jimmyboy - 19-9-2004 at 14:13
I was messing with a synth for ammonium chloride and decided to damp some ammonium sulfate with a little isopropanol (a few drops) and then add
calcium hypochlorite - the reaction was nasty - it bubbled and hissed and a thick acrid vapor formed - after all was done i added some water and was
left with what looked like calcium sulfate on the bottom and ammonium chloride floating around in the solution forming crystals -- what on earth was
the vapor - man was that nasty - it wasnt chlorine (not green) - it was a whitish color - maybe it was the chloride as well but i've been around
ammonium chloride vapor and it was never nasty like this and it didnt have the ammonia scent - almost was like hydrochloric to me. Im still toying
with what happened exactly. Any ideas would be good.
Reverend Necroticus Rex - 19-9-2004 at 17:58
Calcium hypochlorite is acidic, maybe the acid action was sufficient to liberate some ammonia, ammonia+a hypochlorite does generate chloramine, along
with some hydrazine, although not very much in the case of a reaction not optimised for hydrazine production, and I think, some incredibly small
amount of NCl3, although I'm not sure on that last one.
Aparrently, I just UTFSE for chloramine, and it dissociates to Cl, NH3 and free oxygen radicals inside the lungs, could explain it.
I have tried to gas ammonia through bleach before in a failed attempt at making NCl3, I always though chloramine was yellow though, could be due to
trace amounts, and I MEAN trace, of NCl3, I couldn't find a MSDS on google for chloramine, it all came up with chloramine-T, some sort of water
chlorination agent.
jimmyboy - 19-9-2004 at 18:12
hmmm - i always thought calcium hypochlorite was alkaline - my other theory is maybe it was hypochlorous acid - and that reacted with the ammonia
resulting in ammonium chloride and water vapor
Reverend Necroticus Rex - 19-9-2004 at 18:36
Hypochlorous acid is pretty unstable, and wouldnt the combination of that with NH3 yield ammonium hypochlorite?
JohnWW - 19-9-2004 at 19:22
The decomposition should release Cl2 and OH- ions, which would chlorinate any NH3 or ammonium salts present to chloramines, i.e. NH2Cl, NHCl2, and
finally NCl3.
John W.
vulture - 20-9-2004 at 00:31
Solutions of calcium hypochlorite are alkaline, because hypochlorous acid is a weak acid and because it's usually contaminated with
calciumhydroxide.
Esplosivo - 20-9-2004 at 05:08
Sodium hypochlorite is listed as incompatible with ammonium sulfate in the MSDS. Sodium and calcium hypochlorites are quite similar.
What occured is probably due to the fact that a solution of ammonium sulfate in water is acidic, due to the stronger conjugate acid. An acid would
react with the OCl- to produce Cl2. The rxn of Cl2 with the ammonium sulfate were already mentioned.
[Edited on 20-9-2004 by Esplosivo]
jimmyboy - 20-9-2004 at 17:08
After looking awhile in Othmer i found that impurities catalyze a reverse reaction between hydrazine and chloramine which form N2 + Ammonium Chloride
which explains what happened pretty well.
Thanks
JohnWW - 20-9-2004 at 22:03
But, how would hydrazine, N2H4, come to be formed in the reaction solution, with an ammonium salt, under consideration here?
John W.
Careful!
hodges - 21-9-2004 at 15:31
Ammonium salts and hypochlorites can, under the wrong conditions, produce an extremely unstable high explosive (nitrogen trichloride). Have a look at
this link describing what happened when hypochlorite was added to a tank that previously contained urea. I realize there is a difference between urea
and ammonium salts, but some the the same reactions can occur with either.
http://www.chemaxx.com/explosion16a.htm
Reverend Necroticus Rex - 21-9-2004 at 19:40
I take it the right..COUGH..wrong conditions for NCl3 formation include a highly acidic environment?
Judging that is, from that incident with the tank of bleach that was posted, jeebus H christ, that was scary, that much NCl3 simply shouldnt be,
ANYWHERE, EVER