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Author: Subject: Chloropicrin and its Odor
Madog
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[*] posted on 12-11-2003 at 17:01


ah, thanks. i was thinkig about the reaction earlier and realised that there must be H+ for the to procede.

i added about 100ml of chlorox onto .1-.2g TNP. after about 7 hours the presence of chloropicrin was evident. several days later the solution whent off-yeloow-clear and there is a few drops of translucent-off-yellow liquid on the bottom of the flask :-D




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[*] posted on 17-11-2003 at 20:00


After reading through the section on Chloropicrin in War Gasses again, I have found some information regarding the supposed Trichloronitronates and the interaction of Chloropicrin with metals...

"...chloropicrin attacks steel slightly and copper and lead very energetically. American publications, however, assert that chloropicrin attacks all metals."

and

"On treatment of Chloropicrin with an aqueous solution of sodium or potassium hydroxide there is no reaction, but if alcoholic soda or potash is employed, a gradual decomposition takes place and after a time crystals of potassium chloride separate."

Trichloronitronates have caught my interest though, and I can find almost no information about them- much less their potential bioactivity. Perhaps they can be synthesized by chlorinating Nitronate salts?
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[*] posted on 14-12-2003 at 20:37


If you want to dispose of this stuff, how can it be done besides the toilet or letting it evaporate?

Topics changed a bit since first page, this is in relation to CP.

[Edited on 15-12-2003 by Darkfire]




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[*] posted on 15-12-2003 at 09:04


Concentrated alkali would me my first idea.
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[*] posted on 15-12-2003 at 18:30


Sodium Hydroxide should decompose Chloropicrin to less aggressive molecules. As for me, I've always taken the flush-it and forget-it route :D. May the fish forgive me :(.
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[*] posted on 15-12-2003 at 19:24


That would work for me exept in still a stay at home highschool student, parents wouldnt take to kindly to trying to being rudely taken away from a good shit because they had a chemical weapon just splash up their ass...

Im gonna do the mix with naoh then flush and forget method.
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[*] posted on 15-12-2003 at 20:20


Man, I just hate getting a spash with chemical weapons. It takes all the joy out of a nice long relaxing sit on the john.

https://www.denix.osd.mil/denix/Public/News/OSD/UXO/Conferen...
They have a few more methods. Hydroxide seems pretty easy, and cost efficient. Bisulfate to if you don't have any hydroxide handy(but by the sounds of it you do).
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[*] posted on 16-12-2003 at 11:36


Be careful with the sulfates and bisulfates. Reactions between Chloropicrin and these compounds can produce nasty decomposition products, such as Nitrosyl Chloride and Phosgene. I would go with the Hydroxide route because the decomposition products are less aggressive.
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[*] posted on 16-12-2003 at 17:52


Yeah making phosgene, kinda defeats the point of destroying the CP.



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[*] posted on 16-12-2003 at 19:34


That's alcoholic Sodium Hydroxide, btw, as stated in an earlier post concerning reactions with Chloropicrin. Since Sodium Chloride will gradually precipitate out, it puts the Chlorine into a safe form-- as opposed to Phosgene or NOCl. Not sure where the C and the -NO2 will go...
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thumbup.gif posted on 17-12-2003 at 02:12


I think that chloropicrin + sodium hydroxide =. Sodium chloride + water + sodium nitroacetate. The nitroacetate ion could then be alkalysed into sodium nitrite and sodium carbonate.
I made a mistake previously, stating the nitronate ion as CH3NO3H-. It's actually CH2NO2-. Can't see how trichloronitronate is possible, maybe the hbydroxide can join across the molecule?
:(:(:(
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Organikum
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[*] posted on 17-12-2003 at 05:52


Reduce the chloropicrin with ironfilings from cast iron and HCl (aqueous) to methylamine and ammoniumchloride. If only so much HCl is added that the solution stays SLIGHTLY acidic all time predominantly methylamine is formed, if more HCl is added mostly ammoniumchloride will be resulting.

I added "aqueous" to the HCL and "iron filings" instead of Zn, also I believe Zn to work also.


[Edited on 30-12-2003 by Organikum]
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[*] posted on 17-12-2003 at 07:29


:o Reduction of Chlorpicrin in an Acid Environment is very dangerous!! That will not safetly decompose Chloropicrin, it will form much more dangerous Phosgene Oxime. That is actually the synthesis route of Phosgene Oxime: Chloropicrin is dissolved in an Aprotic solvent, HCl is bubbled through, and it is reduced with Tin or Zinc.
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[*] posted on 17-12-2003 at 07:35


The procedure is plain from the article "chloropicrin" from the old ftp. It is said to produce methylamine in quantitative yields. The use of HCL - aqueous and no aprotic solvent may make the difference so I added the "aqueous" to my post before to avoid endangerment by misinterpretation.

