Sciencemadness Discussion Board - Any good uses for Trichloroisocyanuric acid (C3Cl3N3O3)?

Any good uses for Trichloroisocyanuric acid (C3Cl3N3O3)?

vampirexevipex - 24-5-2012 at 17:07

Hello i recently acquired some solid C3Cl3N3O3 (Trichloroisocyanuric acid) and i dont know what to do with it, i know it can be used in pools but i dont need it. So, any good uses? or any good compounds it could be made with it?

I heard that if boiled in water (Or heated) it can release chloride gases and they could be bubbled through water to make HCl. Anything else?

bob800 - 24-5-2012 at 17:32

Our admin Woelen has documented several experiments using this chemical:

http://woelen.homescience.net/science/chem/exps/chemlum/inde...
http://woelen.homescience.net/science/chem/exps/raw_material...

Instead of boiling water, you can also react TCCA with dilute hydrochloric acid for a convenient source of chlorine.

vampirexevipex - 24-5-2012 at 18:38

Hmmm... Cool, anyway... Can you also make copper (II) dichloroisocyanurate with copper hydroxide, instead of copper sulfate?

AndersHoveland - 24-5-2012 at 20:49

Perhaps TCCA could be reacted with dimethylamine, then hydrolysed with a strong base, to make unsymmetric dimethyl hydrazine.

And just to mention, one use that TCCA does NOT have,
http://www.sciencemadness.org/talk/viewthread.php?tid=18920
(for anyone that was thinking about reacting TCCA with silver nitrate, or other such salts, with the idea to make a new explosive, it is not that simple)

[Edited on 25-5-2012 by AndersHoveland]

Adas - 25-5-2012 at 10:17

Quote: Originally posted by AndersHoveland

Perhaps TCCA could be reacted with dimethylamine, then hydrolysed with a strong base, to make unsymmetric dimethyl hydrazine.

Wow, Anders, this seems as a possible thing to me. The only problem is making dimethylamine.

AndersHoveland - 26-5-2012 at 02:27

Quote: Originally posted by Adas

The only problem is making dimethylamine.

Not really. Dimethylamine (or its hydrochloride salt) can be made by refluxing formaldehyde with ammonium chloride in a 4:1 ratio. (lower ratios give methylamine).

Quote:

Methylamine hydrochloride condenses with formaldehyde to form dimethylamine
If formaldehyde is present in excess, at least some of the methylamine is converted to dimethylamine. If too little formaldehyde is present, the methyleneimine polymerizes to its trimer, (CH2=NH)3. Trimethylamine is never formed, as long as the temperature of the solution never exceeds 110°C. With an excess (4 moles) of formaldehyde, enough water and a reflux temperature of 115°C, dimethylamine is the main product, as the temperature rises, more dimethylamine is formed. Dry heating of paraformaldehyde and ammonium chloride produces trimethylamine through reaction of dimethylamine with formaldehyde, giving rise to tetramethylmethylenediamine and formic acid, and the base further reacts with HCl, giving trimethylamine hydrochloride and methyleneimine hydrochloride. A mixture of HMTA and HCl boils between 105 and 110°C, while NH4Cl/CH2O boils at 115°C. No temperature control is really necessary in the former case, as long as your heating plate isn't too hot. If the reaction is carried out at a lower temperature, less dimethylamine is formed, and the yield is higher. Vacuum reflux and distillation can yield at least 95% yield, in contrast to the 45% gotten at 104°C.

This is basically the Eschweiler–Clarke reaction.

Adas - 26-5-2012 at 02:31

Yes, but it would be still easier to react it with NH3 and then use it as a source of hydrazine, maybe.

AndersHoveland - 26-5-2012 at 02:44

Quote: Originally posted by Adas

Yes, but it would be still easier to react it with NH3 and then use it as a source of hydrazine, maybe.

TCCA could, of course, be used instead of hypochlorite solution in the Raschig synthesis to make hydrazine (with perhaps some modification), but the yields would still be poor. The advantage of using dimethylamine with TCCA is that as soon as the hydrazine derivitive formed, it would be protected against further destructive oxidation, so the yields would be high.

As for what potential uses there might be for dimethylhydrazine...

