Sciencemadness Discussion Board
Not logged in [Login - Register]
Go To Bottom

Printable Version  
 Pages:  1    3  4
Author: Subject: Chloropicrin and its Odor
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 18-5-2003 at 04:40
Chloropicrin and its Odor


This morning, I performed the reaction between Nitromethane (mine was 30%, with castor oil and methanol- keep this in mind), and 6.00% Sodium Hypochlorite Bleach.

The way I went about doing it was rather crude... I simply heated up a Mason Jar with hot water, poured in 50 mL of Nitromethane, and then added an excess of bleach. I then stirred for 20 minutes.

A reaction definitely did take place, because there was an immediate color change (from the Nitromethane mix's original blue) occurred and heat was given off.

As I performed this reaction, a strange smell was given off, which I suspect was that of Chloropicrin... but I have never smelled Chloropicrin, and nor can I find any specific details about its smell. It was a sweet odor, but not terribly pungent. However, whenever I smelled it, irritation of the eyes and throat promptly followed. The smell was not painful to breathe, like Chlorine or Ammonia, but it did really irritated the eyes...it felt like Onions. It also caused coughing, and later slight wheezing.

What I need to know is, what does Chloropicrin smell like?? I mean, specifically- not just "strong and sharp and irritating," because that is not very descriptive...

Also, could any side reactions have taken place? I mean, could the Methanol have reacted with the NaOCl, or the Castor Oil with the NaOCl, to produce another compound that has a sweetish odor?

Also- I would like to describe to you what my reaction mixture looked like after the 20 minutes: It was mostly reddish/brown, and at the top of it there was a clearish/bluish looking oily liquid, but not much. Also, there was some flaky compund. I suspect that this would have been the NaOH that is formed from the reaction between Nitromethane and the Hypochlorite.

Anyone want to help their old buddy Samosa? :) Not just for me though; perfection of this method offers an EASY and CHEAP way to Chloropicrin, with 95% yields! Keep in mind, I did this reaction in Mason Jars with impure chemicals...

[Edited on 5-18-03 by Samosa]
View user's profile View All Posts By User
Haggis
Hazard to Others
***




Posts: 238
Registered: 1-12-2002
Location: Mid-America.
Member Is Offline

Mood: Lacrymating

[*] posted on 18-5-2003 at 07:15


Sorry Samosa, but my book only says, 'stinging, pungent odor'. I can give your some other 'stats' on it though to help you figure out what it is.
Real name : Nitrotrichloromethane.
Physical state: Colorless oily liquid
Boiling point: 112 C
Non-flammable. Soluble in organic solvents but not in water. No hydrolysis in water. Decomposes under the influance of light (UV). "Irritates nose and throat; causing tearing; irritates lungs at higher concentrations; causes nausea and vomiting; can cause skin lesions" It's also very soluble in fats and oils, so organs can absorb it.
Well, I'd hate to get this stuff stored in my lungs.;)
View user's profile View All Posts By User This user has MSN Messenger
Krypton
Hazard to Self
**




Posts: 90
Registered: 21-11-2002
Location: Spain
Member Is Offline

Mood: explosive 21

[*] posted on 18-5-2003 at 09:53


The vapours of chloropicrin are extremely
acidic, the best with gas-mask or a fume-box when maked.




In convention with my ancestor.
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 18-5-2003 at 16:52


After reviewing the patent, I see three things that I did incorrectly in my synthesis.

First, there was supposed to be a slight excess of Nitromethane, not the Hypochlorite.

Secondly, I was to add the Nitromethane to the Hypochlorite, I did it the other way around.

Thirdly, I was supposed to add the NM gradually, I did it rather quickly.
View user's profile View All Posts By User
a_bab
National Hazard
****




Posts: 449
Registered: 15-9-2002
Member Is Offline

Mood: Angry !!!!!111111...2?!

[*] posted on 18-5-2003 at 23:39


I tried with the picric acid/CaOCl2 method, without having any references but the fact that these are the reactants. I did the reaction in in an aquous sollution, with mild heat, and I can tell you that the smell of chloropicrine is somewhat like chlorine smell, a little bit sweet and you feel it in the throat instantly. And yes, with copious amonts of tears. I cannot decribe it better as I never felt a similar smell. On the other hand, I'm sure you've got chloropicrine with your reaction.