[Edited on 17-12-2003 by Organikum]
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[*] posted on 26-1-2004 at 21:43


This has been delayed much too long-- I've finally got back to my experiments in Chloropicrin, and this time I've had more success than ever. I have found a way to produce high-quality Chloropicrin from OTC Nitromethane Fuel solution. Mine was 30%.

I found that I wasn't using nearly enough NaOCl solution relative to the amount of NM I was using. But, I will excuse those early experiments as "preliminary." I don't have my actual procedure and calculations with me, as it was contaminated, and thus not brought inside the house.

Here was the procedure, out of memory:

25 g of 30% Nitromethane is added rapidly to 415 mL of 6.00% NaOCl solution, quickly stirred (I stress quickly-- don't want to be around it too long), and covered. It would now be prudent to leave the area, and to let the reaction go for about 10 minutes. After this time, add 30 mL of 30% HCl to the mixture, and stir. The Chloropicrin will sink to the bottom and little globs of saponified Castor Oil will float to the top/cling to the sides. The other impurities will dissolve in the water. The mixture can now be decanted off, being careful not to pour out the bottom layer of Chloropicrin.

It's incredibly simple, but I should give some warnings. Friends, like you, I don't believe in k3W|_ warnings, but I cannot give the procedure without some words of advice. DO NOT try to see if the Chloropicrin is there... trust me on this, it is there; so no wafting and NO SNIFFING. If you feel your eyes watering, leave the area immediately-- you don't want to inhale too much of it or it WILL ruin your day. I think that the chances of it actually killing you are low, but it can make you wish you were dead. Easily the most dangerous part of this reaction is decanting off the impurities...this will be the part where you are exposed to the most Chloropicrin (as there will be less water between it and you), so be forewarned. Hold your breath, if you don't have a gas mask or good ventilation, and do it as quickly as possible.

The HCl proved to be the key ingredient here, in that it neutralized the NaOH that would otherwise destroy the Chloropicrin, together with the alcohol. If you are using 5.25% bleach, you will use 475 mL of NaOCl to 25g of 30% Nitromethane. The Chloropicrin looks like a blob at the bottom of the reaction vessel... Mine came out red, probably from various impurities and coloring. But no doubt, it was, in fact, Chloropicrin. From the size of the blob, it looks like I got very good yields (this is based on the amount of NM I used... I could not actually weigh it, due to some concerns for safety/chemical hygiene).

I did not have any vessel that I could seal and store the Chloropicrin in, so I simply poured Ethanol on top of it and added NaOH-- alcoholic bases can be used to decontaminate this.

There you have it. Happy crying, and happy coughing. I would not try to upscale this, simply because of the danger of it.
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[*] posted on 27-1-2004 at 08:46


You could always dispose of it by detonating it....



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[*] posted on 27-1-2004 at 09:37


I haven't tried detonating Chloropicrin... But, because of its properties as a lachrymator, it's best used as a gas. For explosions, Picric Acid would be more useful. In any case, the situation was rather dire-- more of it had vaporized than I thought-- and late night detonations attract far too much attention.
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[*] posted on 29-1-2004 at 20:46


<blockquote>quote:<hr>You could always dispose of it by detonating it....<hr></blockquote>IIRC I read somewhere it's undetonable (I'm not sure @all). any info on this is greately appreciated..



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[*] posted on 12-3-2004 at 13:40


For some reason I have been bit by the chloropicrin bug again, and decided to produce a small amount via the TNP route.

First, 1g of TNP was measured out into a 250ml Erlenmeyer flask. This was taken out into the garage along with 200ml of 6% bleach. I was going with .004 molar amounts for each chemical, and this ratio is near stoichiometric. I donned my respirator and added the bleach to the TNP. Upon contact, the TNP fizzed a bit with what I remember to be reddish bubbles. This subsided soon as the rest of the beach was added. What I had now was a orangish liquid in the beaker.

I then walked away, leaving it on the garage floor to react. I just wandered around the garage for a while, looking at some the chemicals we have on the shelves, wondering what I could use them for. I remembered the chloropicrin, so I walked over to the flask. My eyes started twinging when I was near it. Suprised, I jumped back. I stepped around 20-30 feet away, removed my mask a bit and carefully sampled the air...and about choked. I had filled my garage with chloropicrin vapors, and had not noticed it because I was wearing my respirator. I only noticed when it started effecting my eyes as I approached the flask. I quickly ran over and stoppered the beast. The garage doors were opened to flush the toxic gas from my house.

That night, I checked on it, and it appeared that nothing was formed. I initially suspected the small amount of PS formed went into solution. I know PS was formed, however, from the odor that escaped the flask when it was unstoppered.

