Sciencemadness Discussion Board

tetramine copper chlorate

avi66 - 22-6-2010 at 05:05

few question about this material:
1)can i use potassium chlorate instead of sodium chlorate, to move the chlorate ion to the copper?
2)after i desiccant this material and pressed it dry to sealed detonator... its will lest for a long time ?
3)moisture help the decomposition of this material over time?
4)is it really safe like lead azide .... like the text say?

woelen - 22-6-2010 at 06:39

Answer to question 4: Tetrammine copper(II) chlorate sounds to me like a very dangerous compound. Ammonium chlorate already is a very dangerous compound (e.g. shipping of this is not allowed at all), then one for sure can say that the tetrammine complex of copper is even more dangerous.

Answer to question 1: Using KClO3 instead of NaClO3 will be harder. Solubility of KClO3 is much less than solubility of NaClO3 and I can imagine that KClO3 will drop out of solution before Cu(NH3)4(ClO3)2 drops out of solution. So, I don't say that it is impossible to use KClO3 for making the tetrammine copper complex, but it definately will be harder.

I do not know about long-term stability of this compound and how easily it can be dried and what influence moisture will have on its stability.

quicksilver - 22-6-2010 at 07:12

With the problems associated with copper exposure to BOTH perchlorate & chlorate I would venture that long term, the material would (at best) decompose. The likelihood of an energetic decomposition would exist if there were some stimulus prior to or during that period.

If anyone said that lead azide was safe I would start to smile as I left that area...... Lead azide is anything - but safe. If not heavily dextrinated, it has one of the highest static sensitivities of common primaries. It also has one of the most dangerous production elements unless steps are take to ensure lack of needle crystal production. Any needles in the azide and generally the material is refused by commercial production. Aside all that, it's extremely toxic....with a pretty nasty LD50 - it absorbs via superficial skin contact.

So many documented plant tragedies have been traced down to brass (or copper) exposure of the perchlorate / chlorate production efforts that I would stay far away for a prepared mixture directed to long term storage. A great deal of information can be gleaned from this however and there may be some very interesting issues applied for short term use, etc - I can see that there is some interesting issues.

There was a type of percussion cap made during the close of the 19th century that used finely powdered copper & a chlorate (however it was highly corrosive to the bore). Chlorates are a powerful oxidizer that respond very distinctly to any fuel or reducing agent in their presence....

Harry Gilliam (of SkyLighter Pyro) used to tell this story & example to new employees.... He would get a very small amount of KCLO3 & some sulfur, placing both on an anvil before smacking them with a hammer. The sound was supposedly unusually loud. He would then explain that the amount was much less than a gram and if just one of the pound packages (or more) exploded, the new employee would have a problem, etc. As it was, the report of the "pinch" of chlorate was pretty damn impressive.

The "safety rules" when working w/ chlorate are pretty damn vast. They have a sensitivity that is pretty tough to get around. They can be unpredictable in a variety of ways to the point of people continually wanting to seek alternatives [simply because of that issue].

unionised - 22-6-2010 at 10:47

Re 4.
It's safe, like lead azide and lion taming while blindfold .

The WiZard is In - 22-6-2010 at 11:11

Quote: Originally posted by woelen  
Answer to question 4: Tetrammine copper(II) chlorate sounds to me like a very dangerous compound. Ammonium chlorate already is a very dangerous compound (e.g. shipping of this is not allowed at all), then one for sure can say that the tetrammine complex of copper is even more dangerous.

Answer to question 1: Using KClO3 instead of NaClO3 will be harder. Solubility of KClO3 is much less than solubility of NaClO3 and I can imagine that KClO3 will drop out of solution before Cu(NH3)4(ClO3)2 drops out of solution. So, I don't say that it is impossible to use KClO3 for making the tetrammine copper complex, but it definately will be harder..



----
On the positive side — if you use water ... you will not
produce explosive tetraammine copper chlorate. Flammable
yes - explosive no. Check out one of the Low Albedo Books.