I suggest you to try the chloroform/nitric acid route. Chloroform is piss easy to make. The drawback is the fact that the reaction is sustained in an enclosed tube, and it takes some time to perform.
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 19-5-2003 at 05:16


Copious amounts of tears you say? Hah. That's what I am suffering through as I type- I'm redoing the reaction with my previous mistakes corrected.

As I add the Nitromethane mixture to the Hypochlorite, I get that sweet smell, and that is promptly followed by coughing (irritation in back of throat, and in chest too!) and lots of tearing.

I am now confident that I have CHloropicrin, now the problem is just separating it out :(.
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 19-5-2003 at 05:43
Success! (Pretty sure, at least)


I am pretty confident I have had success. A distinct, oily, clearish-bluish (i suspect the blue is caused by the Nitromethane's coloring), liquid formed at the bottom of my reaction mixture. This layer was obviously denser than the rest of the chemicals, and was insoluble in water. Furthermore, it caused profuse tearing and severe irritation to my throat. I could barely do anything but cough for a full 2 or 3 minutes. I was coughing so badly, I thought I might vomit from it... Yields were small, but that could be attributed to impurities and to rushing. But, clearly this is an effective, easy pathway to Chloropicirn.
View user's profile View All Posts By User
vulture
Forum Gatekeeper
********




Posts: 3332
Registered: 25-5-2002
Location: France
Member Is Offline


[*] posted on 19-5-2003 at 06:20


Chloropicrin can also be made by reacting TNP with KClO3 and HCl apparently.

I don't know anything about yields though.
View user's profile View All Posts By User
rikkitikkitavi
Hazard to Others
***




Posts: 192
Registered: 17-6-2002
Member Is Offline


[*] posted on 19-5-2003 at 08:51


FYI:

cloropikring is enlisted on UN list of forbidden chemical weapons (CWC directory) so beware that the Bush doesnt come down with a Thomahawk...

/rickard
View user's profile View All Posts By User
Nick F
National Hazard
****




Posts: 439
Registered: 7-9-2002
Member Is Offline


[*] posted on 19-5-2003 at 12:22


Haha, ouch. It fucking works, doesn't it? I just put a few spatulas of TNP into 5% NaOCl bleach at room temp. There was a faint odour, hard to describe... like a cross between CH2Cl2 and really strong English mustard, with hints of chlorine... but whereas CH2Cl2 and chlorine both smell quite "clean," this smelled "dirty." Hence the inclusion of mustard in the description. BUT I really don't know if you have any idea of what I mean by a "clean" or "dirty" smell... I would like to describe the smell as "mottled brown, lumpy and rough," but then I really don't think you would have any idea of what I was talking about. That's what I think the smell would look like if you could see it. I covered the vessel with some cling-film, and went back ten minutes later. The solution hadn't changed in appearance, it was still just a bright yellow, clear solution, but tiny droplets of condensation had formed on the cling-film. Carelessly and foolishly, I peeled back the cling film, and at arms length I tapped the top of the film with my finger, to send a gust of air from inside the beaker towards my face. I didn't think a significant amount had formed, there was no sign of it in the liquid and the solution looked no different. Then suddenly it felt like someone had actually poked me in the eye with a stick that was covered in sand paper. It's VERY strong, especially considering the small amounts I was exposed to!! I bet this stuff clears blocked sinuses fast...
Strangely, I did not notice any coughing... maybe because there was little in the air in the room, I just got a quick burst of it.

(Note to self: be more careful with chemical weapons.)
View user's profile View All Posts By User
a_bab
National Hazard
****




Posts: 449
Registered: 15-9-2002
Member Is Offline

Mood: Angry !!!!!111111...2?!

[*] posted on 20-5-2003 at 03:11


I read somewhere that because of the chloropicrine the victims commited suicide. That was back in the WWI.
Hey, Samosa, beware. It would be pitty to loose such a good member ;)
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 20-5-2003 at 03:52


No worries mate, I only have a little bit of the stuff (less than 10 mL), and it is securely sealed off.

However, now I will list some of my personal observations with Chloropicrin...

