Messy Jam-Jar Experiments with Chloropicrin

[MrSamosa]

Before I start, I would like to stress the very crude tools and chemicals that I used in my experimentation. For a scale, all I had was a cheap diet scale with 20 gram increments. My reaction vessels were mason jars, and I used a pyrex measuring cup to measure liquids. However, the crudeness of my methods reflected on the extremely unsafe conditions...Here, I shall describe the most interesting notes from a week of experimenting with Chloropicrin.

For me, OTC syntheses are not good enough. They must be jam-jarrable! :p

Now, to begin. My test batch of Chloropicrin was made using 30% Nitromethane and 6.00% Sodium Hypochlorite Bleach. The Nitromethane solution also contained Methanol and a fair amount of Castor Oil.

First, I poured an unmeasured amount of the Hypochlorite Bleach into my measuring cup, but if I recall correctly, it was about 50 mL. Then, I slowly (this is done slowly! I learned from past mistakes of doing it too quickly- it bungles the reaction and is very hard on the eyes ;) ) poured in an excess of the Nitromethane (I think somewhere in the area of 200 mL). The entire addition took about 20 minutes. Also, whenever I added the Nitromethane to the Bleach, there would be a smell somewhat like Chlorine, but sweeter, and following that was a burning in the eyes (like cooking with onions) and irritation of the throat. After the addition, I let the mixture sit for an additional hour or so.

When I came back, there were two "layers" in the mixture. The top one was mostly reddish-brown, and I suspect that this was mostly Methanol. The bottom layer was dark green, and I believe this contained the Chloropicrin and the Castor Oil...it may have been mostly Chloropicrin though, as my later flame tests led me to believe. Anyhow, I extracted this layer with an eye dropper and disposed of the rest of the liquid.

Upon my first flame test (throwing a match into the liquid ;) ), some of the liquid did burn (most likely the Castor Oil). This is what I was expecting to happen, and what I wanted... I know that Chloropicrin is non-flammable, and therefore to have a flammable liquid mixed in with it, I was hoping to raise the temperature of the Chloropicrin to its decomposition temperature. To test for Chloropicrin, I had starch paper covered in Iodine from a Tincture. I did notice a color change (From black to blue), which I was expecting since one of the decomposition products of Chloropicrin is Chlorine. There was also the smell of Chlorine in the air. Upon throwing a new match in, the liquid failed to ignite again.

Now, on to the interesting stuff- weaponization! :)

My first test was to use an eyedropper to put the Chloropicrin into a water gun (small one, but has a long range- approx. 20 feet). The idea was that this could be used to spray a chemical several feet above a target area and from a good distance away. As the liquid would fall to the ground, it would aerosolize, and also reach the targets' eye and nose area first- thus allowing the maximum effectiveness for the minimum amount used.

On spraying, I did not quite get the range I wanted...I suspect that some of the Castor Oil was gunking up the gun though. Nevertheless, it flew about 5 feet, at which point it completely aerosolized. On hitting solid targets (Trees/Fence), some of it stayed on the target, but most of it splashed off an aerosolized :D .

Then came time for clean up, and here is where I made my most interesting find. I was using Ethanol to clean off my glassware and water gun, since the Chloropicrin readily dissolves in it. I don't believe I had that much dissolved in the Ethanol, but when I went to pour it down the drain in the bathroom (bad mistake- closed area without my gas mask on), I was greeted almost instantly with severe eye pain, coughing, choking, chest pain (as if I'd swallowed a massive air bubble), nose irritation, and nausea. I had to immediately leave the bathroom and run to a new one, in case i did vomit (i did not, fortunately... it is the worst feeling in the world!). There, among the fresher air, I recovered from this short but terribly painful accident. I am feeling quite good now though - this was just yesterday, by the way.

But this brings me back to the idea of weaponization: Chloropicrin dissolved in a volatile Solvent, so that it evaporates and reaches dangerous concentrations rapidly.

Yes, my methods were somewhat Kewl, but hey- they worked, and I am still reaching many goals from my testing with Chloropicrin. That's all for now; sorry for the messy nature of this post, but it was rather rushed, and I was trying to cover a lot of information ;) .