The American Druggist An Illustrated Monthly Journal of Pharmacy, Chemistry and
Materia Medica
FRED'K A. CASTLE, M.D., EDITOR
VOL. XVIII.
WILLIAM WOOD & COMPANY
PUBLISHERS
56 & 58 LAFAYETTE PLACE, NEW YORK
1889

--------
June 1889
Chlorate of Potassium as an Explosive.
CHLORATE of potassium is the most explosive substance with which chemists and
druggists have to deal. By itself it seldom gives rise to serious accidents, but the
violence of its character is occasionally shown, and most frequently and
disastrously in the case of colored fireworks. We learn from a report of Her
Majesty's Inspectors of Explosives that Mr. Dupre, the chemist to this department,
last year had to investigate an accident in Pain's fireworks factory arising from the
explosion of colored stars. The results are of interest as corroborating previous
observations regarding the highly sensitive nature to percussion and friction of
chlorate mixtures, particularly at slightly elevated temperatures. The chemicals
employed in the manufacture of the stars were found to be chlorates of barium and
potassium, nitrate of strontium, shellac, coal, and lamp-black. Lamp-black is liable
to contain an appreciable quantity of free sulphuric acid, but there was none in this
case. It was found, however, that one of the ingredients (Chertier's copper) of one of
the stars was distinctly acid, and was the cause of the explosion. Chertier's copper is
a mixture of chlorate of potassium and sulphate of copper, which has been
moistened with ammonia and dried, when freshly made it is alkaline, but in time it
loses ammonia, becomes acid, and evolves chlorine compounds, owing to the
decomposition of the chlorate of potassium by the sulphate of copper. In other
words, Chertier's copper is liable to spontaneous decomposition, and the presence
of such a substance in a combustible or explosive mixture cannot but be highly
dangerous. It is marvellous how little is required to produce "spontaneous"
decomposition in these explosives. Thus the paste used for making pill-boxes
becomes acid, owing to a change in the alum of the paste ; and as no chlorate
mixture should ever be brought into contact with materials that are either acid in
themselves or are liable to become acid in the course of keeping, it is obvious that
the spontaneous ignition of such mixtures kept in these boxes becomes merely a
question of time and circumstances. These remarks apply more particularly to
fireworks, but pharmacists will do well to keep the facts in mind when they are
handling powders or other preparations containing chlorates.-Chem. and Drug.


I recommend —

B.L. Bush
Chertier’s Copper(s)
Pyrotechnics Guild International Bulletin (PGI)
129/37

the Z man - 23-6-2010 at 08:43

I made TACC a few times for fun. Blue powder in the form of granules, decomposes at RT, maybe due to moisture, if perfectly dry flashes blue with lots of smoke if touched by flame.

Actually even if its chemical stability is poor it doesn't seem very dangerous.
PATR 2700 gives 15 cm of height for 2 kg in the impact test , density 1,80 g/cc, tauzl test 80% TNT, is able to initiate TNT.
If I remember correctly "The improvised munitions handbook" (or something alike) of the US Army says its sensitivity to impact is similar to lead azide and its friction sensitivity is "moderate", it requires strong confinement to do DDT but easly becomes dead pressed.

I think it could be a very interesting compound, but its synthesis is messy, expensive and yields are poor. It can't be syntesized in water. It requires alcohol, NH3 gas and LOTS of acetone to precipitate and wash.

Maybe KClO3 can be used, as also NaClO3 is very insoluble in alcohol.I think the important is that copper sulfate and the chlorate are intimately mixed.

[Edited on 23-6-2010 by the Z man]

Shotgun Man - 14-9-2012 at 04:56

One of my friends have used TACC for paintball grenades in times of chemical depressions and he is nothing short of a lunatic. Everything below I recall from memory from previous conversations with him and should be taken with a pinch of salt.