The odor reminds me of the smell of some Halocarbons, somewhat like Acetone, but with the strong smell of Chlorine mixed in. About 1 or 2 seconds after smelling it, the eyes feel like they would after cooking with Onions- basically, you're forced to close them. This is also accompanied by tearing. If you stay in the presence of the vapors longer, and actually inhale them, it irritates the back of the throat and causes coughing. However, I never noticed any upper; respiratory irritation, as would be caused by straight Chlorine.

After exposure, coughing continues for a few more minutes; but not too long. The chest gains a slight feeling of tightness, but not so much that it is uncomfortable. This tightness lasts for about a day.

That's all for now! Basically, I've summed up all the symptoms of acute exposure; but I hope to have made it seem more realistic, you know? Reading this off an MSDS sheet just doesn't have the same effect.

All in the name of science! :D
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 28-5-2003 at 14:54
a potent weapon


The Chloropicrin/Castor Oil that I was using in the day's experimenting had hardened onto some of my glassware (measuring cup and jam jars ;) ). So, knowing that Chloropicrin is very soluble in Ethanol, I used that to clean off my equipment.

That was well and good, but then I went to pour out the Ethanol in the washroom (closed area). What I suspect happened is that the Ethanol made the Chloropicrin much more volatile, so that as I poured it down the drain, the concentration of Chloropicrin in the air climbed very rapidly. Naturally, it did what it is designed to do to the body: coughing, eye pain, tearing, throat pain, upper respiratory irritation (surprisingly, this part did not hurt so much, just a tingly feeling in the nose), chest pain, and vomiting (did not actually vomit, but felt like I was about to). So, I rushed to another bathroom to be near a toilet in case I did vomit. There, I noticed a feeling in my chest as if I'd swallowed a huge air bubble, and my heart rate increased.

But now I am good, after breathing some fresh air :D.

Now, what is to be learned? NEVER dispose of chemicals in the bathroom! Or at least, don't do it without a gas mask on.

What else is to be learned? That this is a potent weapon, should that be what you are interested in... Chloropicrin dissolved in a volatile solvent, such as Ethanol. Ether or Methylene Chloride would be even better.

But, experimentation with the Chloropicrin is finished for today! ;)

[Edited on 10-21-03 by Samosa]
View user's profile View All Posts By User
Darkfire
National Hazard
****




Posts: 292
Registered: 3-1-2003
Location: California
Member Is Offline

Mood: Wondering

[*] posted on 29-5-2003 at 14:12


Chloropicrin isnt suposed to be all that reactive, even to the activated carbon in gask masks sure im not sure they would even help...

CTR




\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 29-5-2003 at 18:40


Activated Carbon filters are very effective against Chloropicrin. In fact, Chloropicrin is one of the chemical agents most easily protected from by activated carbon.

However, you will want a full face mask, because it still will irritate the eyes- making it near impossible to work.
View user's profile View All Posts By User
Darkfire
National Hazard
****




Posts: 292
Registered: 3-1-2003
Location: California
Member Is Offline

Mood: Wondering

[*] posted on 29-5-2003 at 19:16


Hmm... I read in more than one place it is un reactive, i found this odd at first because of the chlorine but i ended up taking the word of the web...



\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
View user's profile View All Posts By User
Krypton
Hazard to Self
**




Posts: 90
Registered: 21-11-2002
Location: Spain
Member Is Offline

Mood: explosive 21

[*] posted on 29-5-2003 at 20:31


The hot vapours of chloropicrin can harm your
skin in very short time when maked careless
with a open equipment, or the caustic
vapors of the overheated reaction mixture.
I think the storys of half dead persons
are enormous exaggerated, the concentration
in the air must be high to cause seriously
injurys.




In convention with my ancestor.
View user's profile View All Posts By User
PHILOU Zrealone
International Hazard
*****




Posts: 1126
Registered: 20-5-2002
Location: Brussel
Member Is Offline


wink.gif posted on 2-6-2003 at 05:05


No doubt a little CCl3-NO2 has been made!
But to ensure a better yield you need to neutralise a little the bleach with a little HCl to get a little Cl2 and thus freshly made HOCl.Basic media helps dissolving Cl2 and allow Na nitronate formation what is indispensable for chlorination.
In the industry, they make NM/NaOH/H2O mix and then bubble exces Cl2 in it!