Quote:

MonoMethyl Hydrazinium Nitroformate has a det. velocity of 9134 m/sec, and is also 212% more powerful than TNT on a weight basis (compared with 163% for RDX)
Journal of Chem. Tech. Vol12 2005
"Synth, Characterization, and thermal behaviour of hydrazinium nitroformate..."
H.S. Jadhav, M.B. Talawar (India)

[Edited on 26-5-2012 by AndersHoveland]

vampirexevipex - 28-5-2012 at 04:43

Sorry for late post, but where can i find formaldehyde over here?

Organicus - 29-5-2012 at 03:48

One hast to be very careful when using TCCA in aq. NH3, because the explosive compound NCl3 could be formed!

TCCA also could be used for making Nitriles:
1. http://www.organic-chemistry.org/abstracts/lit2/979.shtm
2. SYNTHESIS 2009, No. 6, pp 0945–0950

Formaldehyde + TCCA is also a bad idea because of cancerogenic Bis(chloromethyl)ether will form.

And btw TCCA + HCl is a very good Cl2 Generator, but that was obvious =)

Here are some interesting reactions with TCCA too:
https://docs.google.com/viewer?a=v&q=cache:a514FLGr4D8J:...

best regards

[Edited on 29-5-2012 by Organicus]

woelen - 29-5-2012 at 04:02

TCCA with NH3 is a no go. As soon as the TCCA comes in contact with NH3 you get a VERY violent reaction. At 5% concentration of NH3 a lot of smoke is produced and you hear a roaring noise. With 12% NH3 the reaction is so violent that pieces of TCCA are scattered all over the place and you hear a loud crackling noise. At 25% concentraion of NH3 you have explosion, as soon as the ammonia comes in contact with the TCCA!

vampirexevipex - 7-6-2012 at 14:33

And another late post.

sorry my neighbor is turning off his internet constantly

. Anyway thanks woelen for the warnings, i didnt know about the violent reactions, right now im trying to get the ammonium chloride gas made in the reaction but since people over here though the tubes i use to bubble gases through liquids was junk, they threw them out :mad:

. So, any other way that i can get the ammonium chloride from the reaction? Btw the concentration of ammonia im using is lower than 10% and i already had tested it with little pieces of TCCA and all i got was smoke. So any help in how to get the ammonium chloride?

Hexavalent - 7-6-2012 at 14:53

Ammonium chloride can be made by neutralizing ammonia solution with hydrochloric acid and evaporating to dryness.

Be warned that diethylamine is used in drug manufacture, so be careful with what you say.

Woelen, I tried your synthesis of copper dichloroisocyanurare using copper sulfate and sodium dichloroisocyanurate, but got a blue compound as a precipitate instead of your purple compound.....any idea why? My Na-DCCA came from baby bottle sterlising tablets and fizzed when added to water. The CuSO₄ was recrystallized lab grade. Any ideas??

dann2 - 8-6-2012 at 13:34

Slightly off topic.
I see DCCA (as opposed to TCCA) starting to appear in UK "one pound" shops as bleaching tablets. Never seen them before.

Dann2

Hexavalent - 8-6-2012 at 16:08

That was where I got mine, although not from a proper pound shop....a pack of NaDCCA tablets were 99p in HomeBargains, so I got some whilst I could.

sargent1015 - 8-6-2012 at 21:09

In response to your thread question, you could chlorinate some pools

Is this an effective means to chlorinate organics? I'm assuming not.

AJKOER - 22-6-2012 at 08:14

What I find most interesting is the formation of potential concentrated HOCl when TCCA reacts with water:

(CNOCl)3 + 3 H2O ---> 3 HOCl + (CNOH)3

as this reaction consumes water. I would cool and separate out the cyanuric acid. Note: HOCl is unstable and can decompose to HCl and HClO3, and also HCl and O2 . How rapidly depends on the HOCl concentration, pH, temperature, light and the presence of organic matter, some metals and chlorides.

