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Author: Subject: Chloroacetone tear gas: A Theory, A Mishap, and Questions
Ioxoi
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[*] posted on 5-10-2008 at 16:27
Chloroacetone tear gas: A Theory, A Mishap, and Questions


Hi everyone,

Recently I read about chloroacetone as a tear gas agent, and decided to make my own, resulting in a mishap that is burning my eyes as of this typing.

What I theorized: (Mono)Chloroacetone can be made by bubbling chlorine through a mix of acetone and water with a tiny amount of dilute sulfuric acid.

(CH3)CO + Cl2 --> (CH3)(CH2Cl)CO + HCl

Unsymmetrical dichloroacetone supposedly can be made the same way with more chlorine, with the advantage that it is comparatively insoluble in water and separates as a dense oily layer and can be sep funneled out, whereas monochloroacetone needs distillation for purification.

Since I don't have an effective glassware setup for chlorine bubbling, I decided to go an alternate route, that of pool TCA and acetone with a small amount of HCl as catalyst:

TCA powder would be added to acetone with a small amount of HCl. The following ought to occur-
(CNOCl)3 + 3HCl --> (HCNO)3 + 3Cl2
3Cl2 + 3(CH3)2CO --> 3(CH3)(CH2Cl)CO + 3HCl
and thus the HCl would act as a catalyst. In practice it should be a problem of having 'just enough' HCl to have a SLOW decomposition of TCA to cyanuric acid. Too fast, and it seemed to just bubble out on small trials (with water added to prevent disastrously fast reaction).

What I did: It was kind of a disaster, but it could have been worse had it been done indoors. I took 30 grams of acetone and weighed out and powdered 39 grams of TCA, roughly stoichiometric amounts. I added a little sulfuric acid (maybe 0.25 grams) and about a mL of water to the acetone. Then I poured about 1/3 of the TCA into the acetone mix. (Noted that TCA is pretty soluble in acetone, about 30% or so). Nothing seemed to happen. No greenish tinge or anything, no smell (other than acetone, of course). I let it sit about an hour and nothing happened.

Eventually I decided I had to speed things up. I took a drop of 10% HCl and put it in the bottom of a test tube and dropped a couple mL of the acetone/TCA liquid (I'd be terrified to pour HCl directly into the ~70 grams of reaction mix!) in the test tube and swirled. A faint green color appeared after a while but nothing else. Deciding that it was not doing anything, I poured the liquid in the test tube back into the reaction vessel (a recycled glass honey jar).

I came in and ate dinner with my family. After dinner my mom started complaining that her eyes were burning. I immediately thought of the liquid I had outside, but decided that it was impossible because we were inside and it was outside. Eventually my eyes began to sting a little and I went outside to find the once clear liquid acetone/TCA solution having turned into what appeared to be a grey-white rock. Immediately my eyes, nose and throat began to burn, and though barely able to see I managed to screw the lid on the glass jar. (There ought to be a gas mask smiley). I am guessing that the reaction did nothing for a while and then suddenly decided it wanted to go runaway and spew out a hot cloud of acetone and chloroacetone vapors into my yard, which then somehow managed to wind its way into our house. Poor outdoor animals! Keep in mind that I only added 1/3 of the TCA. I am not sure exactly what the solid is in the sealed jar, as I've left it outside and will check it out tomorrow.

The questions for you guys: Essentially I am asking on some good ways to moderate the reaction, so that it doesn't go insane and blow forth poisonous gas clouds at inopportune moments, such as when I am ladeling TCA into the mix.

One thing I thought of was having 50% acetone and 50% water, instead of just straight acetone. Would this moderate the reaction? The problem is that I do not have a distillation rig, so separating the water afterwards could not be done, unless I could "salt out" the chloroacetone with CaCl2 or some similar high solubility salt, as was stated on an alternate chloroacetone synthesis I saw on the Net (using different reagents).

Another thing I could try is to have the acetone well acidified with HCl and H2SO4, and add the powdered TCA in SMALL quantities over a long period of time. Is this feasible? The one problem I see with it is a labor problem; it would necessitate adding TCA multiple times to a liquid that was continually fuming lacrimatory vapors at me.

I am searching for a slow, one-step (in terms of adding chemicals into the flask) reaction. Any ideas on moderating this beast?

