Sciencemadness Discussion Board - Exotic Primaries - Complex Salts

Is the cobalt in cobalt diazoaminotetrazole in the +2 or +3 oxidation state? formula?
Also that just plain cobalt azotetrazole, or the tetramine complex with cobalt?

Co(II), precipitated by reaction of sodium diazoaminotetrazole and an aqueous Co(II) salt. The cobalt azotetrazolate made in the same way except using sodium azotetrazole instead, both under regular conditions and no added base or acid present. Formula of the diazoaminotetrazolate ought to be a hydrate of Co3(C2N11)2. Diazoaminotetrazolates have some water solubility and tend to form hydrates.

Cobalt azotetrazolate is a beige orange solid which showed no reaction to moderate hammer blows on an iron plate. Grinding on an iron plate by dragging across with a pestle caused little to no reaction (lead azide shows some reaction there). It indents aluminium sheets. I would think it could form ammonia complexates with very low sensitivity, but likely less brisant. Maybe worthwhile could be a hydrazine complex (trishydrazine cobalt azotetrazolate). Combining some ideas here: maybe azotetrazolato-trishydrazinecobalt perchlorate or nitroformate.

Quote:

That is a complex answer. My opinion is that it is best to combine both.

A combination of the best of both worlds.

NatashaJurievna - 18-2-2012 at 11:12

Is there any data on long term stability of hexahydroxylamine Co(ll) and Ni(ll) nitrate complexes at mild conditions (e.g. at room temperature)? Seems not.

NatashaJurievna - 21-2-2012 at 08:25

Bis and tris(biuret) energetic complexes are also stable and not too sensitive (and cheap). For example, bis(biuret)cupric chlorate, a pale bluish/green powder, is a fairly stable compound and a cool and flashless explosive. A perchlorate is much more energetic (deflagrates with a flame) but too soluble in water and hygroscopic.

AndersHoveland - 24-2-2012 at 11:26

Better to use perchlorate. Chlorates are more chemically reactive, and their salts are much more sensitive (just compare the difference between NH4ClO4 and NH4ClO3 !).

Formatik - 7-7-2012 at 18:22

Quote: Originally posted by Formatik

Another example of large sensitivity reduction is the complex of tetraamminecopper(II) nitrotetrazolate ... with impact sensitivity of manyfold less than copper (II) nitrotetrazolate ...

Correction on the compound which I think I meant here was the salt triaminocopper(II) 5-nitrotetrazolate, described in the paper: Less Sensitive Transition Metal Salts of the 5-Nitrotetrazolate Anion by Sabate and Klapoetke. This copper complex has around the mechanical insensitivity of RDX and does not appear to be that static sensitive either.

RadioTrefoil - 12-7-2012 at 17:03

If anybody's still interested in tetraamminecoppper(II) persulfate complex, I did some deflagration and detonation tests to accompany Axt's. The TeACPS was synthesised from reaction of ammonium persulfate with tetraamminecopper(II) sulfate solution. Ethanol was added to the resulting solution which was then cooled in a freezer to precipitate the TeACPS. I got a brilliant yield. Here are the tests:

<iframe sandbox width="420" height="315" src="http://www.youtube.com/embed/oW6L8d3sO0s" frameborder="0" allowfullscreen></iframe>

I daresay Axt's tetraamminecopper(II) persulfate was probably better quality than mine, although I couldn't find any videos of TeACPS actually detonating.

RadioTrefoil - 12-7-2012 at 17:36

I am still working on trying to find the decomposition products of the tetraamminecopper(II) persulfate as well as the crystal structure. I'm going over to CSIRO in Perth, WA later this year to do some studies on the TeACPS, where I will get some scanning electron microscope photographs of the crystals.

Now to me it's become pretty obvious that the persulfate groups are oxidising the NH3 groups. I raided the university database and found a scientific study on the oxidation of ammonia groups by persulfate (attached), so hopefully I'm a step closer to finding the decomp products.

Attachment: JACS Oxidation of ammonia by peroxodisulfate.pdf (369kB)
This file has been downloaded 1164 times

AndersHoveland - 13-7-2012 at 02:15

Quote: Originally posted by RadioTrefoil

trying to find the decomposition products of the tetraamminecopper(II) persulfate

I do not think it is very complicated.

(NH3)4Cu(S2O8) --> CuSO4 + (NH4)2SO4 + 1⅓ NH3 + 1/3 N2

Only one of the oxygen atoms in the persulfate group is likely to act as an oxidizer. The other oxygen atoms are more strongly bound within sulfate groups.

[Edited on 13-7-2012 by AndersHoveland]

watson.fawkes - 15-7-2012 at 07:08

I do not think it is very complicated.

(NH3)4Cu(S2O8) --> CuSO4 + (NH4)2SO4 + 1⅓ NH3 + 1/3 N2

Provide a citation. You're claiming that the decomposition products of such an explosive reaction don't have either sulfur or nitrogen oxides, which I find ludicrous.

virgilius1979 - 28-7-2012 at 22:00

What would be the formula of hydrazine - copper nitrate/perchlorate complex ? Are there 4 molecules of hydrazine like ammonia in TACN ?
What about guanidine ?
Thanks.

AndersHoveland - 16-8-2012 at 16:46

Quote: Originally posted by watson.fawkes

You're claiming that the decomposition products of such an explosive reaction don't have either sulfur or nitrogen oxides, which I find ludicrous.

This is not like nitrate or perchlorate. Sulfate ions are just not very good oxidizers. There might be some decomposition of the ammonium sulfate, depending on the explosion temperature, but generally the oxygen atoms within a sulfate compound are not really readily available. It takes a significantly larger ammount of energy to break these sulfur-oxygen bonds.

Just because a polyatomic ion contains plenty of oxygen does not necessarily mean most (or any) of the oxygen will be freely available to act as an oxidizer.

watson.fawkes - 17-8-2012 at 07:34

This is not like nitrate or perchlorate. Sulfate ions are just not very good oxidizers [...]

