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aquaregia
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tetraamine copper nitrate sensitivity?
Hi all,
I hope this is the right forum for this post, if not, I do apologyse. I still hope that someone here has an answer to my question...
I made some saturated copper nitrate by disolving some copper in 38% NO3H. I then poured the nitrate solution into 15% concentrated ammonia solution,
where it turned a beautiful deep blue color. Funnily enough doing it the other way round: pouring ammonia into nitrate only makes copper hydroxyde,
why is that?
Anyhow, I kept about 5cc of the solution in a vial. at the bottom of the vial a thick layer of very dark blue cristals have formed. how sensitive is
it?
are these cristals copper tetramine nitrate? Could I have some ammonium nitrate in it as well since the copper nitrate solution was still fairly
acidic?
Is tetramine copper nitrate really a primary explosive? I am concerned with what is laying at the bottom of my vial as I would not like it to blow up
while I handle it...
[Edited on 2-5-2011 by aquaregia]
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aquaregia
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well,
gents, from your lack of response I deducted that this salt was harmless enough and I scaped the cristals and tested them:
It is quite pretty though. trying to burn it with a torch colors the flame in green (as it should). 
[Edited on 2-5-2011 by aquaregia]
[Edited on 2-5-2011 by aquaregia]
[Edited on 2-5-2011 by aquaregia]
[Edited on 2-5-2011 by aquaregia]
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AndersHoveland
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As you can see in the first link, moist crystals of tetraamine copper nitrate (TACN) in a glass tube under flame first seem to melt, then instantly
decompose in an explosive exothermic reaction (not actually a detonation as the thin glass does not shatter)
http://wn.com/Tetraamine_copper_complexes
The poster of this video claims that it can be detonated with only 0.5g HMTD, from the damage caused by the detonation of 100g TACN, it seems much
more sensitive to high order detonation than ammonium nitrate mixtures.
http://www.youtube.com/watch?v=Ua80h7MuRPo&feature=grec_...
Here are some pictures of TACN deflagrating. The salt easily ignites from the flame of a butane torch. TACN rapidly deflagrates with greenish-blue
flare, but there does not seem to be the instant "poof" which is seen with the deflagration of most other primaries:
http://www.youtube.com/user/kuro96inlaila#p/a/f/1/Uj9BkyGo70...
http://www.youtube.com/user/kuro96inlaila#p/a/f/2/HttKMJpJp8...
Edit: the poster appears to have removed the above two videos
There is also a video for tetraamine copper permanganate:
http://wn.com/Tetraamine_copper_complexes
and tetraamine copper persulfate:
http://sites.google.com/site/chemlabchemistry/experiments-1/...
Both of these last two complex salts are much more sensitive, (and probably unstable for long-term storage) than the nitrate.
I think I read somewhere that tetraamine copper nitrate is actually fairly insensitive to mechanical impact, that reliable detonation of this salt
requires another primary. TACN is supposedly also very hygroscopic, and if not free from moisture can be difficult or impossible to ignite. If
preparing the salt for the purpose of deflagration/detonation, pure methanol should be used as the solvent, with dry ammonia gas bubbled in, so that
the product will be free from traces of water.
[Edited on 2-5-2011 by AndersHoveland]
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The WiZard is In
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Study Properties of Tetramino Cupric Nitrate
Title: Study Properties of Tetramino Cupric Nitrate
Personal Author: Phillips, A J
Corporate Author: PICATINNY ARSENAL DOVER NJ
Page Count: 12 page(s)
AD Number: AD0629884
Report Date: 28 JUN 1943
http://tinyurl.com/3rtx2ys
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AndersHoveland
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From the abstract, that paper seems to be only about the unwanted formation of TACN when AN is stored in brass containers, not about the compound's
actual properties.
Apparently, there already exists another topic about the sensitivity of TACN on this forum:
http://www.sciencemadness.org/talk/viewthread.php?tid=2187
Here are some relevant quotes from that topic:
"I can light it with difficulty. If I put a flame of a torch on it, then it first melts and then I get kind of 'poof' with a small cloud of black
smoke. It does not really explode, it is more like nitrated cotton-wool, but with a less visible flame." (woelen)
"the problem (from an energetic aspect) is going to be hydration." (Axt)
"Yesterday i tried to make TACN by dissolving 2g pure copper and 5g ammonium nitrate in 10ml 10% ammonia sulution.
