GB1401120 - Chlorine by TCCA and Salt, utility for Cyanide Production, and more

[nbk2000]

I downloaded this patent from an thread at SM.org and, having the materials on hand, gave it a try.

I can attest to it being factually correct, my kitchen still reeking of chlorine. :)

According to the patent, a mole of TCCA (Pool shock) and 3 moles of Sodium Chloride (table salt) are mixed together and a small amount of water added, the whole mixture being subjected to either vacuum or heating to release the chlorine.

The mixture, upon exhaustion of the chlorine, is composed of water and sodium cyanurate, which is what I was primarily interested in obtaining.

Sodium Cyanurate, Na3(NCO)3, seems like an excellent candidate for carbon reduction to Sodium Cyanide:

Na3(NCO)3 + 3C = 3NaCN + 3CO

I measured out the approximate ratio, at 1/100th mole quantites, thus 2.3gm of TCCA and 1.7gm of NaCl, and just enough water to moisten, in a covered glass jar placed in a hot water bath.

After a couple of minutes, the mixture turned a pale Grape Kool-Aid purple (because of the CuSO4 in the TCCA) and, upon sniffing a waft of the steamy vapor emitting from the jar, the smell of chlorine was overpowering and left me gasping and my eyes watering.

There was still particles of undissolved TCCA circulating, so the reaction wasn't over, but I dumped the mix down the universal disposal receptacle (the shitter ;)) ASAP, the experiment having been proven successful.

Since the reaction can also be run in a dry state, that would be the most desirable one to use, as then the gas would be dry and not requiring drying prior to use.

Cl3(NCO)3 + 3NaCl = 3Cl2 + Na3(NCO)3

The weight of chlorine being produced being almost equal to the weight of the TCCA in the reaction.

Though I wonder what the effect of 1% of copper sulfate has on the reaction. Probably not much.

Having a ready source of anhydrous chlorine gas for use in reactions, and getting a useable by-product, all from very cheap OTC components, seems desirable to me.

Oh, and by substituting Sodium Bromide (spa chemical) for the NaCl, you can get elemental Bromine instead of Chlorine, bromine being very useful for making powerful lachrymators such as bromacetone and brombenzyl cyanide which is even more powerful than CN, on par with CS, and can be made entirely from OTC chemicals. :)

Industrially, Brombenzyl cyanide is prepared in three steps, as follows:

(1) chlorination of toluene to form benzyl chloride (TCCA + Salt+Paint Stripper)

(2) the conversion of benzyl chloride to benzyl cyanide by the action of sodium cyanide in alcoholic solution (Cyanide made from by-product of reaction 1 + Everclear alcohol)

(3) the bromination of the benzyl cyanide with bromine vapor in the presence of sunlight. (More TCCA + Sodium Bromide spa clarifier)

According to Sartori (page 197 War Gases), it's advisable that you skip the use of benzyl chloride and use benzyl bromide instead, converting that to benzyl cyanide, then use more bromine to form the desired brombenzyl cyanide.

[nbk2000]

I downloaded this patent from an thread at SM.org and, having the materials on hand, gave it a try.

I can attest to it being factually correct, my kitchen still reeking of chlorine. :)

According to the patent, a mole of TCCA (Pool shock) and 3 moles of Sodium Chloride (table salt) are mixed together and a small amount of water added, the whole mixture being subjected to either vacuum or heating to release the chlorine.

The mixture, upon exhaustion of the chlorine, is composed of water and sodium cyanurate, which is what I was primarily interested in obtaining.

Sodium Cyanurate, Na3(NCO)3, seems like an excellent candidate for carbon reduction to Sodium Cyanide:

Na3(NCO)3 + 3C = 3NaCN + 3CO

I measured out the approximate ratio, at 1/100th mole quantites, thus 2.3gm of TCCA and 1.7gm of NaCl, and just enough water to moisten, in a covered glass jar placed in a hot water bath.