I don't trust your intuition and I don't find your explanation particularly worthwhile. Provide a citation for your claim or withdraw it as speculation.

PHILOU Zrealone - 20-10-2012 at 08:31

Quote: Originally posted by virgilius1979

What would be the formula of hydrazine - copper nitrate/perchlorate complex ? Are there 4 molecules of hydrazine like ammonia in TACN ?
What about guanidine ?
Thanks.

Did you used the search engine?

Copper is too oxydant to deliver a stable complex with hydrazine... the pale turquoise blue complex precipitate I got the same way you do to get the nitrate nickel (II) hydrazinate...spontaneously bursted into flame while drying.
Most of the hydrazine is destructed as N2 during preparation.

If you understand that Ni (II) perchlorate complex is too dangerous to be handeled even in solution in water (while the nitrate is safe)...what would be your expectations for Cu (II) perchlorate following what I wrote here above about the copper nitrate?

Cobalt (II) nitrate makes a pale brown precipitate with similar properties as the Ni(II) complex.

Maybe a Cobalt (II) perchlorate hydrazine complex might exist, but it must be considered very dangerous until otherwise proved!

franklyn - 20-11-2012 at 22:58

The Burning of Ammine Perchlorates & Nitrates of Copper II Nickel II & Cobalt III
www.dtic.mil/cgi-bin/GetTRDoc?AD=AD0779805 , You must append extension .pdf to file to read

[Edited on 22-11-2012 by franklyn]

gnitseretni - 24-11-2012 at 13:24

Finally got a chance to make some Nickel Hydrazine Nitrate. I decided to make it on a tiny scale for now. I powdered what you see in the pic and let it dry some more. Then I took a very tiny sample on the edge of a small wood splinter and put a lighter to it. It burned as fast as AP does. Then I took the NHN and wrapped it in some alu foil that was folded several times to increase thickness and added a fuse. Got out of my mancave and lit the fuse. Was hoping to get a bang but all I got was just a quick "psssh" sound.

This stuff can be used on its own, right? Or am I supposed to mix it with another primary to get reliable detonation?

PHILOU Zrealone - 26-11-2012 at 12:12

Quote: Originally posted by gnitseretni

Finally got a chance to make some Nickel Hydrazine Nitrate. I decided to make it on a tiny scale for now. I powdered what you see in the pic and let it dry some more. Then I took a very tiny sample on the edge of a small wood splinter and put a lighter to it. It burned as fast as AP does. Then I took the NHN and wrapped it in some alu foil that was folded several times to increase thickness and added a fuse. Got out of my mancave and lit the fuse. Was hoping to get a bang but all I got was just a quick "psssh" sound.

This stuff can be used on its own, right? Or am I supposed to mix it with another primary to get reliable detonation?

In tiny amounts you should not expect a great explosion or detonation that way (not wel confined)! Do the same tiny sample wrapped in one or twofold layers of Al foil and hold it a few seconds over a candle flame with a long tool and you will see/ear the real power of the stuff.

Personnaly I like to mix Ni(N2H4)3(NO3)2 with Ag-C#C-Ag.xAgNO3.yHNO3 in a 2/1 ratio...so you get detonation even with low confinement.

franklyn - 26-11-2012 at 13:04

UAN Fertilizer of Urea + Ammonium Nitrate is readily available as a solution
in a 1 to 1 molar ratio. Urea molar weight is 60 , Ammonium Nitrate molar
weight is 80 , so that Urea is 30 percent , Amonium Nitrate is 40 percent
and the balance is 30 percent water. Acidifying with even low concentartion
nitric acid will form Urea Nitrate in the solution with Ammonium Nitrate. When
dried it can be used as a low velocity blasting agent with slight positive oxygen
balance. http://en.wikipedia.org/wiki/UAN

4 NH4NO3 + 4 (NH2)CO • HNO3 => 4 CO2 + 18 H2O + 10 N2 + O2

Another composition not studied is to compound the UAN solution with
Hydrogen Peroxide. Urea forms an addition compound of Hydrogen Peroxide ,
Urea Peroxidate - see post by Axt
http://www.sciencemadness.org/talk/viewthread.php?tid=3214&a...
Recently Peroxidates of Ammonium Nitrate have been shown to be readily
obtained by vacuum evaporation of Ammonium Nitrate solution with
30 percent H2O2 which is available over the counter.
http://www.sciencemadness.org/talk/viewthread.php?tid=14308&...
http://www.sciencemadness.org/talk/viewthread.php?tid=608&am...

Urea Peroxidate decomposition products have a negative oxygen balance ,
and it does not exhibit any pyrotechnic ability given that it lies outside of the
explosive limits of mixtures of H2O2.
The detonation products of both Ammonium Nitrate and Hydrogen Peroxide
have positive oxygen balance and in 1 to 1 molar proportions this exactly
compensates for the oxygen deficiency of Urea Peroxidate.

2 NH4NO3 => 4 H2O + 2 N2 + O2

2 H2O2 => 2 H2O + O2

2 (NH2)2CO • H2O2 => 4 H2O + 2 CO + 2 N2 + 2 H2

NH4NO3 • H2O2 + (NH2)2CO • H2O2 => CO2 + 6 H2O + 2 N2

Drying UAN then again adding the mixed solute to a stoichiometric quantity
of Hydrogen Peroxide and vacuum evaporating the solution will produce a
double Peroxidate compound. This has not been written about or investigated.

.