[Edited on 5-10-2008 by Ioxoi]
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kclo4
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[*] posted on 5-10-2008 at 17:27


When you say TCA do you mean TCCA, as in Trichlorocyuranic acid?

you probably had a run-away if it was with TCCA
When it reacts it produces HCl as a byproduct, correct? This will then react with the TCCA producing more chlorine, and then that will react producing more HCl and so on and so forth.

Since you had water in it, I'm going to assume instead of the HCl gas just leaving it dissolved in the water allowing it to react more with the TCCA then it would have with out the water.

You seem to have formed chloroacetone, or something very similar if you didn't.

The solid you speak of could maybe be some funky chlorinated condensation product of acetone. Acetone condensation is after all catalyzed by acid.

Perhaps you could try mixing smaller portions of the TCCA, to an excess of acetone while having some base (CaCO3?) in it to react with the HCl formed?

I don't really know your probably better off reading a patent and see what you can do from there.
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smuv
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[*] posted on 5-10-2008 at 17:59


Use the search engine; you were lucky!

To see how lucky you were, grind up a ~500mg TCCA, and mix it with an excess acetone in a test tube, then add a drop or two of H2SO4 (outside mind you); VERY EXOTHERMIC! This is fun on a small scale, but on a larger scale :o!




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kclo4
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[*] posted on 5-10-2008 at 18:18


I believe I've done what smuv is talking about with a common alcohol of some sort and a dash of HCl. It was pretty freaky, I knew it was going to be pretty violent, but it was more impressive then I thought it would be.
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[*] posted on 5-10-2008 at 18:58


Yeah, I have tried the same; I only wish I tried to isolate some products. I'm guessing these would be chlorinated acetic acids through chlorinated acetaldehyde species. IIRC this reaction was not as vigorous as that with acetone, with acetone a runaway occurs almost as soon as you add the acid.

The trick for the acetone reaction, is to get most of the TCCA to dissolve before adding the acid, then it is really vigorous.

Anyhow, loxoi, I would use caution in the future with TCCA, it is a strong oxidizer and prone to runaways. I would also recommend in the future to use the forum search before trying anything, as they say "stand on the shoulders of giants". Of course not everything has been tried here before, but when something has, seeing others' problems, mistakes and solutions always gives your experiments a higher chance of success.

Anyhow, I wish your future experiments luck.

[Edited on 10-5-2008 by smuv]




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[*] posted on 5-10-2008 at 23:09


Quote:
Originally posted by Ioxoi
I am searching for a slow, one-step (in terms of adding chemicals into the flask) reaction. Any ideas on moderating this beast?

I find it unbelievable that after all the warnings and accidents reported here (UTFSE!) there are still people who, rather than following the original patent procedure of chloroacetone preparation using TCCA, they try to do their own immensely irresponsible and irrational modifications.
You are very lucky the whole thing just did not blow into your eyes! Not to mention the stupidity of using a stoichiometric ratio and on such a huge scale! And why the hell you did not just follow the experimental from the French patent which was checked and works perfectly even on a larger scale?

:mad:

I wonder how many times we will still have to read about accidents with chloroacetone? Use the fucking search engine! That's how a responsible person finds the information about "moderating this beast".




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[*] posted on 5-10-2008 at 23:53


Right.
I have just wanted to write about one-pot preparation of chloroacetone (and also chloroacetophenone - scope of this method is propably very wide) from NaCl/H2SO4/KClO3 and acetone, but I am not going to wrtie this. Just because of such nincompoops.
ps. chloroacetone looses with chloroacetophenone in "lacrymatory power" discipline. At least my nose and eyes say so. Flood of tears...

[Edited on 6-10-2008 by kmno4]
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[*] posted on 6-10-2008 at 01:02


Haloacetones only briefly saw use as riot control agents almost a century ago, they quickly fell out of favor because they were way too toxic, for police use, and not toxic enough for military use as lethal agents. Better RCAs were found that were more effective and far less toxic. No need for me to recite them here, due to the nincompoop factor, as kmno4 has so aptly phrased the problem.

Chloroacetone remains an important industrial chemical commodity but its utility as a CW agent is nil.




