Sciencemadness Discussion Board - TACC

TACC

Madog - 27-5-2002 at 16:16

okay, i was reading about TACC the other day, i used to be very intertested in this but i just never got to make any because i got no CuSO4

i thought of my own method of preperation. it says that TACC is made by bubbleing amonia through a solution of Cu(ClO3)2

well, i figured maybe u could make it like this

Cu + 2HCl --> CuCl2 + H2

CuCl2 + H2O + (electricity) --> Cu(2+) + 2Cl(5+) + H2 + 2O(2-)

Cl(5+) + 3O(2-) --> ClO3(1-)

Cu(2+) + 2ClO3(1-) --> Cu(ClO3)2

Cu(ClO3)2 + 4NH3 --> Cu(NH3)4(ClO3)2

so, do u think this will work? i probaly have the last 3 reactions messed up but i know that if u electrolisize a XCl in a solution of water with the anode and cathode placed correctly (so the Cl bubbles over one, i forget the details) it will make XClO3

look in KIPE1 to see a thing on this being done with KCl

oh, and another thought. what about boiling CuCl2 with bleech or HTH?

edit: i fixed the crapy reactions

[Edited on 5/31/02 by Madog]

kingspaz - 23-7-2002 at 06:26

that seems like a good idea although i'm not sure how easily HCl would attack the copper. it may take a while to react all the copper and also some heating. maybe a better idea would be to use CuO powder from a pottery supply place:
CuO + 2HCl ---> CuCl2 + H2O

PHILOU Zrealone - 8-9-2002 at 12:29

Cu is related to noble metals in many regards and is corroded significantly only by strong oxydising acids.
So actually it is easier to get CuCl2 from Cu wire heated and dropped in Cl2 jar.But if you are patient, some should occure from HCl + Cu if in contact with O2...to add some H2O2 or HNO3 or H2SO4 will speed up the reaction significantly.
Grinding Cu to get Cu powder and heat it in a flow of O2 will give you CuO (black) that dissolves quite fast in conc HCl.

Unfortunately for you CuCl2 electrolysis only result in Cl2 evolution and Cu plating!

The Chloride to chlorate and perchlorate process is only true for alkaline and alkalinoheart metals like Li, Na, K, Mg, Ca, Sr, Ba that have metals that can't be isolated in water since they decompose it as soon as they are formed!
NaCl -aqua/eletrolysis-> Na + 1/2Cl2
Na + H2O --> NaOH + 1/2H2
Cl2 + H2O --> HOCl + HCl
HCl + NaOH --> NaCl + H2O
NaOH + HOCl --> NaOCl

NaOCl + NaOCl --heat --> NaOClO + NaCl
NaOClO + NaOCl --heat --> NaOClO2 + NaCl
NaOClO2 + NaOCl --heat--> NaOClO3 + NaCl
2NaOClO + NaOClO --heat--> 2NaOClO2 + NaCl
NaOClO + NaOClO --heat--> NaOClO3 + NaCl
2NaOClO2 + NaOClO --heat--> 2NaOClO3 + NaCl
3NaOClO2 + NaOClO2 --heat--> 3NaOClO3 + NaCl

To get Cu(ClO3)2 you should dissolve Cu(OH)2 or CuCO3 or CuO in a solution of HClO3 (HOClO2) made from Ba(ClO3)2 solution in distillated water and reacted with H2SO4.
HClO3 solution is strongly acidic and decompose over 35% so don't make it too concentrated (since the toxic and spontaneously explosive gas ClO2 will evolve: this gas is responsible of the explosion and fire when H2SO4 is dropped on KClO3/suggar mix and of the unstability of Chlorates towards sulfur and phosphor that contains traces of H2SO4 or H3PO4!).

If I were you, I would go for TACuP instead of TACuC.
Cu(NH3)4(ClO4)2 should be more stable, more powerfull about as sensitive as Cu(NH3)4(ClO3)2.