[Mr Cool]

What is chloropicrin like as a solvent? A while back there was a little discussion of using foamed NM to make charges, the idea being to pour NM into a lighter, seal it all up, and pressurise it with gas. But NM gelled the body of the lighter, making it unable to hold pressure.
Do you think chloropicrin could be weaponised in a similar way? Pour some into a dismantled lighter, re-assemble it (without all the uneccesary stuff in the valve, like that little white stick which soaks up gas, which would slow down the flow), then squirt in butane through the refill valve. It'd be short-range without some more work, but would be very concealable :).

[nbk2000]

Removing the castor oil should be your first priority. I don't remember if NM is water-soluble, but if it isn't, washing your R/C fuel with a water/detergent solution would remove both the methanol and castor oil.

Otherwise, the castor oil is going to react with your bleach as well as the NM, possibly converting into a soap (causing clogging) or become much more viscous.

Are you using household, or pool grade, bleach? Pool grade is 10%, instead of houshold 6%, so it should be more efficient.

Stirring is always good, especially since the PS (chloropicrin) is water insoluble, possibly holding some NM away from reacting with the bleach.

PS is inert (when pure) in contact with most metals, but plastic reactions are probably something you'll have to find out yourself, since its unlikely to be readily available info, giving how PS is a "WMD". :rolleyes:

Denatured alcohol or, even better, ether, would be good for volatilizing PS into an aerosol. Dissolved, and sprayed out under pressure, the ether vaporizes almost instantly, leaving microscopic droplets of PS to drift in the wind. :)

Oh, and PS causes vomiting only if swallowed (from what I've read), like if you swallow your drool after getting gassed by it.

Though it'd be very useful for disabling someone for a while, since ONE drop, ingested, causes the intestinal lining to slough off, meaning horrible (and disabling) diarhea for weeks. :D It's even supposed to be pleasant tasting.

PS is also a good solvent for many other CW agents.

[MrSamosa]

If I remember correctly, Nitromethane is somewhat soluble in water. However, because of the efficiency and ease of this reaction as well as the high yields, in addition to my lack of need for mass-production, as well as how far a small amount of Chloropicrin goes once weaponized, I am willing to lose a bit of my NM :) .

As far as the Hypochlorite goes, I plan to do two new experiments: one using 65% "Pool Shock" Calcium Hypochlorite dissolved in water; the other I will make the Sodium Hypochlorite by reacting said Pool Shock with Sodium Hydroxide. I hope that by this latter method, I may be able to produce in bulk concentrated Bleach. Why all the effort, you ask, when I could just buy the concentrated Pool Bleach? Strangely enough, where I live, I cannot find the stuff. I have tried the local hardware stores and the Pool-Spa store, but none carry it! Also, the Pool-Spa store is terribly overpriced.

For solvents in which to dissolve Chloropicrin, one would need a solvent that is not terribly aggressive to Plastics but is also volatile. That rules out Acetone and Methyl Ethyl Ketone. The problem with Diethyl Ether is that Chloropicrin is not very soluble in it :( . For now, I will do more tests with Ethanol, as that seems to work very well. Another solvent I am considering is Dichloromethyl Ether, since it in itself is a warfare agent and is also a good solvent. Also, it can be made by the simple reaction between Paraformaldehyde and HCl.

I did not get to do too much weaponization testing the other day because that little mishap with the Chloropicrin really put me down for the day. In the future, I will always be wearing my gas mask. The good thing about Chloropicrin is that Activated Carbon filters are VERY efficient in keeping it out :) .

EDIT: Oh yes, and a non-flammable propellant would definately be most desirable. Should the propellant catch fire, the Chloropicrin decomposes...though this is not all that bad, it would minimize its effectiveness if you only have a little bit of the PS. One of the decomposition products is Phosgene- which is more poisonous than the PS itself.

[nbk2000]

Well, now that you've got PS, you may wish to try moving up to CX (phosgene oxime), via tin reduction.

Tin is readily available as "lead-free" solder. Look for the ones without flux or rosin. Chill the solder in a deep freezer, then whack it with a hammer, to powder it.

The powder is added to PS dissolved in a solvent like THF (pipe cleaner) while HCl is added to affect reduction.

There's a patent listed somewhere here that gives more details.

No need to go overboard with it, trying to make ounces, since it's extremely nasty shit to handle, so a small test-tube would be more than adequate for trying out the process.