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[*] posted on 6-10-2008 at 05:12


Having some experience of chloroacetone I think you would have to be bonkers to try and make it on this scale in a honey jar.
It is a powerful irritant and lacrymator.
As for DIY tear gas manufacture, this could get you into really serious trouble!
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[*] posted on 6-10-2008 at 14:40


Indeed!

Haloacetones are awfully irritating!

We made 1-iodoacetone in A-level in a kinetics experiment. Even on a small scale I could detect the odour but it didnt cause discomfort per se. However I made these on a (semi)microscale years ago as perhaps one of the first organic reactions I did! Easy to make but not stable, you have to add (calcium carbonate? IIRC been a while).

Personally I wouldn't recommend anyone make anything lacrymatory at home unless you have a pretty decent hood and are not in a built up area!

Look at these chlorine and bromine "bombs" on youtube... that is quite a scary thing to have, especially if it went wrong in a glass container with flammables, corrosives and extreme irritants!

BE VERY CAREFULL




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[*] posted on 8-10-2008 at 07:54


Really sorry, guys, for acting kind of retarded and pretty unsafe/deadly in my procedure. Organikum, I did eventually find your modified French patent procedure (after an hour of searching though! Search engine on this site doesn't work well; if you type "(chloroacetone)" you get your procedure but if you type "chloroacetone" without parenthesis you don't) and performed it on 1/10 (!) the scale you recommended and got a couple tablespoons of dilute chloroacetone solution in acetone.

I could not, however, find the original French patent FR 2,633,614 on the internet, at least not on Google. The internet was littered with references to it, but could not find the original. Do you have to ask for it in paper form? Anyone have the original?

As for the "tear gas" part, I must make clear I was not planning on launching some kind of terror strike or something ridiculous like that. My interests were simple chemical curiosity; having a tiny vial of liquid that makes you feel like you're cutting onions when you unstopper it. I would never try and do a prank or something because that would at the very least be illegal and at the most a serious felony. I referred to it as "tear gas" because it was once used as a tear gas and have no destructive plans, only for curiosity and perhaps as a cool thing to show to my friends.

Seeing as I've now gotten Organikum's procedure and there probably is little novel academic merit left in this topic, if you guys would like it can be detritused because it probably won't serve you guys much use anymore (other than another example of how NOT to make chloroacetone for other people!:P).




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[*] posted on 8-10-2008 at 08:18


European patents can be obtained from the European Patent office. You can do a number search, do not include commas though.
FR2633614

Also, you can use google to search within websites for example to look for chloroacetone you could type into the google search bar "site:www.sciencemadness.org chloroacetone."

Additionally, I want to emphasize that good research skills come in very handy for any chemist (pro or amateur) so it is something worth putting effort into.




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[*] posted on 8-10-2008 at 22:48


Invest in some glassware. Look on ebay and get one of those organic chem kits. If you do get one in the 19/22 size. 24/40 is more costly and commits you to larger batches. Main use of chloroacteone is for Friedel-Krafts reax. Whatever you do, don't react it with benzene!



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[*] posted on 9-10-2008 at 23:20


Quote:
Originally posted by chemrox
Main use of chloroacteone is for Friedel-Krafts reax. Whatever you do, don't react it with benzene!

What? There are nearly no Friedel-Crafts reactions with chloroacetone described in the literature. Just a couple maybe. It is of very low reactivity compared to other alkyl chlorides in this reaction (due to the electron withdrawing effect of the neigbouring carbonyl and the tendency to become crap in presence of acids like AlCl3).
Chloroacetone is nearly exclusively used in heterocyclic chemistry and even there only rarely. It is commercially available but it is not particularly common outside heterocyclic chemistry labs.




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[*] posted on 10-10-2008 at 04:21


finklstien (damb my spelling sucks).

not the titled compound but an ample solution.

isn't chloroacetone carcenogenic.




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[*] posted on 28-5-2009 at 12:18


Chloroacetone is nifty. A Definite chemical weapon in every sense of the word however. How many of you blokes have actually made it? You'd be stupid to make it without a gas mask on, infact, it's the one chemical which has caused me the most strife in terms of worry, i remember when i made it, i just pumped pure molecular chlorine gas into a 500ml flask filled with acetone, and watched as the acetone turned grey as the chlorine went in, once all of the chlorine was gone, i, outside, with a gask mask on, and heavy gloves, quickly transferred the chloroacetone into an amber container, with a strong glass lid, with which it sits to this day. With a toxic skull symbol on it.

