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MadHatter
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Correction
I should've said that NCl3 can be produced if attempting to produce
NH4ClO3 by electrolysis of NH4Cl. I won't be trying this in any event.
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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clearly_not_atara
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Quote: Originally posted by theAngryLittleBunny  | | Quote: Originally posted by clearly_not_atara | TCCA and its derivatives have caused other explosions as well; see e.g. the chlorination of benzaldehyde. Perhaps we should put a warning in the TCCA
article on the SM wiki, since it is a common chemical that even beginners often use while not being aware of the risks.
The partially dehalogenated TCCA can give off HCl and N2, while alkaline hydrolysis can generate chloramines. And hypochlorites are a concern.
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Oh shiiiit, when I started with chemistry I put solid TCCA to Benzaldehyde in an attempt to make benzoyl chloride. I had no clue this stuff was so
dangerous |
The rxn works under UV illumination in chlorinated solvents, but heating the rxn mixture to
distill BzCl will cause an explosion. It must be done under a strong vacuum, or extracted another way.
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woelen
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In the last reaction, you probably confused the use of TCCA with the use of cyanuric chloride. TCCA is C3N3O3Cl3 and cyanuric chloride is C3N3Cl3 (a
trimer of CNCl). The latter is a good chlorinating agent, which easily replaces hydroxyl groups bij chlorine atom, itself being converted to cyanuric
acid. TCCA is a strong oxidizing agent, it also can chlorinate things, but it does so by oxidation. It can replace H-atoms by Cl-atoms, which cyanuric
chloride cannot do.
Cyanuric chloride also is a nasty one, but it is not explosive. I expect it can be used to make benzoyl chloride from benzoic acid, by replacement of
the acidic OH-group by a chlorine atom.
If you add TCCA to benzoic acid, how would this lead to benzoyl chloride? I see no mechanism for replacement of the hydroxyl group by chlorine. TCCA
cannot exchange Cl by OH. I indeed only see an oxidative reaction, leading to destruction of the structure of benzoic acid in a strong exothermic
reaction, leading to fire or explosion.
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theAngryLittleBunny
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| Quote: Originally posted by Morgan | As an aside, I used to mix prilled ammonium nitrate with calcium hypochlorite and it made some unknown violent snap, crackle, popping sound
spontaneously starting after a minute or so after the granules were combined one on top the other or you could just wet it. Never was it a seemingly
threatening reaction but the pool chlorine hypochlorite product was only 65% with inert ingredients of some sort if that was a factor.
Anyway it seems to liquify and froth somewhat as the reaction takes place if you put it in a wide can and although the popcorn effect was most
entertaining like dozens of mini firecrackers going off at the same time for a little less than a minute duration, it was kind of loud but not too. I
never knew just what the chemical reaction was. Also youtube has never featured it to my knowledge. I mixed about a pound one time.
I can't say it's safe to try but it never seemed to do more than what I described. I would just like to know what cusp of an explosive was formed and
destroyed before it ever became unified enough to become forceful. I avoided the fumes too in which distance from an uncertain reaction is always a
good idea. Some of those hypochlorite and brake fluid videos are pretty snap crackly but the prilled NH4NO3 is just a bit more energetic on that
spectrum. It never made a flame, just steamy smoke and machine gun pops.
Don't take chances with this reaction. I was younger and foolish when I did it. Maybe it's relatively safe, maybe not.
Maybe the heat of the reaction sets off tiny droplets before the formation of any real quantity of NCl3 can happen.
Wiki tidbits on nitrogen trichloride .. .
"Autoignition temperature 93 °C (199 °F; 366 K)"
"The compound is prepared by treatment of ammonium salts, such as ammonium nitrate with chlorine."
"The pure substance (rarely encountered) is a dangerous explosive, being sensitive to light, heat, even moderate shock, and organic compounds."
And for review ...
"Pierre Louis Dulong first prepared it in 1812, and lost two fingers and an eye in two explosions. In 1813, an NCl3 explosion blinded Sir Humphry Davy
temporarily, inducing him to hire Michael Faraday as a co-worker. They were both injured in another NCl3 explosion shortly thereafter."
[Edited on 9-12-2021 by Morgan] |
Maybe it's because in ammonium nitrate there is no chlorine on the nitrogen, so more has to react. With TCCA there is already a chlorine on the
nitrogen which might help form the NCl3 faster.
And I think the ammonia being protonated as an ammonium ion also plays a role in slowing the reaction down, so it's very different then the TCCA
Ca(OCl)2 reaction.
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theAngryLittleBunny
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| Quote: Originally posted by clearly_not_atara | | Quote: Originally posted by theAngryLittleBunny | | Quote: Originally posted by clearly_not_atara | TCCA and its derivatives have caused other explosions as well; see e.g. the chlorination of benzaldehyde. Perhaps we should put a warning in the TCCA
article on the SM wiki, since it is a common chemical that even beginners often use while not being aware of the risks.
The partially dehalogenated TCCA can give off HCl and N2, while alkaline hydrolysis can generate chloramines. And hypochlorites are a concern.