Have you tried washing your PS with detergent water yet? The detergent should have no effect on the PS, but should remove the castor oil impurity.

BTW, Mr. Samosa, do you have PGP?

[MrSamosa]

I am considering moving up to the CX, but not at the moment. First I hope to establish a simple, high-yield, and relatively cheap synthesis for the main ingredient- Chloropicrin. Also, I want to explore all possible uses I can with the PS first. However, that does not mean the CX is not on the near horizon ;) . When I first started with the Chloropicrin, the ultimate goal was indeed CX; but I am taking my time.

I am categorizing my work with PS under my "Pesticide Research" - basically, exploring reactions on pesticides that can form more potent compounds. As we know, Chloropicrin has a history as a pesticide, whether as an alertant/torture gas (as in the case of Zyklon), or as a fumigant on its own. And, as such, to go one step further with potency, I will be "exploring CX" and its uses of interest to us.

I have the patent on hand for the production of CX though, it is rather simple :) . The only problem for me would be forming a reusable and leak-free HCl generator, as it requires dry HCl gas. However, all the materials I have readily on hand to make it, and they are all very cheap!

The solder is something I was looking into. I was thinking of a single-replacement reaction with some Tin Salt and a more reactive metal, to liberate free Tin powder. Alternatively, I could use Zinc powder as a reducing agent, as that is relatively easy to come by. However, doesn't Tin require very low temperatures to become Brittle? If that is the case, I don't believe a kitchen freezer will do the trick...maybe pouring liquid referigent onto it- as obtained in PC dust-blowers.

I will find a way though! Still plenty more stuff to do! Hmm, Next Stop: Clean Jam Jar Chloropicrin and Jam Jar Phosgene Oxime :D. As for the PGP, I do not have it...nor am I quite sure what it is :) .

[rooster]

samosa: would you mind posting that patent or patent # for CX?

[zeocrash]

cleaning the PS may not be as much of a problem as you thought
while searching the internet, i found a UK supplier that sells pure nitromethane for "custom mix" model fuel.
I imagine that there must be some suppliers in the US too. try telling your current supplier of NM/meth/castor oil that you want to custom mix your fuels and see where he points you.

another factor to consider is what you are going to do with the phosgene oxime.
chloropicrin is relitively easy to get rid of as it is only a lachrimator / sternutator / mild urticant. whereas phosgene oxime is much more nasty and i doubt you want to be pouring it down the plug hole in your bathroom :p

if you have access to the ftp i would suggest having a look at fm 3-9.pdf
in the "explosives and weapons\field manuals" it covers most chemical weapons, including CX and lists decontamination methods, properties ld's and more

[zeocrash]

ok today i made myself a small amount of chloropicrin.
i used bleach and some old model fuel i had lying around (methex), i mixed 5 ml of bleach with 5 ml of fuel in a 10 ml beaker. i got a yellowey green top layer and a milky bottom layer. i think the bottom layer is chloropicrin, but because of the small quantities and my chronic hay fever i i cant smell a fucking thing. i'll post pictures, tomorow, anyway i was wondering if there was any way to test it to see if it was chloropicrin.

[nbk2000]

Chloropicrin can be detected by combustion methods. If an atmosphere containing the gas is passed through a quartz tube heated to 450°C., the chloropicrin will decompose with the formation of chlorine. This can be detected by bubbling through a potassium iodide solution containing starch solution as indicator. The liberated iodine will color the starch blue.

(War Gases, their identification and decontamination, pg. 124)

But you'd be better served by observing it's physical properties. It's a slightly oily liquid, with an intensely irritating (though sweet, like anise) odor. The boiling point is 112°C.Specific gravity is 1.65. Practically insoluble in water, freely soluble in alcohol and ether.

So, wash your product with cool water several times to remove excess bleach or NM. Dissolve in warm alchohol (or ether), and pour into a large quantity (10x) of cold water to seperate out the PS. collect the oily liquid at the bottom and heat in a small container of cooking oil till its boiling. Observe the boiling point (use thermometer, duh!) and how sharp the b.p. is. Does it start boiling at 110°C, and boil dry at 115°C? That's a seriously impure product. But, if it's starts at 112°C and stays there till it's all gone, then it's pure. :)

[CyclonitePyro]

Hey Zeocrash try eliminating dairy from your diet for a week and see if your allergies improve.
Sorry this has no relevency to the topic.