Ba(ClO4)2 + CuSO4 --> BaSO4(s) + Cu(ClO4)2
Cu(ClO4)2 + 4NH3 --> Cu(NH3)4(ClO4)2

Enjoy!

PH Z

Madog - 8-9-2002 at 18:22

thanks!! i would like to synthisise some HClO4 and make various perchlorates includeing Cu(ClO4)2 and then TACuP. these compounds interest me

i wonder if there are any organic perchlorates that are sane to make. hmm, perhaps cellulose perchlorate or maybe hexamine perchlorate, that is something i have been thinking about for a while, seems like it would hurt me though.

PHILOU Zrealone - 10-9-2002 at 13:56

Cellulose perchlorate would be an ester of perchloric acid and is prone to detonate spontaneously upon standing...it is only something to play with in tiny amounts and to enjoy immediately; never store.
To see the power of HClO4; you put a drop of it on a sheet of toilet paper...paper will melt and make a kind of glue so rool it over itself and drop that in a fire outside...enjoy the lightnings and sharp cracks from a safe distance...this will show you the real power of perchloric esters and their potential hazard if they runnaway spontaneously in your lab/house!

Salts of amines and perchlorates are all safe until heated or in contact with a flame; moderately sensitive to shock but stil sensitive; very sensitive if transition complexating metals are involved --> primaries most of the cases or sometimes spontaneous ignition/explosion.

It is always a good idea to keep batches smaller than 10g and to dry them 1g at the time.I once had 500mg hydrazine perchlorate detonation in my kitchen on a hot plate (the stuff burn normally upon contact with a flame but shock on a hot plate...damn, my spoon was twisted arround my hand and flew spinning fast at 3 meters high,it had a notch on the side and my ears remember the noise).

Also while making use diluted acid and amines because neutralisation generates quite a lot of heat...if too concentrated heat can be excessive and opperate on nearly anhydrous amine perchlorate.Reaction of 20% concentration reactants is already quite hot!

PH Z

TACC

MRS_X_TSALB - 20-11-2002 at 08:21

Is this simple reaction a good idea to keep TACC
without destroing it, possibly in presence of a
suitable catalyst wich can beside separating the NaCl
from the mixture ?

[ 0,25 CuSO4 + 0,5 NaClO3 ] + [ NH4Cl + NaOH ] -->
[ 0,25 [Cu(NH3)4](ClO3)2 + 0,25 Na2SO4 ] + [ NaCl + H2O ]

KABOOOM(pyrojustforfun) - 10-12-2002 at 17:43

don't use H2O2 in TACC batch Cu++ reacts with H2O2 to form Cu2O3 and CuO2(out of topic this compound seems interesting as an oxidizer

)

[Edited on 16-3-2003 by KABOOOM(pyrojustforfun)]

TACN

alien14305 - 11-12-2002 at 13:27

Does anyone here know anything about TACN? This seems to be easier to make then TACC due to a main precursor being a nitrate instead of sodium chlorate. I have been trying to find some good info TACN but its been hard, there even less info on this primary then TACC.

Polverone - 11-12-2002 at 22:32

There has been some discussion of TACN on the E&W Forum. All results seemed to indicate that it was very difficult to prepare, because it was extremely hygroscopic, and it needed to be anhydrous to exhibit much in the way of explosive properties.

Marvin - 17-12-2002 at 04:11

Same is true of TACC, it gets wet, its a write off, decomposes if you try to dry it, and loses ammonia anyway.

formation of NH4ClO3?

blazter - 27-12-2002 at 19:53

After thinking about the standard procedure of synthesizing TACC, it has occurred to me that there is a possibility of producing NH4ClO3 while bubbling ammonia through the solution. Assuming that the chlorate does not completely react with copper compound, there will still be some residual chlorate ion left in the solution. My question relates more to ammonium chlorate than the actual TACC because i am curious as to how hazardous this compound would be if it indeed occurred in trace quantities. Also i have read little information about NH4ClO3 as far as its properties go, other than it being dangerously sensetive.