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Oh shiiiit, when I started with chemistry I put solid TCCA to Benzaldehyde in an attempt to make benzoyl chloride. I had no clue this stuff was so
dangerous |
The rxn works under UV illumination in chlorinated solvents, but heating the rxn mixture to
distill BzCl will cause an explosion. It must be done under a strong vacuum, or extracted another way. |
I remember the flask getting warm, maybe even hot at some point and I smelled some benzoyl chloride (not BzCl). However I didn't know how to get the
benzoyl chloride out of that mix and just reacted it with some alcohol. I also did it outside in the sunlight, so maybe this might have done something
as well.
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theAngryLittleBunny
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| Quote: Originally posted by woelen | In the last reaction, you probably confused the use of TCCA with the use of cyanuric chloride. TCCA is C3N3O3Cl3 and cyanuric chloride is C3N3Cl3 (a
trimer of CNCl). The latter is a good chlorinating agent, which easily replaces hydroxyl groups bij chlorine atom, itself being converted to cyanuric
acid. TCCA is a strong oxidizing agent, it also can chlorinate things, but it does so by oxidation. It can replace H-atoms by Cl-atoms, which cyanuric
chloride cannot do.
Cyanuric chloride also is a nasty one, but it is not explosive. I expect it can be used to make benzoyl chloride from benzoic acid, by replacement of
the acidic OH-group by a chlorine atom.
If you add TCCA to benzoic acid, how would this lead to benzoyl chloride? I see no mechanism for replacement of the hydroxyl group by chlorine. TCCA
cannot exchange Cl by OH. I indeed only see an oxidative reaction, leading to destruction of the structure of benzoic acid in a strong exothermic
reaction, leading to fire or explosion. |
Hmm? I said I added it to benzaldehyde so that it would get chlorinated to benzoyl chloride and the TCCA would turn to cyanuric acid, at least that's
how I imagined it would go. I did smell a bit of benzoyl chloride though.
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karlos³
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| Quote: Originally posted by theAngryLittleBunny | | Quote: Originally posted by woelen | In the last reaction, you probably confused the use of TCCA with the use of cyanuric chloride. TCCA is C3N3O3Cl3 and cyanuric chloride is C3N3Cl3 (a
trimer of CNCl). The latter is a good chlorinating agent, which easily replaces hydroxyl groups bij chlorine atom, itself being converted to cyanuric
acid. TCCA is a strong oxidizing agent, it also can chlorinate things, but it does so by oxidation. It can replace H-atoms by Cl-atoms, which cyanuric
chloride cannot do.
Cyanuric chloride also is a nasty one, but it is not explosive. I expect it can be used to make benzoyl chloride from benzoic acid, by replacement of
the acidic OH-group by a chlorine atom.
If you add TCCA to benzoic acid, how would this lead to benzoyl chloride? I see no mechanism for replacement of the hydroxyl group by chlorine. TCCA
cannot exchange Cl by OH. I indeed only see an oxidative reaction, leading to destruction of the structure of benzoic acid in a strong exothermic
reaction, leading to fire or explosion. |
Hmm? I said I added it to benzaldehyde so that it would get chlorinated to benzoyl chloride and the TCCA would turn to cyanuric acid, at least that's
how I imagined it would go. I did smell a bit of benzoyl chloride though. |
@woelen, he was probably talking about this here: http://www.sciencemadness.org/talk/files.php?pid=648784&...
Not sure if the acyl chloride can be isolated, but its claimed to be produced as an intermediate in that reaction, and given the products it sounds
relatively plausible to me.
verrückt und wissenschaftlich
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woelen
Super Administrator
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| Quote: Originally posted by theAngryLittleBunny |
Hmm? I said I added it to benzaldehyde so that it would get chlorinated to benzoyl chloride and the TCCA would turn to cyanuric acid, at least that's
how I imagined it would go. I did smell a bit of benzoyl chloride though. |
My mistake. I read your post and later decided to reply to it, but my mind replaced the benzaldehyde by benzoic acid. With benzaldehyde I can imagine
formation of benzoyl chloride (that reaction is oxidative and replaces H by Cl). But it certainly is a risky thing to do.
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AJKOER
Radically Dubious
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Did read about synthesis based on NCl3 diluted in CCl4 (possibly CHCl3) for organic synthesis.
There is apparently a critical level of dilution required for safe handling, but I still would avoid any UV light sources even if reportedly safe.
Obviously only for professional labs with high purity reagents.
Did find a working reference for NCl3.CCl4 here https://aai.solutions/documents/AA_AN005_Monitoring-NCl3-nit... .
For the record, NCl3 is a high explosive and any drops should be respected as such. Discounting the explosive power for small amounts of NCl3 is
likely the main reason for so many reported injuries.
My recollection also is that a previously suggested path based on the electrolysis of aqueous NH4Cl is reportedly a known laboratory explosion hazard.
Here is a source https://iopscience.iop.org/article/10.1149/1.3071370 to quote: "Explosions occurred in some cases but these, it is felt, can be avoided as they
were probably due to faulty cell construction or to too low electrolyte temperature."
[Edited on 12-12-2021 by AJKOER]
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