After 1 day the solution turned blue and bright blue crystals formed at the copper. I filtered the solution and ended up with 0.7g with crystals. I
dried them well. Then i tried to detonate it. It got a very little "poof sound" and some smoke came. I also tried to use CuO insted of pure copper. I
ended up with some very dark blue\purble crystals after i filtrated it. When i heated them up, nothing happend." (mikkello, who is from Norway)
"TACN is easily dehydrated in dry acetone, forming a stable dull-violett powder. Put the crystals in a beaker filled with dry acetone, crush them
carefully, stirr and let it sit for a short time. The acetone will take up the water of crystalization. Pour off the acetone (which now contains
water) and wash with another portion. Repeat until the color of the crystals no longer changes. Of course this works best with dry reagent grade
acetone, but I tried it with the crappy comercial stuff (which contains a considerable amount of water) and even that worked fine. Then decant and
press dry between filter paper. Let the crystals dry in warm air until all acetone has evaporated. Then do a final drying over CaCl2. During the
acetone wash you will notice the chunky crystals change color from deep blue to a light violet and turn into a fine powder. This powder is stable in
air and quite powerful. Its quite sensitive too - smack with a hammer and it goes boom. This is the only useful form of TACN. The hydrated form cannot
be stored because it readily draws CO2 from air. It is also very insensitive and weak. I observed the same effect with TACP: The hydrated form is
useless. It can hardly be ignited with a match and is very insensitive to impact. Remove the water of crystalization and you get a much more sensitive
and powerfull substance. Of course these materials must be stored in a well stoppered bottle to exclude moisture. From the hydrated form of TACN you
will hardly get anything more impressive than a pop sound and some smoke." (edited compilation of quotes from Taoisearch)
[Edited on 2-5-2011 by AndersHoveland]
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The WiZard is In
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Study properties of terammino cupric nitrate
What I take from this is that it is not a primary explosive. It cannot
be detonated by flame. Its Sand test value is close to
to that of lead azide so detonating it could be harmful.
This is a touch more info in PATR 2700. I looked up the ref they
give for Mellor 3:284 nothing on its explosive properties, a check
of DuPont's British patent could be useful.
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aquaregia
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Thx
Thanks to both of you for your replies and valuable information. I have very little interrest in explosives, only in chemistry, which I am starting
again after a 15 years break... My original query really was to make sure I was safe handling that compound. Regarding the "light blue" cristals
obtained from desolving Cu into NH4NO3 solution, I would think that these cristals might be heavily contaminated with ammonium nitrate since copper
tetramine really is deep, deep blue. Also I have doubts, regarding the hydrophylic properties of this compound... The cristals pictured above are now
completely dry (i.e not deliquecent). It does not seem at all like it is "sucking" moisture out of air, as NH4NO3 would (if I remember correctly).
Again, I suspect this compound to be heavily contaminated with NH4NO3 in some cases which can affect tests...
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AndersHoveland
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No, it should actually be considered a primary explosive, although it seems less sensitive than many other primaries, but it can be difficult to
reliably initiate. If free from water, it will deflagrate if subjected to the intense flame of a butane torch. Like other primaries, the deflagration
likely will lead to detonation if the mass of TACN is more than a few grams and there is a small degree of confinement, such as in a little rolled up
paper tube.
The main problem seems to be hydration. Although the crystals of TACN may appear dry, it is quite likely that molecules of water become incorporated
into the solid crystal structure. CuSO4 is known to form such a solid hydrate CuSO4*(5)H2O. For reliable use as an explosive, TACN needs to be
prepared without water, and be kept away from long exposures to air.
Here is a video picture showing a sample of anhydrous tetraammine copper(II) sulfate. It has a light indigo color with a slight violet tint. When left
in open air, it quickly absorbs moisture from the air, with an associated color change to the more common blue form, with a slight greenish tint.
http://www.youtube.com/watch?v=a2GyhcaiWuY
[Edited on 3-5-2011 by AndersHoveland]
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chemoleo
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Any idea as to how much HNO3 was left when the ammonia solution was poured in? What were the quantities, in molar equivalents?