[zeocrash]

thanks man, i'll try that, at the moment i'm just drugged up with pills, eye drops and nose sprays

[MrSamosa]

The way I confirmed the detection of my Chloropicrin was by combustion means... Chloropicrin by itself is not flammable, so instead I relied on the impurities to promote combustion (namely, the Nitromethane).

My logic was that as it burned, it would heat the Chloropicrin to its decomposition temperature because the two liquids were so intimately mixed... So, I simply threw a lit match into a beaker containing the two.. Remember, I'm doing Jam-Jar experiments :D .

I detected the presence of Chlorine using Potassium Iodide on Starch Paper. The KI turned from a black to a light-blue. I imagine it would have become even lighter if I didn't run out of flammable liquid first :( .

You probably will not even need your nose to detect Chloropicrin. From my brief and unpleasant experiences, it causes a greater and more immediate effect on the eyes- comparable to cooking with onions. However, even if you can't smell it, in higher concentrations it causes an irritating feeling in the back of the throat.

Also, if you are dissolving it in a volatile solvent, do be careful. That was my mistake that really screwed me up for a day or two. Volatile solvents will increase Chloropicrin's volatility, and in high concentrations (which can be reached rather rapidly), this will be a very unpleasant experience.

If you're still uncertain as to which layer contains the Chloropicrin, throw the mix into a large excess of water... The chloropicrin will sink to the bottom, while the other crap will either dissolve or float. This is not fool-proof, however, because when I did this I noticed oily droplets on top- and these caused me profuse tearing.

And to NBK- sorry about not getting the PGP sooner, and in fact I still do not have it. The problem is, I do not currently have a computer where I am able to install anything. However, I expect to have one (a very crappy one at that) up and running soon. :(

[vulture]

I think I've said this somewhere else before, but chloropicrin can also be made by reacting TNP with KClO3 + HCl. I know it would be wasting perfectly good TNP, but it might be easier/cheaper to get for some people than NM.

I suspect NaOCl + HCl or any other in situ chlorine generation will work too.

[kingspaz]

Vulture, that sounds like a good method since TNP is relatively easy to make.

[grammarless]

I have a question. While looking at grenades I stumbled across this site (http://www.inert-ord.net/russ02i/gas/index.html) and I was wondering how do they distribute 500g of Chloropicrin?

[MrSamosa]

For the purpose of Bunker clearing, I imagine that the Chloropicrin could be dispersed by conventional explosive. In a confined area, the gas does not have to disseminate 100% to have drastic consequences.

Also, I have come to the conclusion that the TNP route to Chloropicrin is, dollar for dollar, more effective than the Nitromethane route. While the Nitromethane route is much easier and less invovled (just dripping NM into warmed Hypochlorite solution), it requires very pure reactants. The Nitromethane available OTC tends not to be very concentrated- the best I can find is 35%- and is mixed in with methanol, castor oil, and other synthetic oils which are a pain to remove. As such, it is not suitable for jam jar experimenting.

On the other hand, TNP can readily be prepared by Jam-Jar routes, and several methods are available for doing so. The reaction to produce Chloropicrin from TNP is very easy-- add TNP to Sodium Hypochlorite solution. NaOCl is a suitable substitution for KClO3, which is more difficult to obtain (and possibly more suspicious). Furthermore, the product is of a high quality, and the side products are not difficult to separate.

[TheBear]

Regarding dispersal of chloropicrin using explosives:

http://www.ashtachemicals.com/products/msds_chloro.htm
"Chloropicrin possesses some shock sensitivity. A detonator cap ignited in chloropicrin released more energy than from the detonator cap alone."

http://www.emedicine.com/emerg/topic907.htm
"Even though chloropicrin is not flammable, it is a significant explosion hazard if involved in a fire. Bulk containers of this liquid are shock sensitive and can detonate."

http://www.intox.org/databank/documents/chemical/chlorpic/cie528.htm
"Normally stable. Although there are no case reports of dangerous reactions, tests have indicated that there is a "critical volume", above which sufficient shock may cause detonation. Accordingly, chloropicrin is now shipped in special containers not exceeding 700 kg (1500 lb) and special 180 kg (400 lb) drums.(11,18)"

Sounds to me like it can detonate but it's rather insensitive, somewhere in the neighbourhood of AN.