It seems that the risk may be lessened somewhat by letting the solution return to room temperature after refluxing and before filtering, so that extra unreacted chlorate would be filtered out as it precipitates from the solution.

Anyone have any ideas as to exactly how hazardous the ammonia addition is to the copper chlorate solution in light of these concerns, or am i just being paranoid?

Madog - 28-12-2002 at 14:36

its insanely unstable. it is said that it will oxidise things in a similar fasion to Mn2O7. its *really* sensitive. if you are up to it and want to learn more about it perhaps you could make a solution of it, put it on some paper, and let it evaporate and see if the paper cauches on fire. im not sure if you can really isolate it. and if you could you would want to do it in really small quantities

kingspaz - 28-12-2002 at 16:09

blazter, the remaining chlorate ions in the solution will be balanced by the remaining copper ions in solution thus a solution of copper chlorate. you can't have a solution with slightly more negative ions. to som extent NH4ClO3 probably does form but i'd say the instant it does it would likely revert back to the ions from which it was made.

rikkitikkitavi - 29-12-2002 at 09:08

consider also that NH3 binds to Cu2+ in a complex ion, a very strong one to, meaning there is little free NH4+ in solution to form NH4ClO3.

One example. I was trying to dissolve
CuO in (NH4)2SO4 by boiling.

CuO(s) + (NH4)2SO4 => [Cu(NH3)2]2+ + H2O + [SO4]2-

Immediately a violett-blue complex formed, and after several hours of boiling all CuO had dissolved (I used 2 times excess (NH4)2SO4) but I could only smell the faintest of free ammonia.

/rickard

Copper tetraamine nitrate

chemoleo - 26-7-2003 at 23:00

hmm, I hope I am not totally mistaken but I seem to remember an experiment I did a long time ago - adding ammonia solution to a copper nitrate solution. I remember a colour change (so something HAS to happen), and isolating it by cyrstallising it/ evaporation.
The resulting crystal powder, as far as i remember, did sort of burn, leaving a brown residue (copper chloride/oxide?), but nothing like a fast burn or potential explosion if hammered hard... never pursued this tho. Any thoughts?
(oh, its coming back - I made this to create a blue flame, and it seemed to work to some extent if in a mixture with KClO3+sugar)

CROpyrO - 29-7-2003 at 09:12

is it going to work if i put some ammonia water instead of bubbleing ammonium ? im interested in TACC becose i have all the things i need. if somebody knows some good links where i can find info about TACC , post !!! i was already by magalomania ....

Nick F - 29-7-2003 at 09:45

Ammonia solution will work in theory, but you'll have to carefully dry the product after making it. It is very water-soluble and won't work if it's damp.
It is better, though more complicated, to use alcoholic solutions, not aqueous. Form the copper salt by mixing alcoholic solutions of copper sulphate and the corresponding sodium salt (chlorate, nitrate, whatever). Sodium sulphate is insoluble in alcohol, so it pptes, leaving your copper salt in solution in the alcohol. The preferably bubble in dry ammonia, or add the strongest ammonia solution you can find, and evapourate to begin crystalisation. Filter the crystals out and dry them.
There are aminometal oxosalt complexes which work well, but I have never had a lot of luck with ammonia. I have used guanidine, nitroguanidine, and aminotetrazole and all of these form very promising substances with copper or nickel nitrate. The only problems I have with these are a very limited supply of guanidine/nitroguanidine, and aminotetrazole isn't very soluble in alcohol or water.

KABOOOM(pyrojustforfun) - 31-8-2003 at 04:21

rikkitikkitavi I think this reaction happend:
CuO(s) + 2(NH4

2SO4 => [Cu(NH3

4]2- + H2O + 2[HSO4]- u boiled the solution causing some of the ammonia liberate. I think ammoniated copper salts don't just absorbs water becoming wet but form hydrate salts. for example when dissolving CuSO4 in NH4OH then adding alcohol Cu[NH3]4(SO4

2.H2O is precipitated.