Rosco Bodine - 26-11-2012 at 19:25

I am presently looking for references for bis-semicarbazide-copper(II)- diperchlorate and the zinc and nickel and manganese analogues

The copper salt should be Cu[(OC(NH2)NHNH2]2(ClO4)2

Here is a related article for the chloride salt of the complex

http://scripts.iucr.org/cgi-bin/paper?S0365110X65003791

And attached is a related patent US6127564

Attachment: US6127564 Semicarbazide Metal Complexes.pdf (79kB)
This file has been downloaded 1034 times

PHILOU Zrealone - 29-11-2012 at 12:27

Quote: Originally posted by franklyn

UAN Fertilizer of Urea + Ammonium Nitrate is readily available as a solution
in a 1 to 1 molar ratio. Urea molar weight is 60 , Ammonium Nitrate molar
weight is 80 , so that Urea is 30 percent , Amonium Nitrate is 40 percent
and the balance is 30 percent water. Acidifying with even low concentartion
nitric acid will form Urea Nitrate in the solution with Ammonium Nitrate. When
dried it can be used as a low velocity blasting agent with slight positive oxygen
balance. http://en.wikipedia.org/wiki/UAN

4 NH4NO3 + 4 (NH2)CO • HNO3 => 4 CO2 + 18 H2O + 10 N2 + O2

Another composition not studied is to compound the UAN solution with
Hydrogen Peroxide. Urea forms an addition compound of Hydrogen Peroxide ,
Urea Peroxidate - see post by Axt
http://www.sciencemadness.org/talk/viewthread.php?tid=3214&a...
Recently Peroxidates of Ammonium Nitrate have been shown to be readily
obtained by vacuum evaporation of Ammonium Nitrate solution with
30 percent H2O2 which is available over the counter.
http://www.sciencemadness.org/talk/viewthread.php?tid=14308&...
http://www.sciencemadness.org/talk/viewthread.php?tid=608&am...

Urea Peroxidate decomposition products have a negative oxygen balance ,
and it does not exhibit any pyrotechnic ability given that it lies outside of the
explosive limits of mixtures of H2O2.
The detonation products of both Ammonium Nitrate and Hydrogen Peroxide
have positive oxygen balance and in 1 to 1 molar proportions this exactly
compensates for the oxygen deficiency of Urea Peroxidate.

2 NH4NO3 => 4 H2O + 2 N2 + O2

2 H2O2 => 2 H2O + O2

2 (NH2)2CO • H2O2 => 4 H2O + 2 CO + 2 N2 + 2 H2

NH4NO3 • H2O2 + (NH2)2CO • H2O2 => CO2 + 6 H2O + 2 N2

Drying UAN then again adding the mixed solute to a stoichiometric quantity
of Hydrogen Peroxide and vacuum evaporating the solution will produce a
double Peroxidate compound. This has not been written about or investigated.

.

Great idea Franklyn.
If NH4NO3 allows the formation of a peroxydate; and NH2-CO-NH2 also...then maybe NH2-CO-NH3NO3 might too hold some H2O2...
Then the double nitratoperoxydate might be interesting...to increase density and to make some more oxygen available to burn an organic matrix binder.

NH4NO3.H2O2 + NH2-CO-NH3NO3.H2O2 => CO2 + 13/2 H2O + 5/2 N2 + 5/2 O2

franklyn - 29-11-2012 at 16:13

@ PHILOU Zrealone

" maybe NH2-CO-NH3NO3 might too hold some H2O2 "

That had not occurred to me. What's interesting about peroxidates is that
it opens an entirely new and as yet uninvestigated area of formulated
compositions which are solid molecular level mixtures. Because of the
high steam production these may be suitable as environmentally benign
propellants for example for possible use in automobile airbags.

.

Rosco Bodine - 5-2-2013 at 16:17

Here's a paper of interest. Sorry if this paper has already been posted. Also are the excerpted pages from PATR related to energetic hydrazine metal complex salts.

Attachment: energetic_characteristics_of_transition_metal_complexes.pdf (305kB)
This file has been downloaded 1482 times

Attachment: Nitrohydrazinates and analogues PATR Vol. 7 H-L.pdf (374kB)
This file has been downloaded 986 times

[Edited on 6-2-2013 by Rosco Bodine]

Rosco Bodine - 10-2-2013 at 17:05

There is a bis-hydrazine nickel azide which has about three times the small mass initiating impulse of tris-hydrazine nickel nitrate, and a comparable grain size for the microcrystalline precipitate at about 80 microns. It would seem that these two compounds would make a nice complementary mixture. I am uncertain if the reaction conditions would allow coprecipitation or formation of a possible mixed salt or double salt. A reference request has been made to look further into this. Of course the bis-hydrazine nickel azide is interesting by itself as an initiator.
It is mentioned on page 21 of the attached paper, journal page is 313.

Attachment: Environmentally Friendly Energetic Materials for Initiation Devices Mikhail Ilyushin.pdf (1.3MB)
This file has been downloaded 1170 times

DraconicAcid - 13-2-2013 at 20:13

When I was a young lad, I read in the Rubber Bible (aka, CRC Handbook of Chemistry and Physics) that [Cu(NH3)4](NO3)2 was explosive. So, naturally, I tried making some. I don't remember why it didn't work, but this thread inspired me to try it again. Easy prep- I dissolved 0.9 g of copper(II) oxide in about 5 mL conc. nitric acid, and then added enough ammonia (with cooling) that the copper(II) hydroxide redissolved. I then added about 10 mL 95% ethanol, let it sit in an ice bath for a few minutes, and filtered. Let it dry in the fume hood overnight (with a big sign saying "Do NOT Disturb!!"). It burned nicely, but I'd be hard-pressed to call it an explosion. I suppose it might have done so under the right conditions, but a deflagration spoon isn't them.

Rosco Bodine - 14-2-2013 at 08:56

There is a bis-hydrazine nickel azide which has about three times the small mass initiating impulse of tris-hydrazine nickel nitrate, and a comparable grain size for the microcrystalline precipitate at about 80 microns. It would seem that these two compounds would make a nice complementary mixture. I am uncertain if the reaction conditions would allow coprecipitation or formation of a possible mixed salt or double salt. A reference request has been made to look further into this. Of course the bis-hydrazine nickel azide is interesting by itself as an initiator.
It is mentioned on page 21 of the attached paper, journal page is 313.