[MrSamosa]

From what I've gathered, Chloropicrin is not a significant explosion hazard in low quantities. However, in higher quantities-- above said "critical volume" -- it becomes an explosion hazard.

[Dave Angel]

I recently found a source of OTC KClO3 in the form of oxygenating tablets for an aquarium. These are 98% pure, however quite expensive for the amount you get, (a small vial for ~89p / $1.50). Alternatively, if any chlorine source will do, NaClO3 from weedkiller also liberates generous amounts when HCl is added.

[MrSamosa]

Using KClO3 may work for synthesizing Chloropicrin from Picric Acid, but I am not sure about with Nitromethane... The KClO3 could be used to generate some HCl, which could react with another Oxidizer to form straight Chlorine. It is the liberated Chlorine, if I recall correctly, that reacts with the Picric Acid. However, the presence of HCl tends to increase yields, as Vulture stated earlier.

[MrSamosa]

This is much over-due... I have finally revised my synthesis of Jam-Jar Chloropicrin, and I now have a procedure that uses OTC Nitromethane Fuel solution. First, a word of warning... I don't mean to sound k3W|_, but i mean to bring us back to reality. This is a poison, and it is extremely painful to inhale... guys, if you do this on a boring afternoon, please please please take appropriate safety measures. Wear a gas mask, have good ventillation, do not try to detect it via senses-- that means no wafting and definately no sniffing. Trust me on this, it will be there, and it will be pure enough to hurt you.

For a theoretical yield of 20g Chloropicrin...

My reactants were 30% Nitromethane (about 60% Methanol, and the remainder Castor Oil), 6.00% NaOCl ("Clorox" brand regular bleach), and 30% HCl (Hardware Store toilet cleaner).

To 415 mL NaOCl solution is added 25g of 30% Nitromethane, with agitation and without cooling. As the blue NM solution was added to the yellowish/clear bleach, the color first changed to a creamy white, and then to a red-- similar to the KNO3/Sulfuric Acid mixture in the synthesis of Picric Acid. At this time, there can be seen a separation of layers-- the Castor Oil is saponified by the formed NaOH, and floats to the top and dwells. It appears as bluish-green globs, floating at the top, along the sides of the vessel.

To minimize exposure, cover the reaction vessel with some metal plate or something, with ice on top (a crude "condensor," as some of the PS is vaporized and can be hazardous) and leave the area. Let the reaction go for 10-15 minutes. After this time, CAREFULLY remove the plate (so as not to get a nasty cloud in your face), and add 30 mL of 30% HCl, with stirring. Because my acid was not very pure, and probably had some coloring in it, it was a milky color... but, after the remaining NaOH was neutralized ( this is important, since if it isn't, it could destroy the Chloropicrin in storage ), it turned a transparent reddish color. At the bottom of this mixture was the Chloropicrin, which at first appeared as oily "spikes" (though clearly not crystalline-- just a "spiky" liquid pattern along the bottom).

At this point, I had originally intended to dump the whole thing into a much larger volume of water-- as everything, save for the Castor Oil and Chloropicrin-- would be water soluble. However, not having a large enough vessel, I just decanted off the water and those things dissolved in it, leaving the blob of Chloropicrin at the bottom. This is the point where I got some bad whiffs of the stuff ( I am very near-sighted, and it is difficult to work with my gas mask on, as i can't fit my glasses beneath it), since there was less liquid between myself and the Chloropicrin. So decant quickly, but carefully, leaving the blob of PS at the bottom.

There you have it.. Jam-Jarrable Chloropicrin. Naturally, if you have the apparatus, you could get a much purer product by distillation. Not having that, though, this was good enough for me...and was quite annoying to clean-up. After getting an extremely bad whiff of the stuff ( the kind that sends one running from the lab, to the washroom, to cough and drool and cry on the floor), I was fed up with it... I did not weigh it, but immediately destroyed it. Judging from the amount of NM I used, though, the yields looked very good.

[Dave Angel]

Good work MrSamosa, whilst you say it was crude, it sounds like your product was very effective!

I will carry out a similar synthesis with straight NM sometime and compare results. I really like the simplicity of the whole set up you used, showing that anyone can do this with the right know-how.