Zelot - 22-3-2008 at 14:43

For every page I see about TACC, it says that it is decomposed by water. That means that you have to make it in an anhydrous solution. Every synthesis says to use either absolute methanol or ethanol. Do you think that you could use acetone or methyl ethyl ketone instead? And they say to use sodium chlorate, but do you think that you could use potassium chlorate?

I have made copper sulfate and I can get potassium chlorate. I made the copper sulfate by electrolysis of magnesium sulfate with copper pipe as electrodes, and filtering. I know I can get potassium chlorate from armstrong's mixture. I just want to make sure the synth will work before I use up some of my limited acetone or MEK.

The_Davster - 22-3-2008 at 14:46

Quote:

Originally posted by Zelot
I made the copper sulfate by electrolysis of magnesium sulfate with copper pipe as electrodes, and filtering. .

You do not have copper sulfate. Your precipitate is copper hydroxide. You will need to dissolve this in sulfuric acid and then crystallize to get copper sulfate.

Zelot - 22-3-2008 at 21:57

Are you sure that it won't make copper sulfate? Then where does the SO4 ion go? The magnesium from the MgSO4 changed into MgO, and lots of blue crystals were formed. I guess it could be CuOH, but I'm not sure.

BTW, if I had sulfuric acid, I wouldn't bother with TACC.

The_Davster - 22-3-2008 at 23:44

cathode
H2O+2e- -->2H2 +2OH-
anode
Cu-->Cu2+ +2e-

Cu2+ +2OH- --> Cu(OH)2
also Mg2+ +2OH- -->Mg(OH)2
The electrolysis will initially produce Mg(OH)2 and the copper ions will stay in solution, but as the electrolysis continues, or if the solution is stirred, the copper ions will reach the cathode side of the cell and precipitate out as the hydroxide. You would need a divided cell to isolate pure CuSO4

However, if Mg2+ has a much higher mobility(which I don't particularly want to calculate now) than Cu2+ it will be attracted to the cathode faster, but that would still leave your copper(II) in solution, you would have to evaporate to isolate it, you would not obtain it by filtering unless your solution was quite concentrated

Tell me more about how the experiment was done, you may have done it differently than I am envisioning, leading you to somehow isolate CuSO4.

Zelot - 23-3-2008 at 08:31

Well, I got a glass jar, and dissolved as much epsom salts as I could into it. Then I cut two sections of copper pipe and connected those to the 1 amp charger. I submersed the pipes, and bubbles of hydrogen and oxygen came out. I left it to do its thing and left for school. When I got back, the anode was completely dissolved, there were crystals growing on the cathode, and a layer of crystals on the bottom of the jar. I put the stuff through a couple of coffee filters, and dried the crystals in the oven.

The anode and cathode were not that far apart. Maybe an inch or two. There was also a white powder growing on the cathode, which I assumed to be Mg(OH)2.

The_Davster - 23-3-2008 at 12:49

Ok, the concentration issue is what did it. Your concentrated MgSO4 electrolyte means that the copper sulfate would crystallize out as it is formed. I assumed dilute electrolyte. It may still have Mg(OH)2 contamination, so you could dissolve your copper sulfate crystals in water, filter out the insolubles and then crystallize the filtrate and that should clean it up a bit.

Taoiseach - 24-3-2008 at 03:43

"For every page I see about TACC, it says that it is decomposed by water. That means that you have to make it in an anhydrous solution"

No it can be made in aequous solution. Just make a conc. solution of copper chlorate (can be made from Ba(ClO3)2+CuSO4) and pass in ammonia until saturated. Cool down in the fridge. Plenty of blue crystals will form upon cooling.

It is useless stuff tough and possibly dangerous to store. It decomposes even in a sealed glass jar. Make the perchlorate complex - it keeps well for years and isn't moisture sensitive. Or go for the nickel chlorate, it keeps perfectly well too and due to its very low solubilty it precipates even from dilute solution.