Attached are the additional articles Thanks to kmno4

Attachment: Studies on lead free initiators synthesis characterization and performance evaluation of transition metal complexes of c (411kB)
This file has been downloaded 1173 times

Attachment: Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes.pdf (651kB)
This file has been downloaded 2237 times

With regards to the semicarbazide complex of nickel perchlorate or in the alternative the more expensive cobalt perchlorate, these compounds appear to be very promising as fairly easily made initiators. Excerpted from the article:

"The thermal as well as sensitivity characteristics
and limited performance evaluation of these metal complexes
bring out the potential of CoCP and NiCP as energyproviding
component of lead-free detonators for futuristic
programmes. These investigations also reveal that NiCP and
CoCP are superior detonants as compared to mercuric fulminate and service lead azide in terms of low vulnerability
to initiation by mechanical and thermal stimuli. It warrants
further in-depth trials for their adoption in detonators as ecofriendly and chemically compatible primary explosive. Practical data on the effect of ageing on shelf life and performance change (useful life) of NiCP and CoCP need to be generated in future."

It appears likely that a detonator base charge also comprising a perchlorate would have absolute chemical compatibility with the initiator. Guanidine perchlorate, methylamine perchlorate, trimethylamine perchlorate, and possibly other energetic perhlorates would seem to be candidates for the base charge topped with the semicarbazide complex of nickel perchlorate as an initiator.

Experimental from the article:

Synthesis of nickel tris(carbohydrazide) perchlorate (NiCP)

A solution containing 3.66 g (0.02 mol) carbohydrazide in 35 cm3 of water was charged into a stainless steel reactor placed on a water bath. It was kept under mechanical stirring
and heated to the temperature of 58–60 ◦C. 7.32 g (0.07 mol) of nickel perchlorate hexahydrate dissolved in 25–30 cm3 of double distilled water was added to the carbohydrazide solution over a period of 20 min at 58–60 ◦C. The addition of the reactant resulted in marginal exothermic reaction leading to an increase in the temperature of the contents. The reaction mixture was allowed to remain at 58–60 ◦C for about 30 min.

Subsequently, the reaction flask was removed from the water
bath and digested at room temperature with stirring for an
hour. The light blue crystals of NiCP obtained were filtered
through a Buchner funnel. The bluish coloured crystals were
washed with distilled water (4×50 cm3), followed by propyl
alcohol (50 cm3) and dried at 60 ◦C. The yield obtained was
8.9 g (85%). Similar procedure was adopted for the synthesis
of CoCP, CuCP and ZnCP of free-flowing nature. The molar
ratio of copper perchlorate and carbohydrazide used during
the synthesis of CuCP was 1:2.1.

An attempt was also made to synthesize these complexes
at a lower temperature (25 ◦C) adopting the above procedure. The products obtained at lower temperature were found amorphous in nature with less yield (60–70%) and lower bulk densities (0.65–0.74 g/cm3). The intensity of the colour of these complexes obtained at lower temperature was slightly light in comparison to the products obtained at 65 ◦C. The reaction time required to complete the reaction at 25–30 ◦C was of the order 1 h. The compounds obtained at 58–60 ◦C were selected for further studies.

Note: There appears to be errata in Table 1 at the bottom of page 2 of the pdf (page 58 of the journal) where the sensitivity to impact figures are transposed for the Ni and Cu compounds. This table errata would need to be confirmed as it does not match the text of the article.

[Edited on 14-2-2013 by Rosco Bodine]

franklyn - 19-2-2013 at 08:16

Explosive coordination compounds remain obscure and little exploited or
investigated. Some of these show intriguing potential for application as
detonation initiators aside from the few that have seen such use.
For some time I had the notion that a complex with Cyanide can serve
better as fuel than Ammonia based types , but being an anion itself hinders
the prospect of binding with oxidative anions such as Nitrate. I have become
aware of a long forgotten ( it would seem ) compound of this type. The
oxidizer functional group is Chromium IV oxide , CrO4 , which remarkably
forms a double salt with Potassium Cyanide. The temperature of explosion
is a bit low , and may prove to be too sensitive for general application , but
serves to show that compounds of this type can serve as the first charge
in a compound detonator set off by flame or electric element.
It is described in the following first two citations here _

Chromium Teroxide + KCN Hexanmino- chromic Nitrate .gif - 79kB

The third citation above is an excerpt from Explosive Properties of Metal Ammines
www.sciencemadness.org/talk/viewthread.php?tid=1778&page...
featuring the commendable properties of another Chromium based complex
Hexamino Chromic Nitrate which is as powerful as TNT with a sensitiveness
to impact like that of RDX , making it very suitable for use as the base of
a compound detonator with the above compound if that proves capable.

CrO4•3KCN is described on page 96 of
Per-acids and Their Salts , See Chapter VIII Perchromates , pg 92
The precursor compound is detailed here on page 95
http://books.google.com/books?id=kxFDAAAAIAAJ&pg=PA95&am...
Download the book ( enter captcha )
http://books.google.com/books/download/Per_acids_and_their_s...

X-Ray Studies on Some Alkali and Alkaline-Earth Chromates
Acta Chem. Scand. 19, 177 (1965) , K. A. Wilhelmi & 0. Jonsson
http://actachemscand.dk/pdf/acta_vol_19_p0177-0184.pdf
Has prep for CrO4
Cr203 in fused (725 ºC) Li2CO3 => Li3CrO4

The following are excerpted from here _ Inorganic Reaction Mechanisms
http://books.google.com/books?id=jGvRKef2pZIC&pg=PA145&lpg=PA145

Hexamino-Chromic-Nitrate described above is detailed on page 81 here _
A Text Book of Inorganic Chemistry vol X - The Metal Ammines
https://ia600502.us.archive.org/9/items/textbookofinorga0288...
See pg 74 Amino Derivatives of Chromium Salts ,
Another which appears promising , Nitro-Pentamino-Chromic Nitrate
and it's precursor Chloro-Pentamino-Chromic Chloride , are described
on page 94 , excerpted here below.