Now Hypochlorous acid is a very important oxidizer both in inorganic and organic chemistry. For example, add Sulfur (S) and then per Watts' "Dictionary of Chemistry", Volume 2, Page 16, even dilute solution of HOCl can oxidize Sulfur to H2SO4. To quote the relevant section from Watts':

"Reactions.--1. HClOAq acts generally as an oxidiser; it easily parts with 0 while HClAq remains. Thus, As is rapidly oxidised with evolution of light; P, S, Se, Br, I are converted to H3P04Aq, H2S04Aq, &c., even by dilute HClOAq; lower oxides or salts are converted into higher, e.g. SO2Aq to H2SO4Aq, FeO to Fe203, As203Aq to As2O5Aq, FeS04Aq to Fe2(S04)3Aq, Fe2Cl6Aq, and Fe2O3, MnSO4Aq to MnO2; sulphides yield sulphates, c.g. H2SAq gives" H2SO4,Aq and S; NH3 gives N,H2O,and NH4CLAq; HCl forms H20 and Cl. The quantity of the acid expressed by the formula HClO oxidises the same mass of an oxide"

Link to free Google online book.
http://books.google.com/books/reader?id=ijnPAAAAMAAJ&dq=...

Caution: The decomposition of conc HOCl can produce particularly problematic (including explosive) compounds as well. For example, Wikipedia article on Chlorine dioxide (ClO2), notes (link: http://en.wikipedia.org/wiki/Clo2):

HClO3 + HCl --> HClO2 + HOCl

HClO3 + HClO2 --> 2 ClO2 + Cl2 + 2 H2O

Wiki warns, "Chlorine dioxide is a highly endothermic compound that can decompose extremely violently when separated from diluting substances. As a result, preparation methods that involve producing solutions of it without going through a gas phase stage are often preferred. Arranging handling in a safe manner is essential."

Also, I would avoid the reaction of NH3 and an excess of HOCl as Nitrogen trichloride (NCl3) may be produced in an acidic environment. The reputation of even small amounts of this highly explosive and unstable compound in removing fingers, hands and eyes is well documented. Net reaction can be summarized as:

3 HOCl + NH3 --> NCl3 + 3 H2O

I also recall at least one cited instance of a runaway reaction ending in an explosion involving TCCA or DCCA on this forum with the above candidates cited as possible causes.

[Edited on 22-6-2012 by AJKOER]

AndersHoveland - 23-6-2012 at 01:07

Please, AJKOER, do not try to elaborate on the chemistry of HOCl in threads dealing with other topics! The chemistry of HOCl is very complex and complicated. Not everything you stated is entirely accurate, and what you did describe can be very misleading if taken out of context. If you want to discuss HOCl, please make the post in one of the other threads specifically about hypochlorous acid.

TCCA does not really "react" with water (at least not at neutral pH), it just partially hydrolyses in equilibrium.

[Edited on 23-6-2012 by AndersHoveland]

AJKOER - 24-6-2012 at 10:31

AndersHoveland:

My HOCl comments are largely documented quotes or can be. Nevertheless, I agree with your sentiments that the content therein provided is limited and best presented elsewhere.

However, you are guilty of perhaps the same point on noting that TCCA only partially hydrolyses at neutral pH, which while technically correct, is potentially dangerously misleading in cases where this is not necessarily the case. In particular, there is, per my recollection, at least one reported case of a runaway reaction by a chemist (not an amateur) on SceinceMadness leading to an explosion (described as a hand grenade detonating) in the presence of PCl3 (see http://www.sciencemadness.org/talk/viewthread.php?tid=16123#... )

Hence, my admonition on experimentation with TCCA and my brief (yes, limited and perhaps incomplete) depiction of what and how some very dangerous compounds may arise. Well, at least in my opinion, as there does not appear to be a complete consensus on the culprit in the instance I referenced, again per AndersHoveland point, perhaps owing to the complexity of the chemistry and/or the ignorance thereof. Hence my unwelcomed exposition into HOCl chemistry which I, nevertheless, feel is strongly advisable in a discussion of experimenting with TCCA or DCCA on purely safety concerns. Also, I would add Dichlorine monoxide (as Cl2O becomes increasing explosive in high concentrations) as a potential candidate from the conceivable dehydration of HOCl by PCl3 in this instance (as the action of Phosphorus pentoxide, P2O5, on concentrated Hypochlorous acid is a cited preparation route for Cl2O, the gaseous anhydride of HOCl). Note, Cl2O explodes on exposure to ammonia, but ClO2 does not, while NCl3 explodes in the presence of concentrated ammonia (see http://www.guidechem.com/msds/10025-85-1.html ) and Woelen's comments above on the observed reaction between aqueous ammonia of varying strengths and TCCA.