Btw. the corresponding zinc ammine is useless as well (hygroscopic and decomposes within weeks).

Zelot - 1-4-2008 at 14:40

Quote:

Originally posted by Taoiseach

*snip*
Make the perchlorate complex - it keeps well for years and isn't moisture sensitive. Or go for the nickel chlorate, it keeps perfectly well too and due to its very low solubilty it precipates even from dilute solution.

Btw. the corresponding zinc ammine is useless as well (hygroscopic and decomposes within weeks).

If I had some perchlorate, I probably would make TACP. What do you mean by "the corresponding zinc ammine"?

woelen - 2-4-2008 at 22:51

A zinc ammine is a zinc ammonia complex. IIRC [Zn(NH3)2](2+), but I am not really sure about the number of ammonia molecules in the complex.

Zelot - 4-4-2008 at 14:07

I think I'll try TANC, or maybe TANN. Nickel is less expensive than copper. Does anyone know something about Tetra Amine Nickel Nitrate? It seems easy to synthesize, just add metallic nickel to an ammonium nitrate solution...

Taoiseach - 5-4-2008 at 03:10

I think there are 4 molecules of NH3 in the zinc ammine. The persulfate, chlorate and perchlorate are explosive but none of them is stable AFAIK. The persulfates are especially dangerous.

Hexamminenickel(II)nitrate is indeed easy to prepare. Unlike the corresponding copper complex it is stable in air. Bubble NH3 trough a hot saturated solution of nickel nitrate, then cool down in the fridge. Or put nickel wire into a hot AN solution, bubble air through it until all dissolves. Then add ammonia and cool down below 0°C. Reactions going on should be:
2Ni + O2 --> 2NiO
NiO + H2O --> Ni(OH)2
Ni(OH)2 + 2NH4NO3 --> Ni(NO3)2 + 2NH3 + 2H2O
(I dont know if nickel is able to reduce NO3(-) under these conditions but I doubt it. I think air will be needed to oxidize Ni to Ni(2+))
So per mole of Ni you get only 2 moles of NH3. You need to add ammonia to provide the 4 missing ligands to form [Ni(NH3)6](2+). Use in large excess because quite some NH3 will escape when you heat the solution.

The complex forms nice & dry non-hygroscopic blue crystals. It is very insensitive, comparable to TACN. I doubt it can be detonated without lead azide or a comparable primary.

Its possible to grow BEAUTIFUL crystals of it tough so its definetely worth making!!

Zelot - 7-4-2008 at 17:35

I have done some thinking, and want to make some nickel chlorate. The only problem is, where to get nickel and how to get it into solution. Are US nickels made of nickel, or are they an alloy?

not_important - 7-4-2008 at 19:38

There is at least one thread on this. US 5 cent coins are 3/4 copper, 1/4 nickel. That alloy can be used as a source of nickel, as can be nichrome and other heatring/resistive wire.

Often pottery supply houses sell nickel compounds; carbonate, oxide, and sulfate are the common ones.

Formatik - 8-4-2008 at 09:44

Quote:

Originally posted by Zelot
I have done some thinking, and want to make some nickel chlorate.

Hexamminenickel (II) chlorate makes a poor initiator according to Ephraim and Jahnsen (didn't ignite tetryl). Under a flame it decomposes weakly, and in a test tube ignited with a fuse it burns slowly. In a capsule pressed to 80 kg/cm it would not ignite. It detonated partially when a non-initiating ignitor was added to it in order to make it ignite, but it did not cause a significant indentation on a lead plate.

The [Ni(NH3)6](ClO3)2 is a blue solid (d=1.52), averg. expl. temp: 210 deg., shock sensitivity: 25 cm with 2 kg weight (47 cm with 1 kg weight). Trauzl: 68% of TNT. The azide and bromate variants are noted to lose NH3 at
room temperature.