Chloro pentamino chromic Chloride & Nitro pentamino chromic Nitrate.gif - 104kB

___________________________________________________

Continuing with the opening premise of this post , the inclusion of cyanide
in an energetic inorganic compound by the prospect of forming a double salt
whereby it is co-crystallized with a nitrate.
It's been known a long time , as stated in Commercial Organic Analysis - 1896
http://books.google.com/books?id=ppDPAAAAMAAJ&pg=PA428&a...
" Heated with KNO3 or KClO3, the metallic cyanides detonate strongly."
Sodium cyanide is somewhat more reactive; contact with nitrates, peroxides,
chlorates, and nitric acid can cause explosions. It explodes if melted with nitrite
at over 450 °C , but apparently will not from impact when struck.
Potassium cyanide will also explode in contact with nitrogen chloride and some
nitrates. Sodium cyanide is also more dangerous to handle, since the amount
of CO2 in the air is enough to react with it to release hydrogen cyanide gas.
Sodium cyanide is more dense at 1.6 grams per milliliter as compared to
1.52 grams per milliliter for potassium cyanide.
The immediate problem that arises is the disparate solubilities of prospective
salts , making it likely that the cyanide typically less soluble than the nitrate
will precipitate separately from solution. Despite these issues there is in fact
one known double salt of this type , KCN • KNO2 , as described here _

The presence of retained water tends to inhibit explosive propensity and in
this case is difficult to remove by ordinary drying procedures. Anhydrous
solvation may provide a better product. The solubility of KCN and NaNO2
are within a 10 percent of each other at room temperature.
KCN
Solubility in methanol 49.1 g/L (20 °C)
NaNO2
Solubility in methanol 44.3 g/L (19.5 ºC)

It would seem that mixing together two saturated solutions stoichiometrically
balanced for a 1 : 1 ratio , contained in a filtration flask which is sealed and
subject to continuous vacuum while gently warmed , will evaporate the solvent
forcing crystallization of the two solutes as an anhydrous double salt.
Note that in solution double decomposition will result in the formation
of KNO2 , NaCN , solubility for these salts will differ somewhat from
that of the initial KCN , NaNO2. What little data I can find does not appear
to militate against the basic premise at this time.

A compound which is oxygen balanced would be based on Alkaline metal salts.
Ca(CN)2 + Ca(NO3)2 => 2 CaO + 2 CO2 + 2 N2 , for example would prove
to be very powerful given the expected density is well over 2 gm/cc .
Calcium Cyanide is unstable easily hydrolysed on it's own , Magnesium is even
more so. http://magnesium.atomistry.com/magnesium_cyanide.html

.

[Edited on 20-2-2013 by franklyn]

Rosco Bodine - 20-2-2013 at 20:23

Here are a couple of additional articles of interest.

Attachment: nhn1.pdf (175kB)
This file has been downloaded 1652 times

Attachment: JSIR 63(8) 677-681.pdf (70kB)
This file has been downloaded 1350 times

[Edited on 21-2-2013 by Rosco Bodine]

franklyn - 20-2-2013 at 22:47

Metal Hydrazine Complexes , Patents
US 5970703 , US 6481746

franklyn - 25-2-2013 at 03:49

Apparently co-crystallized compounds of Cyanides with Nitrites have been noted
but out of sight and earshot of the mainstream , as mentioned halfway down here _
www.guidechem.com/reference/dic-15333.html ( See " Reactivities and Incompatibilities " )
( Just as I said in my post above here )
" Mixtures of Sodium Nitrite and various Cyanides explode on heating, including Potassium Cyanide,
Potassium Hexacyanoferrate(III), Sodium Pentacyanonitrosylferrate(II), Potassium Hexacyanoferrate(II),
or Mercury(II) Cyanide. Such mixtures have been proposed as explosives, initiable by heat or a detonator.
A mixture of Sodium Nitrite and Potassium Thiocyanate explodes on heating.
There is no interaction between Sodium Nitrite and Sodium Thiosulfate in solution, but evaporation
of the mixture gave a residue which explodes on heating. The mixed solids behave similarly."

__________________________________________

- and now for something completely different

Na2NO2 , Disodium Nitrite ? Huh
http://sodium.atomistry.com/disodium_nitrite.html

See bottom of page " 10 Miscellaneous Cathodic Reductions "
http://books.google.com/books?id=6ghTyzzOzM8C&lpg=PA74&a...

An excerpt from " Reduction of Inorganic Substances "
http://tera-3.ul.cs.cmu.edu/NASD/4dcb85c3-9fee-4c83-9e6d-fe6ce5522b59/China/disk1/46/31004737/PDF/00000119.pdf

Disodium Nitrite, an Additive Compound of Sodium Nitrite and Sodium
http://pubs.rsc.org/en/content/articlelanding/1917/CT/ct9171...

Electroreduction of Nitrate to Nitrite to Hydronitrite
http://jes.ecsdl.org/content/101/5/229.abstract

Mellor 8: Supp. 1, 546 (1964) obtained this from NH4NO3 with sodium

.

trimethylammoniumpentazidodicuprate

Rosco Bodine - 16-3-2013 at 23:06

A similar complex to Diazidodiamminocopper(II) described on page 8 of this thread is a related Trimethylamine complex or compound salt trimethylammoniumpentazidodicuprate

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

Quote: Originally posted by Taoiseach

was prepared according to

CuSO4*5H2O + 2NH3 + 2NaN3 ---> [(NH3)2(N3)2Cu] + Na2SO4 + 5H2O

NH3 was added to a solution of CuSO4 until the precipate of Cu(OH)2 redissolved. A saturated warm solution of NaN3 was added. Upon cooling and addition of an equal volume of ethanol, a nice crop of [(NH3)2(N3)2Cu] precipated.