1)can i use potassium chlorate instead of sodium chlorate, to move the chlorate ion to the copper?

Yes you can, my friend only uses KClO3 as it is easier for him to acquire. KClO3 and Copper Sulfate are refluxed with anhydrous ethyl or methyl alcohol for 30 minutes until the liquid turns lime green with white potassium sulfate powder in solution that gets filtered out. My friend only ever used ethyl alcohol, but he was assured methyl alcohol works fine. I know that afterwards he passes anhydrous ammonia gas through the solution. I do not know more than this about his process of making it.

2)after i desiccant this material and pressed it dry to sealed detonator... its will lest for a long time ?

No. Compression destroys the detonation properties, it must be packed loosely into the detonator. Also moisture from the atmosphere destroys the detonators if stored outside a desiccator. TACC detonators will not detonate secondary explosives, so making a detonator from TACC is useless for this purpose.

3)moisture help the decomposition of this material over time?

Yes, moisture destroys this stuff like you wouldn't believe and very quickly. So much so that its more trouble than it is worth to make, my friend cleverly seals his charges airtight but I don't know how.

4)is it really safe like lead azide .... like the text say?

The WiZard is In and his post above is correct. When I questioned him about his lack of safety, my friend retaliated by mentioning that after a few weeks of storage he discards the TACC batch. He stated that the reasoning for this was that after a few months, copper and chlorate batches of any chemical arrangement would spontaneously detonate. This is the reason why he only uses it during chemical depressions where he has no other alternative on short notice. I advise against having anything to do with TACC in the interest of your own safety.

[Edited on 14-9-2012 by Shotgun Man]

[Edited on 14-9-2012 by Shotgun Man]

virgilius1979 - 15-9-2012 at 07:39

Everything written above is very correct !
TACC is more unstable in time and decomposes, so the color changes from blue-violet to green-blue. I had about 15 g of this partially decomposed TACC, and I mixed it with powder Al (about 5:1) in a small plastic bottle, but the mix was not compressed. The explosion was unexpectedly violent and split a 2" steel pipe in two, although the charge was only half introduced into the pipe.
About the comparing of TACC to NH4ClO3, it is not by far that unstable. Amm. chlorate decomposes, if dried, by the next day (you feel a strong chlorine smell), but TACC decomposes slowly in weeks, especially if you open the container and let H2O vapor get inside.
TACP is much more stable than TACC, but also less powerfull (after 2 months it didn't change in color, and burns with the same speed, even after opening the bottle several times).

[Edited on 15-9-2012 by virgilius1979]

C6(NO2)5CH2CH(CH3)N(NO2)2 - 14-4-2018 at 10:58

I have a few questions regarding TACC. This sight gives a "recipe" involving adding anhydrous ammonia gas to a solution of methanol, copper sulfate, and sodium chlorate (https://sites.google.com/site/energeticchemical/calendar). It is said to decompose on exposure to moisture (which is why you can't make it in aqueous solution). Also, it is said to have a very limited shelf life, as noted above. I have two questions: For one, would it be stable if stored dry in an airtight container (eg. in an electric detonator with the ends closed with epoxy). Also, if it does get exposed to some water (either during production or right before use), what will happen? Will it become inert, or will it become more sensitive/ignite spontaneously? I'm wondering if it might decompose like this: Cu(ClO3)2. 4NH3 + 2 H2O > Cu(OH)2 + 2 NH4ClO3 + 2NH3. It seems that two of the main cations which act unpredictably with chlorates are acids (H+ compounds), and ammonia/ammonium compounds. We have one of those things here. Ammonium Chlorate can ignite spotaneously. I believe that is because it forms NCl3, or something. So, I am basically wondering if (a there is a good way to store TACC, and (b if not, would TACC be "safe" to use in a detonator if it were made immediately prior to use. I know that there is no such thing as a "safe detonator" (one criterion for a chemical to be safe is to not be explosive!). If TACC is going to get contaminated with ammonium chlorate just by reacting with air humidity, then we have to assume it will self-ignite at any moment. That makes it unsuitable for anything besides making a few tens of mg and anticipating it to possibly go "bang" on its own.