Tetramminezinc (II) chlorate precipitates from the preparation solution only if it is saturated entierly with ammonia and the solution kept cool. They are colorless crystals that resolubilize if let stand in the mother liquor. In its behavior it is said to be similar to the copper and nickel salts. Tetramminezinc (II) chlorate is 79%, and the perchlorate is 70% of TNT in the trauzl test. There is also the hexammine coordination compounds of zinc, Zn(ClO3)2.6NH3 will form from the tetrammine although the tetrammine does not absorb any more NH3 at room temperature, in the cold it does. The tetrammine chlorate coordination compound is sensitive (2kg at 15 cm).

In general E & J note about ammonia ammine halogenates:

1)Decomposition temperature of the bromates is not much lower than the chlorates, but the shock sensitivity is much greater (e.g. 2 cm with 2kg for Cu- or Zn(BrO3)2.4NH3 compared to 15 cm for both the respective chlorates of those metals)

2) Ammine iodates: (of Cu, Ni, Zn, Cd) do not explode when heated in air or impacted, but from 20 cm height (2kg) there is seen some decomposition (localized)

3) Their prospects as initiators are gloomy. Especially since the moisture in the air replaces a NH3 molecule with a H2O. For the speed of this you have to see more of their work on this.

Not only with ammonia, but with many other nitrogenous bases are complexes formed e.g. monoamines (allylamine, ethanolamine, methylamine, etc), ethylenediamine, hydrazine, etc. All can be expected to show differing stabilities and sensitivity, like the copper chlorate hydrazine compound Cu(ClO3)2.2N2H4, which is a colorless salt that detonates upon drying in air after about 4 minutes, and at 35°C it takes a few seconds.

Sources: PATR A275-86. And Ephraim and Jahnsen, Ber., 48. pgs. 41-56. Gmelin "Cu" p. 335.

Quote:

The only problem is, where to get nickel and how to get it into solution. Are US nickels made of nickel, or are they an alloy?

If you have any, older Canadian nickel coins are pure nickel.

Phantom - 21-8-2011 at 02:03

First of all it is not a primary explosive. It is very easy to make. You'll need only NH3, NH4NO3 and CuO. It has about 3600m/s

[Edited on 21-8-2011 by Phantom]

plante1999 - 29-2-2012 at 07:58

Does someone have succefully made tacc? I have tried to make some by boiling 25ml methanol/ 2.5g CuSO4/ 1.5g KClO3 and than filter, I get neon green sol. of copper chlorate and than I passed ammonia gass trougth the sol. When it started to smell stronghly ammonia I stopped to pass ammonia and I filtered, I think I got copper hydroxide since the salt did not disolve in water/methanol. I dried the salt and heated it with a torch, It seam to release ammonia when heated but it is not energetic at all. (my objestive is not to to explode something , simply to explore the proprety of coordination complex.

Thanks!

Formatik - 29-2-2012 at 23:23

TACC is easily destroyed by water and the air atmosphere. Everything in its preparation is at best anhydrous, and then it protected form the air. The nitrate salt is easier to make and doesn't degrade as easily.

quicksilver - 1-3-2012 at 16:01

I had experimented with chlorate salts. Tetra-amine-copper-chlorate....The amine often can be resolved using strong ammonia solution (simple source), yet all the warnings of copper and chlorate should be thoroughly understood. It provides an explosive when confined. Yet is deliquescent and must be stored in a sealed container. Recipe for disaster.... (see Formatik 's comment) Results are undefined (broken platelet shape) brittle crystal material that requires continuous desiccant.
Does it provide a strong initiation as used in a primary explosive? Generally [and in practical terms], no. The requirements for maintaining an anhydrous form would be a challenge at best and the weight to initiate a sensitive secondary such as PETN are generally unstudied. I believe that the Journal P.E.P. may have some wider-range metal chlorate salt studies, perhaps lumped together with chlorate initiation (I am not sure: a Search would be in order). However it would take some weight (must likely more than a gram) and would not propagate in a compressed manner; so there is a volume issue.