Green-blue glistering crystals. Unlike copper azide these are not friction sensitive. Explodes upon flame contact.

Obviously the compound is oxygene-deficient, so addition of a strong oxidizer should increase its power.

trimethylammoniumpentazidodicuprate is a similar compound about which I can find very little information. It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide. It would seem possible that different metals may also form analogous compounds as does copper.

See attached excerpt from PATR for description of

trimethylammoniumpentazidodicuprate

(CH3)3N-HN3-2[Cu(N3)2]

Attachment: TMA - PATR Vol. 9 Q-T.pdf (103kB)
This file has been downloaded 999 times

[Edited on 17-3-2013 by Rosco Bodine]

AndersHoveland - 17-3-2013 at 10:23

It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide.

(CH3)₃N-N3-2[Cu(N3)2]

dark red crystals, explodes at 201°

I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.

I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably also be too electron-withdrawing.

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(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]

Rosco Bodine - 17-3-2013 at 11:28

I think perhaps you mean (CH3)₃N-N3-2[Cu(N3)2]

You are correct ....my typo above has been edited to show "3" for the trimethyl and I see it would also be better to show the trimethylamine as hydro-azide analogous to TMA hydrochloride...which is what I think is probably the case here. If I am on the right track then an anlogous compound may be possible with chlorides as is showing for the azides.

Quote:

I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.

I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably also be too electron-withdrawing.

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(CH3)₃N]₂Ni⁺²(N₃)₄ 2(ClO₄^-)

The nickel center can only complex to 6 ligands, so that would leave a +2 ionic charge, so that perchlorate could be part of the complex salt also.

[Edited on 17-3-2013 by AndersHoveland]

I'll have to do some reading on these complexes to be sure.
My first inclination would be to disagree about the metal being "complexed" by the azide, as it would be more my inclination to expect the complexation involves the substituted ammonia with the metal to form the complex which then forms a mixed salt or compound salt with the uncomplexed metal salt. The complexation of the metal by the substituted ammonia would seem to be analogous for what happens with complexation by hydrazine or semicarbazide, where an "ammonia value" is present as some multiplier. However that value is 0 for trimethylamine, which does not form a complex with copper. It seems almost as if part of the compound is trimethylamine "hydro"-azide which exists or can exist as a distinct compound, cocrystallized as a double salt with 2 copper azides.

This behavior may be peculiar because trimethylamine does not form a complex with copper as does ammonia.

AndersHoveland - 17-3-2013 at 11:36

The article listed the possible formulas as either:

Quote:

(CH₃)₂NH[(N₃)₂CuN₃Cu(N₃)₂ or

(CH₃)₃N.HN₃.2[Cu(N₃)₂]

It seems they were not entirely sure what the structure actually was. I think the name "trimethylammoniumpentazidodicuprate" is therefore probably very misleading.

Perhaps I am just overthinking this too much, and the salt just consists of trimethylammonium cations and Cu(N₃)₃⁻ complex anions.

[Edited on 17-3-2013 by AndersHoveland]

Rosco Bodine - 17-3-2013 at 11:45

Yeah it is intriguing huh. It sort of looks like a complex ...but not exactly, and may simply be a multiple salt.....which is what my impression was that led me to speculate even other multiple salts could form as series. But it may not follow at all that way because it could just be a peculiar anomaly that is true for only this one case. Clearly some other investigators were definitely scratching their heads looking at this one ......and we can agree it is red.

And it is energetic ...but what are its properties?

Anyway it's a possible "green energetic" so it caught my notice.

Just for giggles Google

trimethylammoniumpentazidodicuprate

What do you get ?

Consider the possibility that a compound salt could form between Trimethylamine Perchlorate and Copper Azide , now that would be interesting.

All right Klapotke, enough loafing, time to get back to work

[Edited on 17-3-2013 by Rosco Bodine]

metal carbohydrazide complexes

Rosco Bodine - 21-3-2013 at 15:38

With regards to my post on the preceding page

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

there is information in the hydrazine thread which has bearing upon preparation of carbohydrazide from hydrazine cyanurate but this is uninvestigated and will require experimental confirmation.

http://www.sciencemadness.org/talk/viewthread.php?tid=1128&a...

Also one of the articles which was posted previously as an attachment evidently has too long of a name and is not downloading true as a pdf so I am attaching the name edited file here.

Attachment: Talawar Studies on Lead free initiators metal complexes of carbohydrazide.pdf (415kB)
This file has been downloaded 2106 times

In my earlier post is a typo which I need to correct or clarify
Where I wrote "semicarbazide" should be corrected to read "carbohydrazide" as is the context for the attached article.....even though the same may be true for the semicarbazide complex analogue, I have not yet found references for the semicarbazide complex to verify this.

"With regards to the semicarbazide [should read carbohydrazide] complex of nickel perchlorate or in the alternative the more expensive cobalt perchlorate, these compounds appear to be very promising as fairly easily made initiators."

Attached is an article of interest Thanks to gsd

Chemistry of carbohydrazide and thiocarbohydrazide
Frederick. Kurzer, Michael. Wilkinson
pp 111–149
Publication Date: February 1, 1970 (Article)

franklyn mentions that carbohydrazide is also known as diaminourea ( DAU )
http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...

Attachment: THE CHEMISTRY OF CARBOHYDRAZIDE AND THIOCARBOHYDRAZIDE.pdf (850kB)
This file has been downloaded 8653 times

Attachment: Explosives Based on Diaminourea (carbohydrazide).pdf (240kB)
This file has been downloaded 1325 times

[Edited on 22-3-2013 by Rosco Bodine]

AndersHoveland - 10-6-2013 at 22:25

I just had an idea, I thought I would mention it here.