I have tried bubbling the chlorine gas from the KClO3 / HCl reaction through NM in an attempt to make PS but to no avail. Perhaps it needs heating or intense UV light, or perhaps it just won't work at all. Anyhow, this route was very wasteful of chemicals so I think MrSamosa's route may be the way to go - simple and effective.

[mongo blongo]

I have tried this method before. I have found that the product is far from pure using RC fuel. There is not enough NaOH formed to get rid of all that castor oil for sure! After using pure Nitromethane I obtained a very different product which was more liquid like and colorless with a much more potent odor rather than having a tint of yellow from using the RC fuel.
Another step which I feel is needed after obtaining the product is dissolving it in an organic solvent like ethanol and filtering it into a beaker of distilled water. You will be surprised how much crap in there. There is also some shit that precipitates out in the water but stays in the water phase.It would probably also be more storage stable after this step but you should destroy it ASAP because it hurts bad.

[MrSamosa]

One thing that I did not understand... Why didn't the Chloropicrin dissolve into the methanol that was present? If so, couldn't you skip the last step of dissolving in Ethanol, and just pour it into a larger vessel of distilled water?? I didn't bother to try dissolving the PS into the Methanol, because I feel more "secure" when I can see where it is. Also, when I poured it from the reaction vessel into a Mason Jar, there was still some water present. The water took on a yellowish color, similar to bleach, but much more watery. Chloropicrin is partially soluble in H2O, so this could explain the color.

I'm still bugged about the Castor Oil problem, as I don't feel it's been solved sufficiently. I don't want to just abandon OTC Nitromethane, because the goal here is to make PS as accessable as possible-- that means, no chemical orders. After the reaction between NaOCl/NM, do you think that excess NaOH should be added, to saponify any remaining Oil? To prevent it from breaking down the PS, which is in the presence of Alcohol (thus, a ready made decontamination solution), the HCl could be added to neutralize it. As far as I've read, PS has no reaction with HCl-- save for in the presence of a reducing agent, at which point it can become Methylamine.

Looks like I'll have to cook up another batch to do some more testing. :(

[mongo blongo]

I'm sure that some of the PS is lost due to it dissolving in methanol but only a small amount because methanol looses it's solvent properties with the large amount of water present in the Sodium Hypochlorite solution. Another problem is you need to add more bleach than the theoretical amount because Sodium Hypochlorite reacts with the methanol to form Methyl Hypochlorite. I forgot to say that when PS is dissolved in volatile solvent then the PS is going to diffuse much more quickly into the air reaching much more potent levels so be careful. As for removing the castor oil after production, that would be desirable but I think NaOH is just going to break down the PS and the oil together. If you can solve that last problem then the OTC syntheses is sorted. :)

[MrSamosa]

As we speak, my PS is dissolved in Alcoholic Sodium Hydroxide, in a sealed Mason Jar. It's been in the solution for about 14 hours now, and it's still not completely broken down-- I opened the jar to check on it, and I still could smell irritating amounts of PS. Therefore, the conclusion is that the reaction with Alcohol Soda is very slow...though clearly it's happening. As such, I'm not concerned about brief contact with NaOH. Some of the product may be lost, but it will most likely be a negligible amount, and worth doing to get rid of the Castor Oil which would otherwise be a pesky side product. Another thing which may be useful... on cooling, the saponified Castor Oil becomes very solid, and can be spooned out.

I have already had one uncomfortable experience with PS in Ethanol several months ago, during the Summer and in a small space... I am making sure not to repeat these mistakes. Fortunately, the area I'm working in is about 0*C, so volatility isn't as big of a problem-- but it's bloody cold!

[MrSamosa]

Well, the decontamination mixture I mentioned in the above post did not work very well. If Alcoholic NaOH breaks down Chloropicrin, it does so very slowly; or I wasn't using the right alcohol (I might have had more success with Methanol...I used Ethanol instead). So, needless to say, the clean-up was rather messy and I'm sure I've killed plenty of fish. In the future, I will try KI or simple burning.

Anyhow, I recently obtained about 500 mL >90% Nitromethane and several useful pieces of glassware from a generous Forumite. So this isn't exactly "Jam Jar" anymore, but it isn't a big step from it. The reaction could still be done in Jam Jars, if need be, but it is much easier with the help of a Separatory Funnel.