Bert - 14-4-2018 at 11:04

I have never tried to make this, nor shall I.

As far as I can recall?

This stuff may spontaneously decompose on storage, even when handled by an knowledgable and capable pyrotechnist. There is a description of a related accident in one of the issues of Pyrotechnica.

I will try to find my reference

symboom - 14-4-2018 at 18:17

Finnally a answer to the process of making tetramine copper chlorate is its made an anhydrous alcohol and ammonia gas and used along with sodium chlorate and copper sulfate

Interesting it is water unstable
So this makes tetramine zinc permanganate the second least stable And tetramine copper chlorate in the same catagory
And the most stable being tetramine copper persulfate
Lasting a lot more hours


Great an answer to a reaction between silver nitrate or copper nitrate with tin. Forms hydroxamine?
[Edited on 15-4-2018 by symboom]

[Edited on 15-4-2018 by symboom]

Laboratory of Liptakov - 15-4-2018 at 10:29

Here in picture is method preparation of Cu - KClO3 some.

http://www.sciencemadness.org/talk/files.php?pid=508947&...

woelen - 15-4-2018 at 14:13

No, the most stable is not the persulfate, but the perchlorate.

Laboratory of Liptakov - 15-4-2018 at 23:22

Of course, that tetraamine copper perchlorate is holy grail between all energetic salts. [ Cu ( NH3 ) 4 ] ( ClO4 ) 2.
His properties are exact it, what we need. But few researchers has NH4ClO4. Against HNO3, KClO3 which is easily available. It is main problem, I an estimate.....:cool:

symboom - 16-4-2018 at 00:40


Tetramine copper chlorate
https://m.youtube.com/watch?v=Fj_Z09fTPc4

[Edited on 16-4-2018 by symboom]

C6(NO2)5CH2CH(CH3)N(NO2)2 - 18-4-2018 at 14:54

@Bert: Thanks for the quick reply! Wish I could have got on here again sooner. What you said confirms my suspicions: that the material might decompose over time even when dry. I'm glad you were alright with me asking these questions after only reading a small amount of research on my own (even though I had not done any experiments). Had I read this thread a bit more closely, I would have learned that this material is not really suitable as a primary, because of its low power as well as instability. At this point, this area of research (energetic reactions) is all theoretical for me.
@Symboom: I just realized that the alcohol serves a second purpose, other than to create an anhydrous solution. Apparently, sodium sulfate is insoluble in methanol, so when sodium chlorate and copper sulfate are added, it precipitates leaving copper chlorate in solution. The sodium sulfate precipitate can be filtered out. To create the complex with the Cu(ClO3)2, the ammonia gas is bubbled through the solution. Also, thanks for linking that video! Looks pretty sensitive.
@Laboratory of Liptakov: You're completely right about the chlorate vs perchlorate issue. The perchlorates are definitely better, especially in the case of TACC vs TACP. However, the perchlorates can be hard to get, but chlorates can be found in some weedkillers, or made by heating bleach, or even by an electrical process I think. So almost anyone can obtain them. The idea of a good primary from chlorates was too good to be true! I found an investigation you did with a cap-sensitive mixture of KClO3 and Vitamin C. It had the same type of result I worry about with tetrammine copper chlorate: The material would sometimes stay stable, but sometimes it would ignite unexpectedly due to traces of chloric acid (https://www.sciencemadness.org/whisper/viewthread.php?tid=19...). Thanks for showing those other copper chlorate complexes. They look like almost the same thing, except with ligands a lot more powerful than ammonia. Triazoles and tetrazoles?
I have also learned that as well as acids and ammonium compounds, chlorates can react badly to copper. So tetraammine copper chlorate actually has two chemical incompatibilities!