Take a look at the structure of Manganese(III) acetate. It has a surprisingly complicated inter-coordination structure. Each cluster consists of 3 manganese atoms, 6 acetate groups, a central oxygen atom, and each cluster has a positive charge, typically with an extra outside acetate ion associated with it. The bonding in the cluster is very delocalized, I would draw an analogy to acetylacetone with copper ions (copper acetylacetonate is almost aromatic).

So would it be possible to use dinitrosomethanate in place of the acetate? (dinitrosomethane has an aci-tautomer)
That would leave a positively charged cluster, and then presumably some other oxidizing anion like perchlorate or nitroformate could be associated with it.

Mn3O[CH(NO)2]3⁺ C(NO2)3^‒

The cluster also has 3 water molecules of hydration, not shown, but those could possibly be replaced with NH3.

resonance diagram of dinitrosomethanate ion:
O=N‒CH=N‒O^‒ <--> O^‒‒N=CH‒N=O

resonance diagram of formate ion:
O=CH‒O^‒ <--> O^‒CH=O
similar to acetate ion

[Edited on 11-6-2013 by AndersHoveland]

papaya - 19-8-2013 at 13:01

While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?

PHILOU Zrealone - 27-8-2013 at 01:26

Quote: Originally posted by papaya

While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?

The facts are that...
Zn nitrate forms a stable hydrazine complex
Ni (II) nitrate forms a stable hydrazine complex
Cd(II) nitrate forms a stable hydrazine complex
Co (II) nitrate forms a stable hydrazine complex
But...
Cu (II) nitrate forms an unstable hydrazine complex
Hydrazine and iodine or iodate are uncompatible...
Silver nitrate is unstable towards hydrazine...

So watching closely to the oxydoredox potential table
There must be an electrochemical explanation to this...
See hydrazine at potential at +0,11... Zn, Ni, Cd, Co are above in the negative potential...while Cu, Ag, Iodine and Iodate are below...

Cr(3+) and Cr(2+) seems to be on the safe side!

papaya - 27-8-2013 at 06:00

Quote: Originally posted by PHILOU Zrealone

Quote: Originally posted by papaya

While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?

Well, once I tried to mix dilute Cr(NO3)3 + HNO3 solution with 50% hydrazine hydrate (few ml scale) and immediately obtained green precipitate which didn't burn and actually was metal hydroxide. However supernatant liquid turned into pink color which indicate something more interesting happened there besides that classical acid-base reaction. There was no formation of gas observed, so hopefully no worries about hydrazine decomposition. I didn't investigate it further because I have no source of decent quality chromium nitrate (pure solid salt), perhaps with a proper synthesis method this is doable. It may be fun for anyone here to try and report results and properties here for a first time before it get's published in academic journals (if it's really new)!
Also as there are 3 nitrate anions - more oxygen is available and it must be worth to try to prepare some (insoluble) complex with organics like acetonitrile, real pain is that many of these things may be soluble in water and require anhydrous conditions (as well as anhydrous chromium salt).

papaya - 26-9-2013 at 13:31

Hi, a long thread so I might miss something - did anyone actually try to synthesize bis- nickel hydrazine azide, that is mentioned on p.13 here? How stable is it (to storage, humidity, etc.), ? Is it a "real" primary with a short DDT, or merely deflagrates/explodes? It's characterized as even less sensitive than tris- hydrazine nickel nitrate in Ilyushin's paper attached there, which is counter-intuitive (azide!). What about other azide complexes(Zn, Co,..) - was any tried here? Thanks.

DraconicAcid - 26-9-2013 at 13:53

Quote: Originally posted by papaya

Chromium(III) is a very non-labile ion. Once you've got [Cr(H₂O)₆]³⁺ in solution, the water ligands don't really want to come off very rapidly. If you let your solution mixture of chromium(III) nitrate and hydrazine stand for extended periods of time, you might form the complex.

If the solution is basic, that can speed it up (a base can catalyze it by forming a hydroxy complex, which is more labile), or you can sometimes catalyze it by reducing chromium(III) to chromium(II), which is much more labile.

papaya - 26-9-2013 at 21:36

Thanks Draconic, so perhaps I had to keep that Cr(OH)3 formed in contact with solution for a long time until it converts to the desired product.
And what about bis- nickel hydrazinium azide ?

DraconicAcid - 27-9-2013 at 10:10

Nickel(II) is quite labile- if it forms, it should form quickly.

I'm not sure how well azide works as a ligand, though- I don't have much experience with azides.

DraconicAcid - 27-9-2013 at 10:14

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(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]

Sorry, but that's not going to work. Azide is an anionic ligand. To get [NiL₃(N₃)₃]ClO₄ (where L is a neutral ligand, such as ammonia or trimethylamine), you would have to have nickel in the +4 oxidation state, which is not preferred for nickel.

papaya - 27-9-2013 at 10:24

http://www.tandfonline.com/doi/abs/10.1080/00945719608004763...
This might help if somebody has access...

Rosco Bodine - 29-9-2013 at 12:51

Thanks to Dany for the following article attached

Synthesis and Characterization of Some Cobalt(II), Nickel(II), Zinc(II) and Cadmium(II) Hydrazine Azides

K. K. Naranga, M. K. Singh (Mrs), K. B. Singh & R. A. Lal

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry
Volume 26, Issue 4, 1996, pages 573-589

Also attached is a related article of interest

Attachment: Metal Hydrazine azide complexe.pdf (508kB)
This file has been downloaded 970 times

Attachment: Hydrazine complexes of transition metals as explosives chemik_2011_65_1_24-27.pdf (193kB)
This file has been downloaded 1241 times

papaya - 6-10-2013 at 13:51

Lately I managed to prepare and test some 0.2-0.3g of Ni[N2H4]2(N3)2 complex - it's a very fine light blue powder, that readily catches fire (flashes) when exposed to fire, I didn't notice it to be highly sensitive and can be handled without too much risk in my opinion (was a small quantity and I never tried to see how it behaves under different mechanical stimuli). However that 0.2g did NOT detonate when confined(slightly hand-pressed) into soft PVC tube having about 4mm of internal diameter and 1mm of wall thickness and lit from open side. So not a first class primary

DubaiAmateurRocketry - 14-12-2013 at 14:46

Perchlorate complex salts of hydrazine are dangerously friction sensitive. Hydroxylamine perchlorate is very sensitive, having a drop height value of only 2cm.

