]
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Tsjerk
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[*] posted on 22-9-2016 at 04:34


I repeated Axo's experiment a long time ago and I can tell that the reaction works. I do advice though to recrystallize the product a couple of times as it seems that HCl ''sticks'' to the crystals.
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nitro-genes
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[*] posted on 22-9-2016 at 07:09


Both sulfuric drain cleaner and hardware store HCl can be contaminated with substantial amounts of transition metals, especially iron. Copper and copper salts ares known to catalyse decomposition of hydroxylamine, not sure if this is the same for Fe3+ or still applies under very acidic conditions, though maybe something to keep in mind?
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[*] posted on 22-9-2016 at 08:46


I just looked into it. ~0.2% of either ferrous or ferric iron contamination induces extremely violent (boiling) decomposition of 50% hydroxylamine in water. See the attached paper.

However, the authors of that study performed their tests under neutral conditions. The presence of acid stabilizes hydroxylamine as hydroxylammonium, much like acid stabilizes hydrazine as hydrazinium.

In fact, this https://infoscience.epfl.ch/record/176224/files/Billeter%20e... says that under acidic conditions, ionic iron doesn't do much of anything to decompose hydroxylamine.

Thus, as long as you keep the solution acidic and crystallize the hydroxylamine salt out of solution, I wouldn't worry about iron contamination too much.

Attachment: je030121p.pdf (132kB)
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[Edited on 22-9-2016 by Cryolite.]
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[*] posted on 22-9-2016 at 10:49


Thanks for looking that up, wouldn't have guessed 10 ppm ionic iron would have such dramatic effects. Better recrystallize the acid hydroxylamine when planning to use the freebased hydroxylamine in a synthesis. :)
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Khemi
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[*] posted on 2-10-2016 at 18:49
Thanks for the input!


If performed I would use a flask, fitted with a condenser, with a pressurized equalized additional funnel with a male outlet on top to direct any gas that is evolved, outside.

I do not like the idea of making this in a pressurized vessel. I do like the idea of making it in the manner I laid out, even if the yield is slightly less.

Can someone confirm if my ratios (in my original post) are on point if I intend on carrying out this synthesis in this manner?

648g of 31.45%
450g H2O
366g Nitromethane

Im guessing 175g of Hydroxylamine.HCl would be about the yield, give or take a few grams.

Do my ratios look ok?
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