Nevertheless, here's how my latest adventure went. 7 mL of Nitromethane were added to 454.5 mL of 6.00% NaOCl in a 600 mL Beaker. The addition was very quick, I didn't split it up. After a few quick stirs, I covered the flask with saran wrap (the funny thing is, this actually worked in keeping the PS vapors inside the beaker... but I didn't use the duct tape :p ). After 20 minutes, when I decided the reaction was "complete enough," the bottom of the beaker was covered with a heavy reddish liquid. I have no idea what this was, or why it was red--perhaps someone can explain it? I decanted off as much of the "useless" layer as possible, leaving only the heavy red liquid at the bottom. This was then poured into a separatory funnel, where on sitting, yet another layer showed itself. It sank to the bottom, and was clear and watery. I poured this into a graduated cylindar, and measured about 10 mL of it. This was the Chloropicrin. I poured it into an empty Iodine tincture, where it still sits-- safely sealed away. I have named it "Chokey." :cool:

How does Chloropicrin look, when pure? It looks almost like the original Nitromethane. However, it looks more like water. It isn't as viscous and it is colorless. This is my "control" sample--the sample I will compare future Chloropicrin experiments to that use Hobby-Store Nitromethane as a precursor.

Needless to say, this reaction eats Hypochlorite like a madman. However, I've calculated that with 10 Liters of 6.00% Bleach, about 220 mL of Chloropicrin can be made. That's not bad at all, considering how cheap Bleach is. I will have to check the patent again, but out of memory, they said that up to 12% NaOCl could be used... This would cut volumes dramatically, and make things much easier (cheaper?).

[SweNMFan]

Tried it today.. man this stuff really stings... After adding 10g 99% NM to the 400ml 5% bleach my solution also turned orange/red.. Got 9ml out of it.. there also formed some crystals in the solution.

[MrSamosa]

Of late, a little bird has told me of another method of generating Chloropicrin with Nitromethane. Instead of Sodium Hypochlorite, Cyanuric Chloride (Pool bleach) was suggested. This looks like the way to go:

1. Nitromethane + Cyanuric Chloride --> Chloropicrin + Cyanuric Acid

2. Cyanuric Acid + Sodium Carbonate (aq) --> Sodium Cyanurate (aq) + CO2 + H2O

3. Put the mess in some kind of separatory vessel and collect the heavy layer of PS. The final product should be very pure, since PS is hydrophobic and the other stuff is water soluble.

The advantage to this method is that it is much nicer for large-scale production of Chloropicrin; it gets rid of the need for huge volumes of Hypochlorite solution. After all, who feels like working with 400+gallons of Bleach? And how the heck will you dispose of that much waste? Impractical, I say, but easy for small-scale experimenting.

[xyz]

MrSamosa, another option for large(r) scale production is "liquid pool chlorine". All it is is a 12.5% solution of sodium hypochlorite, and it can be found in 5 litre containers in the pool chemical aisles of most Australian hardware stores. I looked into using it once for production of chlorates, and worked out that it was much cheaper than bleach (per gram of hypochlorite). With a little searching you should be able to find some somewhere.

I just wish I had a source for nitromethane... :(

[cyclonite4]

I just wish I had a source for nitromethane... :(

I remember you saying in the "Great OTC survey" that you knew of a chem supply company in WA. If your in WA (like myself), there is a hobby store in perth (can't remember exact location, but not too far from the Hay st. Mall, which sells "Nitromethane Racing Fuel" for thoe model cars. I doubt it's pure, but with the right equipment, it can be purified. Last time I was at the store was about 2 years ago when I was buying rocketry supplies, but the guy refused to sell me the NM (but still sold me the rocket supplies). It cost about $50 for a 5L bottle, the expense probably indicating it's relative purity.

Thanks for bringing up the part about "Liquid Pool Chlorine", I was making chloroform not too long ago, but I had to do it with Ca(OCl)2 because all the store bleaches didn't work (probably some additives in them). Unfortunately the Ca(OCl)2 leaves a huge chalky mess (probably Ca(OH)2 which clings to the chloroform layer.