Why CH3-OH is in your reaction?
CH3-OH + bleach --> CH2=O + ClCH2-O-CH3, HCO2H, ...all are lacrymators.

Last weekend when attempting a CTeAP synthesis (tetrameric instead of trimeric) I mixed 100ml H2O2 (200V/50%) with Aceton (100 ml) with 30 ml HCl (35%)... the batch was not cooled and products were at ambiant temperature...I added the catalyst (Sn IV chloride) and the batch heated until aceton was bubbling...then my brother and I were really irritated (nose, eyes)...I believe the catalyst had free a little Cl2 in HCl with aceton to yield boiling CH2Cl-CO-CH3 (strong lacrymator).

A later trial was made by dilluting twice the amount of H2O2 with water and all ingredients were freezing cold...I got moderate heating to ambiant temperature..a trouble appeared and cristallisation started; soon I got a solid wet cake (I think the yield is near 100%).

Funny to see the same reaction produces two different effects!And now on will I can make 5 liters lacrymator gas with a very long remanence smell in less than 20 sec!The 300 ml batch that runnaway and sprayed all over the place had stayed lacrymator for a complete day in open air.




PH Z (PHILOU Zrealone)

"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
View user's profile View All Posts By User
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 20-10-2003 at 22:45


Two or three days ago I got around to checking on my box of chemicals, which had been terribly neglected over the summer. Guess what I find? A jar of left-over Chloropicrin/NM/other stuff mixture left over from my tests in this thread. I've learned, though, not to try to store the stuff-- it seems to attack the lid of my mason jar, which of course was some metal... But the strange part was, on the outside of the lid, some weird crusty substance was forming which mildly irritated/burned the skin.

On the note of the Nitromethane route to Chloropicrin, I don't think it is the best "Jam Jar" route. The best source for Nitromethane OTC is from hobby shops, and is sold as race car, helicopter, and boat fuel. The problem is, you can expect ALL of them to contain Methanol, Castor Oil, and other Synthetic Oils in addition to the desired NM. These impurities cause real pains during the synthesis of Chloropicrin. As such, I am eyeing the Picric Acid route- the way Nick F went. It's a bit more involved, but judging from Nick's response, you get a high quality product (and for significantly less cost than the NM route- though, comparatively, the NM route is much easier).

Philou- have you tried your uncooled synth of CTeAP again? Reading over it again, it is suddenly very interesting to me... Going off topic a little bit, do you suppose one could synthesize Chloroacetone by combining AP with HCl? That is, would the AP (strong oxidizer) cause the release of straight Cl gas which, in turn, would react with the AP and hopefully form Chloracetone?
View user's profile View All Posts By User
Theoretic
International Hazard
*****




Posts: 672
Registered: 17-6-2003
Location: your mom's bedroom
Member Is Offline

Mood: red

[*] posted on 10-11-2003 at 07:45


I think the crusty stuff was a trichloronitronate of the metal of the lid (or a mixture of trichloronitronates if the lid is made from an aloy). The chloropicrin vapours that seeped out probably reacted with moisture and the metal.
The trichloronitronate ion is CCl3NO3H-. The nitronate ion is CH3NO3H-.
View user's profile View All Posts By User
Haggis
Hazard to Others
***




