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papaya
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Hope it didn't hurt you woelen, please be more careful. When dealing with a thing I'm always frightened that it can accidentaly generate some phosgene
when reacted with other organics (or just by itself), I'll be thankful if someone posts with what it should NOT be mixed to not create an hazard.
Regarding chlorine generation - am I getting it right, that when you mix TCCA+NaCL+boric acid, nothing is happening, but when purple complex is added
(insoluble?) there's a reaction? If so can we conclude that the reaction is really catalyzed with copper complex? Also it's not clear form the text -
if it worked very slow without boric or didn't work at all? Is heating a must for the last case?
Hearing about you accident I wonder if some mixture like TCCA/kerosene will be an energetic if initiated properly, unfortunately I can't test this
even if I wanted (at least boric acid is going to interfere). To anyone who wants to find this out : NEVER store such a mixture, also I'm not
responsible if something goes wrong..
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woelen
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Nothing serious happened. My heart skipped a few beats and I had to cleanup the mess, but no personal injury. It was quite hefty though! NH3 + TCCA is
a very dangerous combination. I knew it could react violently, but such a violence with only 10% NH3 is not what I expected. I think that the fact
that I had crushed the TCCA to a powder contrinuted to the explosive violence. The reagents were cold, so heat was not a factor in this reaction.
If I mix TCCA+NaCl+boric acid, then indeed nothing happens, but if I do the same with copper (in any form) added, then there is a reaction, albeit a
slow one. So, the copper certainly does something to the reaction rate, but it is not a spectacular thing.
If I heat the mix, then with the same amount of heating, the mix with boric acid added shows more activity than the mix without boric acid.
So, boric acid seems to be required for the reaction, and copper ions have a clearly noticeable catalytic effect. No boric acid present? Then the
copper also does not add much to it.
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papaya
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It's pity, I hoped the reaction to be possible without any acid, it seems boric acid just keeps pH not to go too high with hydrolysis of sodium
cyanurate forming, but what does the copper (especially in already-cyanurate form!)? What will be next logical step - looking for other catalysts
maybe (I posted a little test before, seems iron is a candidate).
Also I wonder - couldn't the generated gas be not just a chlorine, but contain also oxygen (mostly oxygen?? )? Because if hypochlorite cam be destroyed catalyzed by some metal ions giving oxygen, this might explain such a
bubbling..
I like this compound - too many possibilities, yet no practical usage is clear.
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woelen
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The generated gas is mostly chlorine. Even a test tube filled with the gas shows a clearly visible green color through only 1.6 cm of gas. If the gas
were mainly oxygen, then the green color would be invisible.
I think that the presence of acid indeed is a requirement for decent chlorine production. If chlorine could be formed easily without acid, then I'm
quite sure that it would not be such a common pool chlorinator. A pool contains quite some chloride ions (from old pool chlorinator) and if this could
react to chlorine with TCCA then that would lead to a lot of irritation or even more serious health effects.
Practical use of TCCA is indeed fairly limited. I use it, combined with dilute HCl, for making chlorine. This works very well and gives a nice
continuous stream of chlorine. The remaining cyanuric acid can also easily be extracted from the mix, just boil with some distilled water and assure
there is excess HCl to destroy all remains of TCCA and drive off the Cl2.
TCCA is an interesting chemical for experiments. It shows many perculiar reactions, but it is somewhat dangerous. It is a highly active and very
concentrated oxidizer and it is remarkable that in these times of overblown safety and fear of chemicals the pure chemical TCCA is still widely
available for the general public.
Actually, there are more of such very reactive chemicals, which still are easy to obtain. Some examples are:
- swimming pool chlorinator: calcium hypochlorite, Ca(ClO)2.2H2O
- swimming pool chlorinator: Na-DCCA
- swimming pool brominator: BCDMH
- water purification and MMS: sodium chlorite, NaClO2
E.g. NaClO2 is more reactive than NaClO3 and the latter is banned from nearly all western countries.
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papaya
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TCCA/kerosene(10%) mixture didn't show any evidence of reaction, even when stored for 1 day(200g.). Though it didn't ''react'' also when initiated,
but this I find non conclusive.Someone wants to prove me false?
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woelen
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Please do not prepare such large amounts of this kind of mixtures. With this one you had good luck, but with other mixes you may have nasty accidents.
If you have 200 grams of mix, then REALLY nasty things can happen.
The explosion I had a few days ago was with a few 100's of mg. I must not think of what would have happened if this were 100 g or so.
Kerosene is fairly inert at room temperature. I think that a burning mix of kerosene and TCCA can be quite spectacular. Powdered TCCA, wetted with
kerosene and then ignited. But only make a gram or so, not more!
If you want to be impressed by TCCA's reactivity, then take a piece, as large as a pea and pour some household ammonia (5% NH3) on it. This is a
violent but non-explosive reaction.
Then do the same with powdered TCCA and pour household ammonia on it, using a long stick to pour the ammonia on the TCCA!