But before that i also made it, once, and i kept it in a clear 250ml flask with a rubber stopper, it turned the most evil looking dark color after a few days, and drops of it use to suspend on the rubber stopper, i sealed it in a air-tight container, and buried it deep far away from civilization. As for it's riot control status, it is apparently the most effective riot control agent of all, according to the book "A Laboratory History of Chemical Warfare Agents", not nessecerily causing death at all, unless you where unluckly, but serving the goal of complete incapacitation towards enemy militants/rioting civilians. I'm glad that i have it to protect my family to be honest. :o



[Edited on 28-5-2009 by TheMadMen]
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[*] posted on 28-5-2009 at 13:44


Quote: Originally posted by TheMadMen  
Chloroacetone is nifty. I'm glad that i have it to protect my family to be honest.

Nice to see you have an irreverent sense of humour, guys. . .
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[*] posted on 29-5-2009 at 07:14


The reaction of halogen with acetone is acid catalysed, and, IIRC (I did the same kinetics experiment as panziandi) the rate equation is:
rate = k[H+][acetone]

As you can see the concentration of the halogen does not appear! So I suggest making iodo- or bromoacetone, purely because you can mix the halogen and acetone, then a small quantity of acid catalyst. If you still persist on making chloroacetone, then make it in a gas generator and bubble it through acidified acetone - making the chlorine in situ as you have seen is dangerous and should not be attempted.
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[*] posted on 30-5-2009 at 02:10


Vh;oroacetone is an industrial chemical, period.

It is an OBSOLETE lachrymatory agent and LESS effective as such than chloroacetophenone (CN) or o-chlorobenzalmalononitrile (CS) which are what eclipsed it almost a century ago.

No one stockpiles haloacetones as CW agents. They are of historical interest only as such.




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[*] posted on 31-5-2009 at 07:16


Chloroacetone presents itself as a useful, powerful, incapacitating agent, and ..... is also a useful industrial chemical in it's own right.

Quote:
As you can see the concentration of the halogen does not appear! So I suggest making iodo- or bromoacetone, purely because you can mix the halogen and acetone, then a small quantity of acid catalyst. If you still persist on making chloroacetone, then make it in a gas generator and bubble it through acidified acetone - making the chlorine in situ as you have seen is dangerous and should not be attempted.


I Might just do that next time to be honest. Sounds alot easier. Bubbling chlorine gas through acidified acetone you mean?:D

EDIT by Davster: the bulk of this message was personal attacks which has been removed.

[Edited on 31-5-09 by The_Davster]
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[*] posted on 31-5-2009 at 08:46


Ok, back to the chemistry NOW:mad:
Any more personal attacks and I will purge this thread...

That said, chloroacetone is amusing stuff. Organikum posted a procedure years ago using TCCA as the chlorination agent, which can be done without a gas mask easily. In acetone solution the stuff is manageable.

That said, themanmen, you do not have pure chloroacetone, to convert 500ml of acetone to chloroacetone you would have needed to add 482g of chlorine gas, which would have left your chloroacetone very acidic after the reaction. Acidic chloroacetone is known to not be stable on storage. You likely had a dilute solution of it, and now because of residual acid, you likely have nothing.




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[*] posted on 31-5-2009 at 09:01


Thankyou for the informative information The_Davster, you may well be right, it is stored in an amber glass bottle though, would that help?

Maybe i'll just have to make another batch oneday soon. Your calculations make sense, and i will definitely make use of them next time if i do.
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[*] posted on 31-5-2009 at 11:44


How would storing it in an amber bottle help if its too acidic INSIDE the bottle. Especially when The_Davster states explicitly
Quote:

Acidic chloroacetone is known to not be stable on storage.
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[*] posted on 31-5-2009 at 11:54


monochloroacetone is stablised with calcium carbonate powder in amber bottles stored in the cool.



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[*] posted on 31-5-2009 at 12:59


I found that MgCO3 worked as well. Must be that any carbonate destroys any acid that happens to be around.

http://www.sciencemadness.org/talk/viewthread.php?tid=2713




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