You say that a precipitate of copper hydroxide was formed when adding ammonia to your copper nitrate/HNO3 solution, what happened when you started
mixing these well?
In theory, there should be no precipitate - as any Cu2+ should be complexed; Cu(NH3)4(OH)2 is also well soluble in water.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Jor
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Quote: Originally posted by AndersHoveland  | As you can see in the first link, moist crystals of tetraamine copper nitrate (TACN) in a glass tube under flame first seem to melt, then instantly
decompose in an explosive exothermic reaction (not actually a detonation as the thin glass does not shatter)
http://wn.com/Tetraamine_copper_complexes
The poster of this video claims that it can be detonated with only 0.5g HMTD, from the damage caused by the detonation of 100g TACN, it seems much
more sensitive to high order detonation than ammonium nitrate mixtures.
http://www.youtube.com/watch?v=Ua80h7MuRPo&feature=grec_...
Here are some pictures of TACN deflagrating. The salt easily ignites from the flame of a butane torch. TACN rapidly deflagrates with greenish-blue
flare, but there does not seem to be the instant "poof" which is seen with the deflagration of most other primaries:
http://www.youtube.com/user/kuro96inlaila#p/a/f/1/Uj9BkyGo70...
http://www.youtube.com/user/kuro96inlaila#p/a/f/2/HttKMJpJp8...
Edit: the poster appears to have removed the above two videos
There is also a video for tetraamine copper permanganate:
http://wn.com/Tetraamine_copper_complexes
and tetraamine copper persulfate:
http://sites.google.com/site/chemlabchemistry/experiments-1/...
Both of these last two complex salts are much more sensitive, (and probably unstable for long-term storage) than the nitrate.
I think I read somewhere that tetraamine copper nitrate is actually fairly insensitive to mechanical impact, that reliable detonation of this salt
requires another primary. TACN is supposedly also very hygroscopic, and if not free from moisture can be difficult or impossible to ignite. If
preparing the salt for the purpose of deflagration/detonation, pure methanol should be used as the solvent, with dry ammonia gas bubbled in, so that
the product will be free from traces of water.
[Edited on 2-5-2011 by AndersHoveland] |
It's funny you post the last link. It's my old website, I even forgot about it 
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aquaregia
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@chemoleo
What I did mention is that dumping the ammonia into Copper nitrate solution produced cupper hydroxide precipitate as well as copper tetramine, while
dumping the Cu(NO3)2 into ammonia did produce the tetramine and no precipitate whatsoever. The nitrate solution was saturated, with some acid left.
unfortunately, I did not perform a titration (no very professional, I know!). the ammonia was household 13% concentated. the end product still smelled
of ammonia which means there was more ammonia than nitric acid reacting.
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aquaregia
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What I'll try to do is dehydrate a few mg in acetone, and see how it fares.
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The WiZard is In
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Anhydrous?
The primary explosive tetramminecopper chlorate is made
by dissolving copper sulphate in the obvious non-aqueous
solvent and bubbling in ammonia gas. One wonders what
would result if anhydrous copper nitrate dissolved in whatever
works non-aqueous solvent ammonia gas was used?
NB - Making anhydrous copper nitrate takes a bit of chemistry
for as la books sez it was previously though that Cu(NO3)2
could not exist.
Wonder I too - two. How 'bout using Na3NO4?
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AndersHoveland
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Anhydrous Cu(NO3)2 is apparently very reactive;
"at temperatures below –5°, the reaction of diethyl ether with copper(II) nitrate yields exclusively gaseous ethyl nitrite and complexed
acetaldehyde. At higher temperatures, the acetaldehyde is further oxidised to acetate, with liberation of gaseous NO and NO2"
Anhydrous copper(II) nitrate as an oxidising agent. L. C. Coard and R. E. Powell
J. Chem. Soc. A, 1967, 296-297
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aquaregia
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tested it dehydrated
Right, I dehydrated the above (see photo) in acetone after reducing it to a fine powder in a mortar and pessle. and....
It deflagrates energetically!
I'd say it is an explosive, but, quite insensitive, while crystalised (bound water in matrix).