If you have 25% ammonia then also repeat the experiment with a pea-sized piece of TCCA, but use a long stick to pour the ammonia on the TCCA! You will
be impressed!
NEVER USE MORE THAN PEA-SIZED CHUNKS OF TCCA IN THE ABOVE EXPERIMENTS!
[Edited on 3-5-13 by woelen]
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papaya
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Yes, woelen, I know what you mean, I just omited here parts of testing small quantities before . Btw, kesrosene burning with TCCA is not spectacular
at all - it seems like kerosene alone is burning, with little greenish flames sometimes, very slow and incomplete,resembles that ov PVC. Must be
kerosene contains mostly alkanes and they seem to be totally inert, this is why my last experiment failed (though ratios and purity may be important).
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papaya
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Wanted to impress myself lately followed by woelen's suggestion  , instead of
ammonia solution I decided to take more 'spicy' 50% N2H4, few crops of TCCA were placed on some paper, a cotton wetted with hydrazine was carefuly put
on top of it. Besides hissing sound and white smoke it gave (some hydrazoic acid in it? )and warming (cotton blackened a little) no accidents evidenced even when pressing two with a stick.
I'm completely disappointed 
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woelen
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I think that if you pour 50% N2H4 on a piece of TCCA you will get a very violent and spectacular reaction. But try it with ammonia as I explained in
my previous post, that really is spectacular.
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papaya
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As I wrote it was violent with N2H4, but without explosion, though in larger quantities it will be unsafe for sure. One question is - if one could
oxidize hydrazine to hydrazoic acid (salts) directly with TCCA and without nitrite, also taking into account that TCCA is highly soluble in acetone,
this may simplify things, for example to add dropwise NaOH/N2H4*H2O to TCCA/acetone solution (do NOT try this, it's never proved to be safe). Is this
possible even theoretically?
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woelen
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I do not believe that this will work. I expect the mix to ignite or even explode. You could try it at a very small scale. Just take 2 or three drops
of the TCCA/acetone solution on a watch glass and add a single drop of hydrazine hydrate/NaOH mix and see what happens. With single drops you won't
have heavy accidents. Just do this outside and use a pipette for adding single drops of liquid. Use eye protection, just in case the stuff
splashes around.
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testimento
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Can I use sodium di- or trichloroisocyanurate in radical chlorination processes initated by peroxides or UV light?
I also have problem with TCCA purity. It has been severely contaminated with citric acid, boric acid and sodium carbonate. TCCA is quite soluble in
acetone(source cites), while the mentioned impurities aren't, but I was alarmed that could the reaction, in where one dissolves TCCA in hot acetone
until it is all dissolved, filters it from impurities and distills off the acetone using water bath(60-70C), cause formation of chloroacetone, or even
worse, lead to extreme runaway during this purification step? I have understood that boron and citric acids are not a problem in radical chlorination
reactions in smaller amounts since the reactants are vacuum distilled afterwards, but sodium carbonate is an obvious problem.
[Edited on 25-10-2013 by testimento]
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AJKOER
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Quote: Originally posted by woelen  | ......
TCCA is an interesting chemical for experiments. It shows many perculiar reactions, but it is somewhat dangerous. It is a highly active and very
concentrated oxidizer and it is remarkable that in these times of overblown safety and fear of chemicals the pure chemical TCCA is still widely
available for the general public.
Actually, there are more of such very reactive chemicals, which still are easy to obtain. Some examples are:
- swimming pool chlorinator: calcium hypochlorite, Ca(ClO)2.2H2O
- swimming pool chlorinator: Na-DCCA
- swimming pool brominator: BCDMH
- water purification and MMS: sodium chlorite, NaClO2
E.g. NaClO2 is more reactive than NaClO3 and the latter is banned from nearly all western countries. |
Well, near me, the Home Depot and Lowe's both recently appear to have discontinued their entire pool chemical section.
When I asked, I was told (most likely by someone who really doesn't known what is occurring) that the store was probably not rural enough to justify
the pool/spa accessories.
So, enjoy them while you can, as possibly coming to a store near you, the chemicals of interest will not be available.
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chemrox
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Sauron is the expert on this material.
"When you let the dumbasses vote you end up with populism followed by autocracy and getting back is a bitch." Plato (sort of)
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woelen
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This answer is of no use, Sauron (unfortunatyely) left sciencemadness several years ago and will not answer anyone's questions on chlorinated
organics. His speciality, btw., was not particularly on chemicals like TCCA, but was more related to highly reactive acyl chlorides and related
chemicals (e.g. CH3COCl, SOCl2, POCl3, PCl5, cyanuric chloride, not to be confused with TCCA).
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testimento
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Is it safe to purify impure TCCA tablets via dissolving them into acetone? I understood that heating the mixture may cause severe problems, even
explosive so. So should it be possible to dissolve it into cold(10-20c max) acetone, filter out the gunk and then vacuum distill off the acetone?
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