So please take appropriate safety precautions in choosing the quantity of reactants, lab safety gear, etc. I would also be aware of the sensitivity of the various unwanted compounds I noted with respect to shock, heat, light and the presence of NH3 and select organic compounds.

[EDIT]: I also came across a reported surprisingly explosive aqueous reaction upon heating an aqueous solution of Ammonium nitrate and TCCA (see https://www.sciencemadness.org/whisper/viewthread.php?tid=14...). My take on the pathway, first the hydrolysis of TCCA forming HOCl and then:

2 NH4NO3 + 2 HOCl + 2 H2O --> 2 NH2Cl + 4 H2O + 2 HNO3

Support is based on an article ("Understanding DBP Formation during Chloramination" by Ying Hong, Suibing Liu & Tanju Karanfil, November 2007) where the test chloramine stock solution was prepared by mixing aqueous NaOCl and (NH4)2SO4 (link: http://www.fwrj.com/techarticles/0608%20tech%205.pdf ).

At this point, there are numerous possible reactions, but some dominate reactions with excess HOCl (see discussion at: http://www.troublefreepool.com/chloramines-and-fc-cya-t10257...) include:

HOCl + NH2Cl ---> NHCl2 + H2O

HOCl + NHCl2 ---> NCl3 + H2O

leading to the highly unstable/explosive NCl3. Note, if my speculation is correct, caution should be exercised upon heating TCCA with aqueous NH4Cl or (NH4)2SO4 also.

[Edited on 25-6-2012 by AJKOER]

AJKOER - 25-6-2012 at 11:15

I appeared to have accidentally missed the fact that my suggested pathway noted above in the reaction of heating an aqueous solution of Ammonium nitrate and TCCA in the AN+TCCA thread (https://www.sciencemadness.org/whisper/viewthread.php?tid=14...) was nicely expressed originally by Franklyn. Sorry, here is his comment:

Quote: Originally posted by franklyn

It is not immediately evident, chlorination of ammonium produces chloramimes. Initialy at nearly neutral pH ~ 7 ,monochloramine predominates. As the solution becomes increasingly acid from the released Nitric and Cyanuric, Trichloramine is produced, an oily sensitive primary explosive which floats on the surface and very readily explodes in the small amount produced. Excercise great care , it is unpredictable and will explode without apparent reason.

[Edited on 8-8-2010 by franklyn]

He also supplies a file for download.

AJKOER - 28-6-2012 at 02:05

Caution: Per a prior ScienceMadness thread (http://www.sciencemadness.org/talk/viewthread.php?tid=11763&... ), I suspect that the reaction of an aqueous solution of TCCA and S (and also P), could potentially be very vigorous, or even explosive as Cl2O, the acid anhydride of HOCl, reacts explosively with Sulfur.

If interested in performing this experiment, please work only with a dilute aqueous solution of TCCA at first.

Reactions:

2 HOCl + S + H2O --> 2 HCl + H2SO3

HOCl + H2SO3 --> HCl + H2SO4

I am expecting the (CNOH)3 to be largely unreactive in this dilute acid environment. Also, the previously described reaction between TCCA and aqueous ammonia described by Woelen above, could at least in part be due to the reaction between Cl2O and NH3, which is also explosive. The other NCl3 pathway requires first the formation of the oily yellow explosive Nitrogen trichloride followed by a trigger to detonate it (light, heat, organic compound,..).

[Edited on 28-6-2012 by AJKOER]

AJKOER - 15-7-2012 at 07:11

Quote: Originally posted by AJKOER

AndersHoveland:
..............
Well, at least in my opinion, as there does not appear to be a complete consensus on the culprit in the instance I referenced, again per AndersHoveland point, perhaps owing to the complexity of the chemistry and/or the ignorance thereof. Hence my unwelcomed exposition into HOCl chemistry which I, nevertheless, feel is strongly advisable in a discussion of experimenting with TCCA or DCCA on purely safety concerns. Also, I would add Dichlorine monoxide (as Cl2O becomes increasing explosive in high concentrations) as a potential candidate from the conceivable dehydration of HOCl ...