I'm gonna run down to bunnings sometime and pick up a few Litres of "Liquid Pool Chlorine", so many uses :D

[MrSamosa]

The issue with Pool Chlorine, as with regular bleach, is still volume. For 220 mL of Chloropicrin, 5 L of Pool Chlorine would have to be used (at 12.5 concentration). Cyanuric Chloride (also availabe in the Pool Stores) on the other hand, takes the form of solid crystals. Furthermore, the molar ratio of Cyanuric Chloride/Nitromethane is 1 to 1. As you can see, the volumes required for the reaction are signifiantly less. Another major advantage is, aside from the PS, the other products will all be water soluble (that is if the neutralization step is carried out). This would make the layers extremely easy to separate since Chloropicrin is markedly denser than Water--meaning all one would have to use is a separatory funnel.

[xyz]

Cyclonite4, yes, I know of a chem supplier in Perth, they have a lot of goodies at fairly cheap prices but unfortunately no NM :( If you want the details then email me.

Was your choloroform synthesis the one in NBK's pdf? If not then I'd be interested to have a look at it.

[cyclonite4]

The one I went by was similar to the NBK pdf one (they both go about the haloform reaction).
I tried it with Ca(OCl)2 because I had lots of it, and the bleach from the supermarket didnt work with the reaction (all those stupid surfactants and other additives).

I'll send an email to the address in your User Profile.

EDIT: The admin(mega) has disabled sending to your email address, so I sent it to your MSN address.

[NightStalker]

350mL of generic bleach was placed in a 1liter jar.

7.5mL of 99%+ NM was added over the course of 5 minutes, in 1mL increments, with swirling and shaking of capped jar between additions.

At first, the reaction liquid turned cloudy white, like highly aerated water from a tap. As each additional NM increment was add, the reaction turned yellowish, finally ending as a deep yellow-orange, like piss after not drinking any water all day, with an oily film on top.

Reaction started out at ambient (~50F), but ended up warm to the touch at the end.

After letting it sit a few minutes to settle out, the top orange waste layer was drained from the clear PS layer at the bottom.

After washing twice with ~500mL of cold water, with vigourous shaking and settling each time, final yield was 6mL of PS, though a little might have spilled during the collection.

No sniffing or wafting was done, and it was done outside with a strong breeze to my back/gasmask worn/one-piece coverall/jar capped as much as possible.

Later, while removing the last layer of wash water (indoors), I started to get the 'onion' burn effect, but cleared myself out of there ASAP, so had only minimal irritation. Since I was wearing a half-face respirator, no respiratory irritation was possible, though, after removal, a definite odor was present, but too faint to characterize.

I'll provide a link to a rapidshare with pictures and video once I've repeated the experiment, and a variation.

[NightStalker]

http://rapidshare.com/files/18470885/PS_underwater.flv.html

This is from my previous experiment. Weather was too foul outside to try it again today.

I'm going to video the entire next experiment using Bleach+NM.

Then I'm going to try the TCCA+NM process mentioned on SM, just to see if it actually works.

[nbk2000]

I did the math on this reaction, based on the assumption of using sodium hypochlorite of a strength of 5% to 10% (household or pool), pure NM, and an excess of NM of between 2% to 10%, according to the patent.

(and, yes, I accounted for the varying weights and densities of the starting materials)

Given these assumptions, you'll need 60mL of bleach for every 1mL of NM.

The 60-to-1 volume ratio applies only to pure NM and bleach between 5% and 10% in concentration, allowing for a slight excess of NM to prevent decomposition of the resulting PS from the NaOH byproduct, as per the patent.

I went with volume, instead of weight, since both reactants are liquids and everyone can measure volumes, but not everyone has a scale.

[NightStalker]

I videoed the production this time.

I used NBK's ratios, doubling the amounts of reactants from my previous experiment, and I managed to do everything this time without gassing myself. :D

600mL of generic bleach and 10mL of NM.

I added the NM to the bleach in several portions over 2 minutes, with much shaking, and let it sit for 10 minutes before pouring off the waste water from the PS and pouring the PS into clean water to remove any NaOH.

The solution only turned milky white this time, not yellow-orange like originally.

I'm awaiting a friend who's going to loan me an analytical scale, so I can then get weight and precise volume, thus density, ensuring that it actually is pure PS, and not a partially reacted NM/PS mixture.

Manufacture (12MB Flashvideo):
http://rapidshare.com/files/20762492/PS_M.rar.html

Seperation (8MB Flashvideo):
http://rapidshare.com/files/20764878/PS_S.rar.html

Password:
roguesci.org