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QHarryQ
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Can I get the dehydrated form of TACN by baking it for 4 hours at the tempreture abaout 50 ℃？Because acetone costs a lot and I think it's
not worth dehydrating TACN with acetone.The baked TACN seems to be really dry.When I burn it,it melts at first and then deflagrates with a "poof".Then
little black solid(CuO perhaps) is left,is it the dehytrated form of TACN?
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Etanol
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VoD of TACN
Hello, friends
Someone asked me to test Detonation Velocity of [Cu(NH4)4](NO3)2
TACN vs frozen trees (-10С)
http://youtu.be/YaCLTWsHEpI
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TGT
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I did this awhile ago and thought my notes on making it might be useful to some that are interested. Just making it for the beautiful crystal
formation is reason enough to follow through on the procedure.
---------------------------------------------------------------------------------------------------
How to Make Tetraamminecopper[II]nitrate (TACN) with Copper Metal
Materials: Several copper pennies, 2 - 500 ml beakers, glass stir rod, concentrated Nitric Acid, liquid Ammonia, water (preferably distilled, but
clean tap water will work also) and optional is a coffee filter or paper towel.
Procedure: Pour 75 ml of nitric acid into a 500 ml beaker and then put in three copper pennies. Stir as needed and be sure to do this under a
fume hood or outside as the gasses are very poisonous. After they are dissolved or the reaction has calmed down add another two pennies and
stir. Continue slowly until as many pennies will dissolve into the solution. Usually this is about 5 or 6 if the acid is really strong. If the
reaction stops before some of the copper pennies are dissolved, take them out. You should now have a fairly concentrated solution of copper
nitrate and it should be clear, light blue to dark blue in colour.
Next, get some Ammonia and pour into the blue copper nitrate solution a small amount and stir with your glass rod. You should immediately see a
precipitate form. This is copper hydroxide. As you slowly add more you will start to see a beautiful dark blue liquid form on the surface and
disappear into the chunky light blue solution. Keep adding more and stirring until the precipitate dissolves and the dark blue begins to
remain. The solution should soon turn a dark blue/purple colour that is clear and not cloudy. This is what you want. You can hold it up to the
light or use a small flash light to shine through and see if it is clear. After you are sure it is ready, add just a tiny bit more ammonia to
ensure the reaction is complete and then stir for a few minutes longer.
Note: I have read many times that others say to add the copper nitrate solution to the ammonia. The reason they say this is, there has to be an
over abundance of ammonia so that yield will not be contaminated by copper hydroxide. This is true but I have done it this way many times and
my way still ensures an over abundance of ammonia. As long as you add enough ammonia to the solution until it goes clear you have successfully
rid the solution of copper hydroxide. Once it is formed does not mean it will not successfully convert to TACN if more ammonia is added.
The reason I do it this way is not just to be different. It is because all store ammonia concentrations are never the same so there is not an
actual amount I can give you to mix. My way when the solution goes clear you know the reaction is complete and knowing the molarity of ammonia
is not needed. Still, some suggest to do it their way and that is fine, what ever works for you. But, I find some times you end up adding too
much ammonia and then have problems with crystal formation. I assure you my way has worked many times for me in the past and I have always
procured a good yield with no copper hydroxide impurities.
So continuing on, after a good stir let the solution sit for 24 hours. After this time you should be able to slowly pour out the remaining
liquid into the other 500 ml beaker leaving your TACN crystals behind. They are usually stuck to the bottom of the beaker and are amazingly
beautiful in shape and colour. Just the looks of them should be a good enough reason for anyone to do this project at least once. You can
strain it through a coffee filter if you want to catch all of them, but I find the purist crystals will stick to the bottom and the remaining
floating pieces might not be as pure, so I don't bother. The majority of yield will be on the bottom stuck to the glass and up the sides.
After removing as much liquid as possible, place your beaker with crystals somewhere warm like near an incandescent light or on top of a fridge.
This will dry the crystals quickly. Do not place them in the sun to dry as sun light has been known to decompose them. Once dry, grind them
up and put them into a bottle and they should keep for years if kept out of light, remain dry and fairly cool. When dry and ground up the
crystals form a beautiful violet colour and are not terribly hygroscopic like some have suggested. At least this is my own personal
observation.