OK, so I went out on the limb by adding Cl2O to ClO2 and NCl3 as conceivable culprits. Well, apparently not as here is a newly discovered (by me) quote by Nicodem in February of this year:

Quote: Originally posted by Nicodem

I just like to quote myself:

Quote: Originally posted by Nicodem

I issued warnings about TCCA many times and still accidents like this happen. I really do not understand why people underestimate the dangers of such powerful oxidants. For example, the accident that happened to Hinz was the consequence of his own carelessness and his unthoughtful "modification" of the acetone chlorination otherwise nicely described in the patent. Things like this are common. I saw other examples of members posting their use of TCCA in irresponsible way (and doing their first experiments on a huge scale!). In the particular case described in this thread it is quite obvious what happened. The guy forgot to quench the reaction with sulfite and distilled the whole reaction mix still containing the oxidant and the acid thus causing Cl2O formation and disproportionation to chlorine dioxide which together with organic vapors form a terribly light sensitive explosive gas phase. While working in the lab only thinking about what you are doing can save you from injuries or even death. I'm glad he described his accident as this might give some thought to all those who start their first reactions on a huge scale without thinking much what they are doing. And of course it is nice to hear he got trough it without glass shrapnels in his face.

Source of the referenced thread, "Thermal decomposition products of TCCA in water at extraction from chlorinating tablets", at http://www.sciencemadness.org/talk/viewthread.php?tid=18953

See also comments by Bahamuth supporting the Cl2O path referred to in the link as gaseous hypochlorous acid:

Quote: Originally posted by bahamuth

Edit: Apparently hypochlorous acid may indeed detonate at elevated temperatures and it may very well be that phenomenon I observed.

Of gaseous hypochlorous acid

And it may have been traces of sodium carbonate forming sodium hypochlorite further reacting with hypochlorous acid causing the "detonation" as mentioned in several MSDS on both compounds.

Also, there is an interesting reference provided by Polverone giving more detail on the NCl3 path in support of AndersHoveland comment:

Quote: Originally posted by Polverone

According to Bretherick's Handbook of Reactive Chemical Hazards on TCCA,

"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."

In your case it makes sense that the explosion could take place in the vapor phase, since the boiling solution would not retain nitrogen trichloride as a liquid.

As my reputedly novel suggestion of Cl2O has been already presented, I will not disappoint and suggest yet a new possible culprit by the formation of some NH4ClO3 (in addition to NCl3 which requires an excess of HOCl) in the presence of NH4+ cation. My, albeit weaker argument, is based on two points. First, some warm/concentrated HOCl formed from TCCA, could disproportionate to Chloric acid and/or Chlorate. Second, even aqueous solutions of the highly unstable Ammonium chlorate are prone to powerful denotations (similar to Nitrogen trichloride). To quote from Wiki: "Ammonium chlorate is a very unstable oxidizer and will decompose, sometimes violently, at room temperature. This results from the mixture of the reducing ammonium cation and the oxidizing chlorate anion. It will explode when exposed to sunlight for a few minutes. Even solutions are known to be unstable."

Now that everyone has hopefully properly addressed the potential explosion hazard, note also the comment on the creation of small amounts of Phosgene (COCl2) gas in the presence of an organic solvent as per Weiming's comment "then dissolve the TCCA in it [meaning CHCl3]. Pour the solution onto a wide plate under the sun OUTSIDE, because small amounts of phosgene will form." Per another source in the case of CCl4, the author notes: "For CCl4, HClO4 is insoluble in CCl4, and gives upon shaking, a green emulsion, which discolors brown after several minutes welling up under formation of HCl and COCl2 (Vorländer, v. Schilling, Lieb. Ann. 310 [1900] 374)" and further, "So mixing something like CCl4 and HClO4 can cost one their lives if not wearing protective gear, doing under fume hood,etc. It is dangerous to extrapolate so assuredly." Link: https://sites.google.com/site/energeticscribble/perchloric-a...

So, the formation of even trace amounts of perchlorates in an acidified medium in the presence of CCl4 (or CHCl3?), may present an additional safety concern.

[Edited on 15-7-2012 by AJKOER]