After a couple of minutes, the mixture turned a pale Grape Kool-Aid purple (because of the CuSO4 in the TCCA) and, upon sniffing a waft of the steamy vapor emitting from the jar, the smell of chlorine was overpowering and left me gasping and my eyes watering.

There was still particles of undissolved TCCA circulating, so the reaction wasn't over, but I dumped the mix down the universal disposal receptacle (the shitter ;)) ASAP, the experiment having been proven successful.

Since the reaction can also be run in a dry state, that would be the most desirable one to use, as then the gas would be dry and not requiring drying prior to use.

Cl3(NCO)3 + 3NaCl = 3Cl2 + Na3(NCO)3

The weight of chlorine being produced being almost equal to the weight of the TCCA in the reaction.

Though I wonder what the effect of 1% of copper sulfate has on the reaction. Probably not much.

Having a ready source of anhydrous chlorine gas for use in reactions, and getting a useable by-product, all from very cheap OTC components, seems desirable to me.

Oh, and by substituting Sodium Bromide (spa chemical) for the NaCl, you can get elemental Bromine instead of Chlorine, bromine being very useful for making powerful lachrymators such as bromacetone and brombenzyl cyanide which is even more powerful than CN, on par with CS, and can be made entirely from OTC chemicals. :)

Industrially, Brombenzyl cyanide is prepared in three steps, as follows:

(1) chlorination of toluene to form benzyl chloride (TCCA + Salt+Paint Stripper)

(2) the conversion of benzyl chloride to benzyl cyanide by the action of sodium cyanide in alcoholic solution (Cyanide made from by-product of reaction 1 + Everclear alcohol)

(3) the bromination of the benzyl cyanide with bromine vapor in the presence of sunlight. (More TCCA + Sodium Bromide spa clarifier)

According to Sartori (page 197 War Gases), it's advisable that you skip the use of benzyl chloride and use benzyl bromide instead, converting that to benzyl cyanide, then use more bromine to form the desired brombenzyl cyanide.

[nbk2000]

US4432959 Process of producing sodium cyanuarate from cyanuric acid

Cyanuric acid and Baking Soda are dry mixed and heated to 60-80°C. The reaction generates CO2 as byproduct, and results in a free-flowing dry powder of Sodium Cyanurate.

[fractional distiller]

Very interesting NBK. You included, IIRC a method for Ferro-cyanide production in your manual which was a great read by the way.

I was going through my usual routine of checking out small hobbyists sites for chemicals and what not when I came across something interesting. www.unitednuclear.com is selling Sodium Ferrocyanide. It claims that it does not exhibit the deadly toxicity found in other Cyanide compounds due to the strong chemical bond between iron and the cyanide groups.

Theoretically how hard would it be to have a single replacement reaction take place causing Sodium Ferrocyanide to Potassium Ferrocyanide, which after two seconds of research tells you that it is almost non-toxic.

But if you decided to dissolve it into a solution with water and an acid it would give of lovely Hydrogen Cyanide gas! I hope you will find this interesting, and not just a kewl trying to insult your intelligence.

Also do you think there is any way to change the non toxic Sodium Ferrocynaide to something that has more of a kick to it with relative ease?

[nbk2000]

Distilling ferrocyanide with an acid creates HCN. Simple mixing won't do it quickly enough, but if heated to boiling...:)

But all this is elementary if you USTFSE.

[chemdude1999]

We use a similar process to extract trace CN from waters for colorimetric analysis at work.

Add about 50 mLs of 1:1 Sulfuric Acid and boil for 1.5 hours over a cold-finger. The HCN formed travels past the cold-finger into a collection vessel containing about 20 mLs of around 1 N NaOH. This pulls the HCN back into solution for analysis.

With modifications and experimentation you could try the method on the Na ferrocyanide.

Note we add sulfamic acid and magnesium sulfate along with the sulfuric acid. These chemicals help initial pH adjustment and eliminate interferences.

Additionally don't over-complicate things with CN. I have found that it can be bitchy, but is quite simple to work with. Sometimes it can be "technique-y".

NBK's finds could provide a summer worth of fun. Just keep the windows open or fume-hood on.