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Author: Subject: Cyanuric acid/Trichloroisocyanuric acid Energic derivatives
niertap
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[*] posted on 8-9-2012 at 22:48
Cyanuric acid/Trichloroisocyanuric acid Energic derivatives


This is a fairly cheap pool chemical that seems like it has potential. Cyanuric acid has a lot of keto/enol tauting, so it would be difficult to do much that wont destroy it. However I think the trichloro derivative has potential to be nitrated. A nitramine would probably decompose, but nearly anhydrous nitration (without H2SO4) might work. 1,3,5-Triazinane-2,4,6-trinitrate may be possible, but likely a bit unstable. (O2NO)3-C3N3

aka 3 NO3s with the O attached to the carbon in the aromatized triazine




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[*] posted on 9-9-2012 at 10:07


NO2+ appears not act so on trichloroisocyanuric acid in aprotic conditions, you get nitration systems (briefly looking at doi: 10.1016/j.cclet.2010.05.016, 10.1002/chin.200319081, etc.).

The possibly of forming a triazido derivative from TCCA has been speculated here. Similar in structure to cyanuric triazide, it would likely also be water insoluble. The performance equivalence could be similar to RDX, but much more sensitive. Another compound, nitrogen azide a.k.a. nitrogen triazide, N(N3)3, is also speculated, though I'm having some doubts the syntheses of both compounds is as straight-forward as presented.

N10 should have high unstability and insane explosive properties. The latter has already been tried by interaction of NCl3 and NaN3 at low temperatures and with solvents in the 1960s by German chemists, but it yields only theoretical nitrogen and NaCl, and N10 is not even present as an intermediate (doi: 10.1002/ange.19620740904, 10.1002/zaac.19643320504).

Discussion of azidamines was also done in this thread: http://www.sciencemadness.org/talk/viewthread.php?tid=9370

[Edited on 9-9-2012 by Formatik]
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[*] posted on 15-9-2012 at 09:11


As background, I just thought reading another thread where mixing a touch of aqueous ammonia with CuSO4 and a source of Chlorate (see "tetramine copper chlorate" at http://www.sciencemadness.org/talk/viewthread.php?tid=14048 ), produced an eventually explosive mix upon drying and the lowing of the pH (as the NH3 evaporated). Now, what would happen upon mild heating of a Copper sulfate hydrate and Trichloroisocyanuric acid?

First reaction hydrolysis (which increases as pH differs from 7 especially with commercial TCCA products that contain Na2CO3):

Cl3(NCO)3 + 3 H2O --> H3(NCO)3 + 3 HOCl

If the mixture eventually explodes, I would speculate the creation of HOCl (low pH in the water from the acid hydrate), which being warm and concentrated, the Hypochlorous acid disproportionates creating some HClO3 (and ClO2). Support, see comment from "Process for production of an alkali metal dichloroisocyanurate and trichloroisocyanuric acid", United States Patent 4395548, to quote:

"It has unexpectly been found that the inability to form sufficient hypochlorous acid to fully chlorinate the available dichloroisocyanurate to TCCA (a mol ratio of less than one) adversely affects each of these three factors. This low mol ratio can be caused by the decomposition of hypochlorous acid to form hydrochloric acid according to the following reactions: 2HOCl➝2HCl+O2, 3HOCl➝HCl03 + 2HCl, or by a reaction consuming hypochlorous acid, such as the formation of chloroamine: HOCl+NH3 ➝NH2Cl+H2O,
or by the consumption of available alkalinity as in the destruction of a triazine ring: 2C3H3O3N3 +9Cl2 +18NaOH➝6CO2 +3N2 +18NaCl+12H2O"

on the 3rd page, column 3, at link: http://www.google.com/patents?id=TNowAAAAEBAJ&printsec=a...

Now, the reactions leading to the creation of ClO2 (from HClO3 and HCl) include per the Wikipedia article on Chlorine dioxide (link: http://en.wikipedia.org/wiki/Clo2):

3 HOCl --> HClO3 + 2 HCl
HClO3 + HCl --> HClO2 + HOCl
HClO3 + HClO2 --> 2 ClO2 + Cl2 + 2 H2O

As such, the creation of HClO3, I would expect, would soon be followed by an explosion. Just another example of what not to mix with TCCA.

Another path includes the HOCl forming Copper hypochlorite (and/or NaOCl in the presence of Na2CO3). An interesting fact is that Cyanuric acid is attacked readily by hypochlorites. Per a source (see "CYANURIC AND ISOCYANURIC ACIDS", Volume 8, page 202 at http://www.scribd.com/doc/30133467/Cyanuric-and-Iso-Cyan-Uri... ) to quote:

"5.2. Oxidation.
Although the triazine ring of cyanuric acid is stable to oxidizers such as peroxydisulfate, it can be cleaved by alkaline hypochlorite: 2 H3(NCO)3 + 9 ClO- --->3 N2 + 6 CO2 + 9 Cl- + 3 H2O (24). Chloroisocyanuratesare similarly decomposed by alkaline hypochlorite (8)."

As such with the non-alkaline conditions associated with CuSO4, one, per above, would not expect the oxidation of the H3(NCO)3, however, sources differs. For example, here is a reference originally supplied by Polverone (http://www.sciencemadness.org/talk/viewthread.php?tid=18953 ) citing Bretherick's Handbook of Reactive Chemical Hazards on TCCA. To quote:

"If mixed with a small amount of water, the conc. solution (with pH around 2) may explode, owing to evolution of nitrogen trichloride. It is believed that hydrolysis leads to formation of hypochlorous acid and dichloro-s-triazinetrione, and the protonated acid then attacks the C=N bonds in the triazine ring leading to formation of chloramines and nitrogen trichloride. The dichloro compound is stable to acid in absence of hypochlorous acid."

Polverone further notes that an explosion could take place in the vapor phase, since a boiling solution would not retain nitrogen trichloride as a liquid. However, the low pH cited appears to be unnecessary as per another source (Kagawa et al) cited in the Patent 4,395,548, the max yield of NCl3 occurs in a pH range of 5 to 7.

My final comment is not precisely understanding while a detonation occurs is perhaps secondary to expecting the explosion event itself.


[Edited on 16-9-2012 by AJKOER]
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[*] posted on 10-10-2012 at 10:06


I've tried reacting trichloroisocyanuric acid with sodium azide in the milligram scale and at room temperature, but got no product. In the first case, aq. sodium azide solution reacted with TCCA either as an aq. suspension or aqueous solution (solvated fraction) gave no reaction.

In the second case, using a solution of trichloroisocyanuric acid in dimethylformamide, when to this was added solid sodium azide, it caused effervescence. It's doubtful the evolved gas was either ClN3 or HN3 because attempts to ignite it with an open flame were not successful. It think it was just nitrogen. Taking some of this solution and adding it to water gave no precipitate. Lastly, the residue from the evaporated dimethylformamide solution was not energetic.

Concerning the caution above on TCCA, the only source for that Brethericks entry on TCCA is a private communication, which I think is very odd. There is supposed to be info on conditions surrounding the formation of chloramines from trichloroisocyanuric acid even in absence of NH4+ in a French paper cited in later Brethericks (Paul, J-M., Actualité Chimique (2004) 274, 10).

Nevertheless, a great and safe way of generating chlorine is with trichloroisocyanuric acid and moderately diluted hydrochloric acid. I and many others have used larger amounts and never had any issues.
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