Flash to today, around 47 hours after reaction, I decided to check on the vessel. I was suprised to find an opaque white, dense liquid sitting ominously in the bottom of my flask. Upon seeing the liquid, it gave me the same feeling one would get from going to the bathroom in the middle of the night, then turning on the light to find a rather large spider on the toilet. I stopped in my tracks, startled, then went to inspect it.

There really isn't much to say about it, I am going to see if I can get some more from the reaction. The surrounding liquid now is more of a bright yellow color, opposed to the orange from the beginning of the reaction.

Overall, the TNP route is more time consuming due to the nessesary production of picric. I decided that the NM route would prove better yeilds, but I do not have access to NM at this time. One could cut down drastically by using a higher concentration of hypochlorite, and one needs large amounts of bleach for small batches, and the volume could be a hassle.

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[*] posted on 12-6-2004 at 02:43


Sorry. Another dead topic resurrected.

Now some of you may understand why I was so interested with picric acid ;)

OKay! What the hell? How is CCl3NO2 made from (NO2)3-(C6H2)-(OH) and NaOCl? This one really has me boggled. Where does chloropicrin get its carbon from picric acid? Wouldn't this break the aromatic ring? What's the equation!! There has got to be a multitude of products.

Anyone care to enlighten me?

Thank you kindly.




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[*] posted on 12-6-2004 at 10:29


chloropicrin can be synth otc from chloroform and HNO3 :

CHCl3 + HNO3 --> CCl3NO2 + H2O

and the choloroform can be make from acetone and bleanch:)
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[*] posted on 12-6-2004 at 11:24


Quote:

The nitroacetate ion could then be alkalysed into sodium nitrite and sodium carbonate.


Acidify the nitroacetate solution, distill over a column and you have your nitromethane back. :)

EDIT: According to Organikum (the book)Nitroacetic acid should decarboxylate when distilled...

That is, if the other components do not interfere.

If it works, you have a way of converting TNP to nitromethane...


[Edited on 12-6-2004 by vulture]

[Edited on 12-6-2004 by vulture]




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[*] posted on 29-8-2004 at 22:35


Sorry for bringing up this old topic again, but the chloropicrin thread will surely never die.

I also have read the german book "Die Chemie der Kampfstoffe" and I understand it because I am from germany. This book is extremely valuable and informative, it gives a fully outlined laboratory synthesis for every war gas used in WW1. Including a synthesis of dichlorodiethylsulfide from disulfur dichloride and ethylene.

I have read about an undiscussed way of destroying chloropicrin there. Chloropicrin reacts readily and rapid with a solution of sodium sulfite (Na2SO3) to form the sodium salt of nitromethane disulfonic acid. The reaction must be carried out at elevated temperature and occors in alcoholic and in aqueous solution.

CCl3NO2 + 3 Na2SO3 + H2O ---->

CHNO2(SO3Na)2 + 3 NaCl + NaHSO4

This is a far better method to destroy CP than alcoholic NaOH.

I am also wondering about the equation for the formation of CP from TNP and NaClO.
I have not been able to find this out!!!
It would be very helpful if someone could post this equation.

I can also say that aqua regia + acetone is not a good method of preparing CP, the reaction is very violent and can get out of control quickly.

When I have time and some bromine, I will try to make bromopicrin! (NaBrO + TNP)
It is a stronger lachrymator than chloropicrin but about ten times less toxic.

[Edited on 30-8-2004 by garage chemist]
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[*] posted on 30-8-2004 at 15:44


I made some chloropicrin today employing both TNP and NM routes with sucess both times.

The TNP route left a few plastic'ish looking foaters similar in color to TNP that appeared after adding the hcl even though all TNP went into solution upon the addition of the bleach. Curious. as all the starting chemicals were commercial except the clorox.

I have never smelled CP before but it was really very similar to chlorobenzylidene malonitrile (CS agent) which I have smelled on many occasions.

The only difference I can think of was the CP description of hints of "licorice" smell, was really very accurate whereas the CS has a peppery note in it's flavour.

Mmm I'm getting hungry!
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[*] posted on 30-8-2004 at 17:12


I find the Sodium Sulfite route of destroying PS (this is the NATO designation for it and proper abbreviation) to be very interesting. Do you know how long this reaction takes or how high the reaction temperature has to be?

I have personally tried the NaOH/Alcohol destruction method and it does not work very well. I had the PS flooded in the decontamination mixture and after several days, there was still the detectable and irritating odor of PS. And on the note of odors, CS definately has that "peppery" odor while PS has that "thick" and "penetrating" and "irritating" odor. However, from my experience, PS causes a more painful reaction that makes you feel like you will pass out; CS's throat and chest pain didn't feeel the same to me (i felt it a while ago...I might test it again to give a more accurate description).

Also, what is this book "Die Chemie der Kampstoffe" (or should it be "Kampfstoffe"?) ? Is that simply "The War Gases" in German? Who is the author? Is it an online e-book for us all to see? :D




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