Sciencemadness Discussion Board

Tetraamine Copper Azide Perchlorate

APO - 15-3-2013 at 20:43

I saw this and wondered if I could just add Copper Perchlorate to Sodium Azide and Ammonia solution.

AndersHoveland - 16-3-2013 at 00:20

No, cobalt happens to have some special properties that allow the ion-ammonia complex to ligand to two azide groups, while retaining a single positive charge. The chemistry of copper complexes is not nearly as complex. If those precursors were reacted, it would just result in copper azide. If an alcoholic solution of ammonia was used (no water), you might get tetramine copper perchlorate.

Because the complexation/ligand chemistry is so complex, a detailed discussion would probably belong in the "Chemistry in General" section. Woelen probably knows more than I do about this field of coordination chemistry.


"double azido cobalt perchlorate" (DACP), the formula is trans-tetraamminediazido-cobalt(III) perchlorate [(NH3)4(N3-)2Co3+](ClO4-). What is interesting about this complex is the fact that it contains azide ligands, fuel and an oxidizer in a single compound.


ammonium-cobalt-azide-perchlorate.jpg - 7kB


(The sample shown in the picture was prepared and posted on this forum by another member, Taoiseach.)
Quote:

It is briefly investigated in a freely available paper "Lead Azide Replacement Program NDIA Fuze Conference" by Bichay and Hirlinger. The compound is a powerful initiating explosive with properties comparable to BNCP (bis-nitrotetrazolate-cobalt-perchlorate) and has been proposed as replacement for both BNCP and lead azide.

A German paper "light absorption of azido-cobalt-ammines" is available in reference section and sheds more light on this family of complexes.

Experimental:

2,6ml 70% perchloric acid was neutralized with basic cobalt carbonate and filtered. Another 1ml of perchloric acid was neutralized with ammonia and the solutions combined. The resultung solution was a light magenta color .

In another beaker, 4g sodium azide was dissolved in 50ml water and 9ml 25% ammonia was added with stirring. The solutions where then combined. Complexation occured, as evidenced by deep blue coloration of the liquid.

A stream of air was then drawn through the solution for 3 hours. During this time the color changed from a deep blue to a lavender color. After standing for several hours, a microcrystalline powder had settled which was filtered and air dried.




since hydrazine is much more energetic than ammonia, I had speculated about the possibility of Hydrazine-diazido-cobalt nitroformate
(N2H4)2(N3)2Co+ C(NO2)3-
but was concerned the nitroformate anion might act as a ligand, which would be bad for several reasons.

Cobalt hydrazine perchlorate apparently is dangerously friction sensitive (you might google search an accident which occurred at Texas Tech University, in which a chem student lost his hand in 2010 mixing a wet slurry of this substance in a mortar and pestle). In terms of safety, hydrazine is probably not very compatible with perchlorate in the same compound, which is why I proposed nitroformate.

A hydrazine complex of Co+3 would probably have to be prepared by displacement, since solutions of Cu+3 do not exist uncomplexed, (and hydrazine is a reducing agent so the cobalt cannot be oxidized after the hydrazine is in solution). Furthermore, the nitroformate would immediately oxidize the hydrazine if the pH was allowed to fall, since trinitromethane is somewhat of an oxidizer (though hydrazinium nitroformate is perfectly stable, for example).

(although nitroformate and trinitromethane are basically two forms of the same compound, and although trinitromethane easily forms dangerously explosive mixtures, the chemical/physical properties between trinitromethane and nitroformate are vastly different)

[Edited on 16-3-2013 by AndersHoveland]

APO - 16-3-2013 at 10:31

Any metal other than Cobalt that can from the Tetraamine Azide Perchlorate compound? It's my understanding that the Cobalt Carbonate needed to make this is carcinogenic.

APO - 16-3-2013 at 11:51

Also, if only Cobalt can form this are there any non carcinogenic cobalt salts I can use? Is Cobalt Hydroxide carcinogenic?

AndersHoveland - 16-3-2013 at 11:58

Cobalt compounds are slightly carcinogenic/poisonous, but it is not really anything to worry about. Cobalt chloride was actually added (in small ammounts) to beer at one time to help with foaming. And cobalt chloride is also included in children's chemistry sets. We all know how watered-down today's chemistry sets are, so this chemical can not be that hazardous.

If you are concerned about potentially toxicity, there is much more to worry about from the azide.
Quote: Originally posted by APO  
Any metal other than Cobalt that can from the Tetraamine Azide Perchlorate compound?