Posts: 238
Registered: 1-12-2002
Location: Mid-America.
Member Is Offline

Mood: Lacrymating

[*] posted on 10-11-2003 at 12:04


As of late, I have also played a bit with chloropicrin (PS). What I did was place .25 gram of TNP in the bottom of a beaker. Then 50 ml of 6% bleach was poured on. I remember somewhat of a fizz or effervesence as the bleach hit the TNP. I stirred it around some and there was still some TNP in the liquid, so I added 50 more mls. This was poured into a 250ml flask and stoppered. The next morning...the flask was opened. I smelled the stopper, and, yes, there was a horrible scent I've never smelt before, although it is vaguely reminiscent of a pesticide or poison I either smelled or imagined smelling as a child. Then, I sniffed the mouth of the flask, and I felt the pain/stinging/irritation in the back of my throat. Also, upon another 'hit' of the PS, I got a higher dosage, and was reeled back in my chair, eyes and throat stinging. My eyes had pain, and I instinctively started rubbing them, but I'm not sure if that helped or hindered the effects. The eyes stung for arund 5 seconds, while the stinging in the throat subsided after around 3. Also accompaning was an increase in heartrate, either from the shock of being teargassed, or the agent itself. Also keep in mind this was from .25 grams of TNP, and is diluted to 5% or more. Not having a single want to distill the stuff, I plan on purchasing some xylene, swirling in the flask, separating the xylene/PS solution, then evaporating off the xylene. Can anyone see any difficulty to this procedeure? I was thinking that as Samosa said the ethanol sped up the vaporization of the PS, the xylene could too, lowering storable yields. This is one concern of mine. I plan to also experiment later with 68% Calcium Hypochlorite from pool chlorinator, for less solution to hassle with. Ugh, even while typing this, I get 'sensory flashbacks' and imagine that I am smelling the agent, when I am quite far away from it. Fun stuff!



Great ideas often receive violent opposition from mediocre minds.
<b> <a href=\"http://pgp.mit.edu:11371/pks/lookup?op=get&search=0xEE41A2B1\">PGP Key</a> </b> 0C0A 7486 B97F 92EE AE50 A98C A4F3 087E 8CE9 A782
View user's profile View All Posts By User This user has MSN Messenger
DDTea
International Hazard
*****




Posts: 910
Registered: 25-2-2003
Location: Freedomland
Member Is Offline

Mood: Gauche

[*] posted on 10-11-2003 at 19:32


Haggis - you get those "sensory flashbacks" too?? Lately, I've been getting it a lot- I can smell the Chloropicrin in my nose, and on occasions I feel an irritation in my nose/throat (though not pain)... Interesting effect, I wasn't sure if it was just me.

Chloropicrin is very insoluble in water. I'm not sure about TNP, but I know Sodium Hypochlorite is soluble. Would it not be possible to separate it simply by pouring it into a large volume of water? Volatilizing Chloropicrin even further is the absolute last thing I'd want to do.

Do you have any idea how much Chloropicrin you made? Try adding the Hypochlorite to the TNP, but more slowly. Aim for complete addition in about 20 mins or so-- see how that affects yields. I know when I added the Hypochlorite to to the Nitromethane right away, yields sucked and I had a lot of Chloropicrin vapors (not easy to work with)... But on adding more slowly, though I still had the vapors, it was a bit easier to work with- and I actually had visible yields.

On these trichloronitrate salts... The only information I can find to something similar to these is on straight Nitronate salts- as produced by reacting a base with Nitromethane. Do you suppose that, by leaving the resultant NaOH in the Chloropicrin mixture, it reacted to form a Trichloronitronate salt?? Also, keep in mind that it was irritating to the skin-- this could prove to be an interesting group of bioactive chemicals, so long as they are just irritating and not actually corrosive. There are plenty of corrosives in this world, and one more would not be very interesting.



[Edited on 11-11-2003 by Samosa]
View user's profile View All Posts By User
Mongo Blongo
Unregistered




Posts: N/A
Registered: N/A
Member Is Offline


[*] posted on 11-11-2003 at 10:34


I made it ages ago and I remember getting those flashbacks. It wasn't painful but I could smell a hint of it every now and again. I would discribe the smell as painful chlorinated Liquorice :D
Also I remember yields being very bad using TNP and sodium hypochlorite.
Theoretic
International Hazard
*****




Posts: 672
Registered: 17-6-2003
Location: your mom's bedroom
Member Is Offline

Mood: red

thumbup.gif posted on 12-11-2003 at 07:33


I do think that by reacting alkali with chloropicrin, you get trichloronitronates - especially as chloropicrin is described as "extremely acidic". I think the raction is just kinetically hindered, so heating could help ( if you are looking forward to this reaction as a way of storing chloropicrin).
:);):cool:
View user's profile View All Posts By User
vulture
Forum Gatekeeper
********




Posts: 3332
Registered: 25-5-2002
Location: France
Member Is Offline


[*] posted on 12-11-2003 at 15:51


For the people that are using the TNP route:

Don't forget to add HCl. HCl + NaOCl will produce free chlorine and greatly speed up the reaction.




One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
View user's profile View All Posts By User
 Pages:  1    3  4

  Go To Top