TACN can be considered a high explosive, but it is not sensitive and you should not worry about storage. To detonate you would need probably a
number 8 blasting cap and I believe the VOD is 3600 meters per second. Storage is not dangerous and also static is a non-issue. The powder
does ignite and give a quick burst of energy similar to gun cotton, but first the powder must totally liquefy and evaporate, making
accidental ignition almost impossible. If it did ignite it would only deflagrate and not detonate. A blasting cap is needed for that.
No Crystal Formation?
If you find that after letting the beaker full of solution sit for 24 hours and still you have no crystal formation, it may be because you added far
too much ammonia. All is not lost and usually this can be fixed quite easily. Mix in one half the amount of solution you have with ethanol (at least
95%, although some lower percentages probably will also work, but more would need to be added) and then place the beaker in the fridge. This should
force crystals to form in 12 to 18 hours. When the time expires, you can try again and pour out the solution to recover the crystals. This has
happened to me when I tried adding the solution to the ammonia and I didn't properly predict the amount needed. With this fix I still got an
excellent yield.
----------------------------------------------------------------------------------------------------
Sorry for weird format errors, my copy past from my notes didn't go as planned, but should be legible enough.
TGT
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Laboratory of Liptakov
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TACN sensitivity?
Hmm ... Interesting. But: Use concentrated HNO3 for production TACN? It is in my opinion a shame. And what about the sensitivity? Maybe No. 8?
(Subject: tetraamine copper nitrate sensitivity?) You have made some tests? For example ETN 0.3, or HMTD 0.3 or LA 0,3g or FHg 0,4g? It detonate pure
powder TACN? Density?....... .......LL
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Fantasma4500
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i think by concentrated he means below azeotrope..
TACP or anhydrous TACN could be interesting, recall theres some hexamine copper ammonia complexes that can be formed, but the question would be if
these complexes can be isolated or 'concentrated'
AN molten and CuO added should form more or less anhydrous TACN, but the question would be to isolate it again...
using *a specific ammonium fertilizer which is not a good idea to mention* ammonia and copper have been done before to produce TACN, but it takes long
time, gradually becomes more and more intensively coloured
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TGT
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TACN does detonate if a large booster is used. I have filled a test tube with TACN, about a third full, then Picric Acid another third, then the last
third (or close to) with ETN. I detonated it with a sparkler (I know, not very technical) with a band of loose ETN wrapped in tin foil, then wrapped
around the sparkler and placed in the top of the test tube. It was detonated in a large box so that I could see if any explosive compound was not
detonated. There was no undetonated TACN left to be seen, so I assume it detonated fully, especially how large the explosion was.
I know this is not a controlled experiment, it was really all just for curiosity and fun, so take this info as is. Hopefully in the future I will try
more controlled experiments with TACN. I still have almost an ounce left to fool with. Just for informational purposes, the TACN I have is now over
a year old and no sign of color change or decomposition has happened to my knowledge. Although it has been kept in the dark and a consistent
temperature of around 20 to 25 degree's celcius. Also, it is not very hygroscopic as everyone seems to think.
TGT
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Laboratory of Liptakov
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safety
TGT. It seems that many do not know about TACN. You've read the thread Cyklonan? Modified TACN can detonate only 0.3 g LA, or HMTD. And you look at
the thread HMTA safety. Use sparklers are dangerous. Very.... ...LL
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TGT
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Thanks for the safety info, I will look at the thread Cyklonan. The sparkler I understand is dangerous because of the chance one of the sparks can
fall into the energetic material being used and ignite prematurely. But, I take all precautions necessary and make sure the device is sealed well at
the top so that no stray sparks will ignite it. I will read the thread and if I missed something please let me know. Thanks.
TGT
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Laboratory of Liptakov
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TeACN
If you use a sparkler, a bomb buried in the sand is not possible. For example, 10 g TACN composition makes a horrible noise. I recommend using an
electric initiation. A pit with sand. It is safe and discreet. In the pit you can do a lot of accurate tests. The sensitivity of net TACN, different
densities, different types of initiation. Available information TACN are still unclear. For all researchers. If you do research in this direction, it
will be a benefit for all ......LL
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Little_Ghost_again
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Those are amazing crystals! I wonder if there is a safe way to store them for display? or maybe make something very similar thats not actually an
explosive, Iron and copper compounds are the crystals I like the most
Dont ask me, I only know enough to be dangerous
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