I am not sure. I am not all that knowledged in the field of coordination complex chemistry. I would guess vanadium, nickel, or rhodium might have a chance of forming similar complexes, if you want to investigate.

The cobalt ion is rather unique in that it seems to be able to coordinate with 4 lewis bases, and 2 addition anions. If you look at the structure of cobalt carbonyl, you will see that the cobalt center exhibits an unpaired orbital.

Ruthenium also can an interesting complex with azide, of the type (NH3)4RuX(NO)ClO4, which actually dimerizes. (where X is a halogen or pseudo halogen ligand, such as an azide group)

Palladium can also form the ion Pd(NO2)42-.

Some of the +2 ruthenium coordination complexes which contain a nitrosyl ligand can actually act as a source of NO+, oxidizing azide to N2 and N2O.

[Edited on 16-3-2013 by AndersHoveland]

APO - 16-3-2013 at 12:07

I'm worried about carcinogens, I'm OK with toxins. Should I worry about Cobalt Perchlorate Hexahydrate?

APO - 16-3-2013 at 12:09

Ya know, in terms of being a carcinogen?

AndersHoveland - 16-3-2013 at 12:51

Not unless you plan on eating it. Might be better to avoid breathing in the smoke during deflagration/detonation also, though I would not worry about it.

I will just put it this way: you have a greater chance of getting cancer from using spiral CFL light bulbs in your home, what with all the traces of carcinogenic plastic resins that are baked out over time, and all the UV radiation that leaks out through the cracks in the phosphor coating and thin spiral glass tube. And that's all just if the fragile glass spiral doesn't break. :o

Speaking of toxic mercury, this transition metal can form the interesting compound Cl-Hg-NH2 (easily prepared by reacting mercury(I) chloride with ammonium hydroxide) It might have some interesting coordination chemistry with azides also.
Quote:

Mercury Nitride
Mercury(II) nitride forms a chocolate colored powder, which is slowly decomposed by water. The dry nitride tarnishes in air. Mercury(II) nitride is very explosive, and must be handled with extreme care. It detonates violently, yielding a white flame with a bluish purple border, when heated. The salt is so sensitive that it can be detonated by rubbing it with a glass stir rod. It is formed by reacting HgO with NH4OH, initially at 10°C, but thereafter heating the reaction.

Mercury(I) nitrate can also react with ammonia to form a white precipitate, but I am unsure if this is mercury(I) nitride, or simply a less soluble ammonia complex of mercury(I) nitrate, both of which would be explosive.

The reaction between mercury(I) nitrate and aqueous ammonia produces a mixture of a white basic amido salt and metallic mercury, both of which precipitate out.

(2)Hg22+ + (4)NH3(aq) + NO3- + H2O --> (2)Hg + Hg2ONH2NO3 + (3)NH4+

Apparently this reaction can give either a brownish black color, or a white color. I have seen pictures of both.

It is possible that different reactant ratios could give different products with correspondingly completely different observable color changes in the reaction. It is likely that with excess ammonia, the reaction would turn black, instead of the white precipitate.

A possible explanation for the all-white colored precipitate is that the ammonia, because it is a base, causes mercury(I) to precipitate out as basic mercury nitrate. Even if dissolved in plain water, mercury(I) nitrate is somewhat acidic due to its slow reaction with water:

Hg2(NO3)2 + H2O --> Hg2(NO3)(OH) + HNO3

The Hg2(NO3)(OH) separates out as a yellow precipitate. In the presence of ammonia, it may be possible that some other double salt, with an unknown structure, would form having a white color.

for further reading, see
Hand-book of Chemistry, Volume 6, Leopold Gmelin, starting p91, "Nitrate of Mercurous Oxide and Ammonia"



[Edited on 16-3-2013 by AndersHoveland]

AndersHoveland - 17-3-2013 at 11:21

Quote: Originally posted by APO  
Any metal other than Cobalt that can from the Tetraamine Azide Perchlorate compound?

Again, not certain, but in another thread I proposed the possibility:

[(CH3)3N]3Ni+1(N3)3 • (ClO4−)

The nickel center can only complex to 6 ligands, so that would leave a +1 ionic charge, so that perchlorate could be part of the complex salt also.

The electronic configuration of the nickel in this proposed compound would correspond to the nickel complex NiF62−, which has been described in the literature.

It could perhaps be prepared by reacting nickel(II) perchlorate with trimethylamine in excess hydrazoic acid.

[Edited on 17-3-2013 by AndersHoveland]