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View Full Version : Azido-Dithiocarbonic Acid (ADCA), Analogs and Derivatives


The_Duke
November 5th, 2005, 02:07 AM
An interesting piece of literature recently came to my attention while researching an unrelated compound. I was looking through some old chemistry books in my universities library when I found half of a torn out page from one of the books (I am unsure of which book though), anyway the page discuses a brief process for the manufacture of Azido-Dithiocarbonic Acid from HN3 and CS2 and mentions that several of the heavy metal salts of Azido-Dithiocarbonic Acid explode with great violence from shock or when exposed to flame. I have done further research and have found that Azido-Dithiocarbonic Acid and derivatives are explosives and that they are fairly well documented in many books, journals, patents etc. But they have never been discussed here at the forum. From what information I have thus far gathered, I can see minimal possibilities for practical applications for several of the heavy metal salts of Azido-Dithiocarbonic Acid for use in the Art, but over all the unavailability and high cost of the precursors would seem to limit this group of explosives to being of general interest only.

I have found Details for a process for the manufacture of Azido-Dithiocarbonic Acid from Sodium Azide and Carbon Disulfide from one of the JACS articles referenced in PATR 2700 (volume 1 page A632). Basically, equal molar amounts of Sodium Azide and Carbon Disulfide are allowed to react on each other in an aqueous medium (such as water) for 48 hours at a temperature of 40C. Conc. Hydrochloric Acid is then used to convert the Sodium Azido-Dithiocarbonate salt into the free Azido-Dithiocarbonic Acid. The free acid is then filtered and dried.

The Pb salt of ADCA looks like the only one which were ever seriously considered for practical use as initiating explosive and seems like a possible candidate for Azo-Chlathrate type complexes with other Lead compounds.

I will be preparing several of the salts in the weeks to come, once I purchase the Carbon Disulfide. Has anyone had any real success making Carbon Disulfide? Over at ScienceMadness there has been but little success with very small yields of CS2 actually being produced. That thread can be found here (http://www.sciencemadness.org/talk/viewthread.php?tid=1066).


The more relevant references can be downloaded below.

JACS 45 pg 2604 (http://www.easy-sharing.com/58557/JACS%2045%20pg%202604%20Azido-Dithiocarbonic%20Acid,%20Formation,%20Preparation% 20and%20Properties.pdf.html)
JACS 52 pg 2806 (http://www.easy-sharing.com/58550/JACS%2052%20pg%202806%20Azido-Dithiocarbonic%20Acid%20&%20Salts%20of%20Cu,%20Ag,%20Au,%20Zn,%20Cd,%20Hg,% 20Tl,%20Pb%20and%20Bi.%20.pdf.html)
JACS 49 pg 917 (http://www.easy-sharing.com/58566/JACS%2049%20pg%20917%20Azido-Dithiocarbonic%20Acid,%20Azido-Dithiocarbonates%20of%20Li,%20Na,%20Rb%20and%20Cs. pdf.html)
GB188302 (http://www.easy-sharing.com/58559/GB188302%20Initial%20explosive%20priming%20composi tions%20and%20process%20for%20their%20manufacture. pdf.html)

quicksilver
November 5th, 2005, 11:00 AM
I have found Details for a process for the manufacture of Azido-Dithiocarbonic Acid from Sodium Azide and Carbon Disulfide from one of the JACS articles referenced in PATR 2700 (volume 1 page A632). Basically, equal molar amounts of Sodium Azide and Carbon Disulfide are allowed to react on each other in an aqueous medium (such as water) for 48 hours at a temperature of 40C. Conc. Hydrochloric Acid is then used to convert the Sodium Azido-Dithiocarbonate salt into the free Azido-Dithiocarbonic Acid. The free acid is then filtered and dried.


Actually the only problematic issue would be the carbon disulfide, which is a tough item to come by in quantity. I heard of someone who was burned badly by same due to it's very low flash point. Really, setting up an OTC source for it would be the way to go but I can't think of any at this point. Making it would be just as much work as distilling fine HNO3. On the other hand I have found so much sodium azide pellets from air bag units that I am set there. One needs to extract the azide from the pellets (they are coated) but with the solubility of azide, it's been a "non-issue". You really can get pounds of azide for very little work. The best are air bags in Fords and Cryslers as they are the easiest to open. Others have proven to be a serious hassel to open up. The worst being Infinities.
That's some interesting material there. However I am interested in your comparison to the clathrate issue. Are you saying that one could bind a crystal latice with a Azido-Dithiocarbonic or the other way around? Expounding on that issue would be apprieciated....this may be a winner...(?)

FUTI
November 5th, 2005, 12:43 PM
CS2 is AFAIR used in agriculture as some kind of pesticide for heavy rooted weed in wineyards (grape production) so look Mega's page or google on the web. Anyway I don't know does those supposedly OTC products contain enough CS2 for anyone to try to extract it taking the risk involved. CS2 is highly flameable with flashpoint almost the same as boiling point and as they told me have a habit to spontaneously self-ignite in contact with steam/water vapour. Happy hunting though...:cool: I wonder did you found what are the products of decomposition reaction. This explosive can't be judged by OB, it can be conversion of crystal latice energy and/or some kind of explosive polymerisation. It have a nitrogen but in its reduced form without NOx group near by to be used to convert it to N2. Does it produce S8 or H2S during reaction? If that is the case maybe some kind of isothiocyanate forms and then start polymerisation reaction causing the energy of crystal lattice and polymer formation to be rapidly released...of course I'm just guessing and asking did you bump into an answer so that I don't have to do it myself where you have been before.;) And if it produce HCN you can become blue:D may the Gods of Explosive construction be with you!