Can I have a reference for the 2cm drop height value ?

That sounds very extreme! I've never seen a explosive with an positive OB of +42% can have such a sensitivity.

DubaiAmateurRocketry - 14-12-2013 at 14:58

franklyn mentions that carbohydrazide is also known as diaminourea ( DAU )
http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...

Di-dinitramide salt of this also seems to be interesting derivative.

[Edited on 14-12-2013 by DubaiAmateurRocketry]

franklyn - 5-2-2014 at 22:21

Hydrazine complexes of transition metals as prospective explosives

www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf

Coordination explosives

www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf

.

Rosco Bodine - 6-2-2014 at 10:35

Quote: Originally posted by franklyn

Hydrazine complexes of transition metals as prospective explosives

www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf

Coordination explosives

www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf

Here attached is the second linked file and the first is a few posts above.

Attachment: chemik_01_2010_023_024.pdf (173kB)
This file has been downloaded 988 times

detonator - 26-4-2014 at 10:19

Quote: Originally posted by Formatik

Quote: Originally posted by Chainhit222

http://pubs.acs.org/cen/science/88/8834sci1.html

oh oh..

but then again, he did put what looks to be a primary explosive in a mortar and pestle.... I would not have tried to break up a large crystal of primary... maybe dissolve it in something and try to precipitate it out.... what the fuck was he thinking...

An hour in the library sometimes saves hours and days of work in the lab, but it can also save extremities. Here was used far too large of an amount of a material which they knew very little about. In Gmelin a citation for a nickel hydrazine perchlorate, [Ni(N2H4)2(ClO4)2], pale-blue precipitate made from standing of aq. Ni(ClO4)2 with N2H4, describes it as extremely explosive and that even in aqueous dilute suspensions it explodes. There is also a reference (H. Ellern, D.E. Olander, J. Chem. Educ. 32 [1955] 24) which claims that the nitrate (which has been investigated as a primary), Ni(NO3)2.3N2H4, as a moist compound occasionally deflagrates spontaneously, but that the dry salt can explode spontaneously.

Actually,the molecular formula of Nickel hydrazine perchlorate is [Ni (N2H4) 5] (ClO4) 2, In a paper published in JACS.The title is "Ionic Polymers as a New Structural Motif for High-Energy-Density Materials",Received: October 13, 2011,Published: December 17, 2011。
The thesis describes the NHP molecules and the crystal structure obtained by X-ray diffraction.

[Edited on 26-4-2014 by detonator]

Attachment: NHP-JACS.pdf (780kB)
This file has been downloaded 1144 times

[Edited on 26-4-2014 by detonator]

DubaiAmateurRocketry - 6-5-2014 at 06:42

Some hydroxylamine and hydrazine complex and hydrates

The advantages of hydroxylamine complex or hydrates in a compound give higher gas production, and better oxygen balance than amine/hydrazine complexes. Hydroxylamine also give greater densities. Hydrazine's complexes offer good gas production, extensive hydrogen bonding, and increase the heat of formation.

Complexes

https://docs.google.com/viewer?url=patentimages.storage.goog...

This patent show the interesting compound -

[Mg(NH₂OH)4]²⁺ salt of perchlorate. The nitrate salt is also interesting. Li(NH₂OH)2 [ClO₄]^- is also synthesized with specific impulse estimated to exceed ammonium perchlorate.

The procedure is not much different of making the hydrazine complexes. In this patent - https://docs.google.com/viewer?url=patentimages.storage.goog...

This compound detailed the synthesis of [Al(N₂H₄)6]³⁺ [ClO₄]^-3. and also [Mg(N₂H₄)2]²⁺ salt of perchlorate.

Hydrates

http://pubs.acs.org/doi/abs/10.1021/i360030a021
I need someone to help me un-lock this file since I only saw the 1st page. Maybe important data like densities are given.

Anyways, This paper gave some synthesis of some hydroxylamine hydrate of some hydroxylamine salts, such as the nitrate salt [⁺NH₃OH] [NO₃]^-•[NH2OH] and the monohydrate and dihydrate of hydroxylammonium perchlorate [⁺NH₃OH] [-ClO₄]•[NH₂OH] and [+NH3OH] [-ClO₄]•[NH₂OH]2 respectively

These salts are described in the abstract to be less hygroscopic.

Hydroxylammonium-Hydroxylamine dinitramide is detailed in this paper http://link.springer.com/article/10.1023%2FA%3A1011362427996...
The compound contain both neutral and zwitterionic hydroxylamine moieties involved in the hydrogen bonding scheme. This structure the hydroxylamine exists in its three possible forms: protonated, neutral, and zwitterionic.
[NH₃OH]₂ [N(NO₂)₂]₂•[N⁺₃OH]•[NH₂O^-]

Klaptoke has synthesis few hydrazine hydrate of hydrazine compounds such as this one.
http://www.ncbi.nlm.nih.gov/pubmed/11421707.
5,5’-azotetrazolate dihydrazinate

(⁺N₂H₅)2 [(CN₄^-)2N₂]•(N₂H₄)2 Containing nearly 86% Nitrogen by weight.

he also made hydrazine azide hydrazinate https://www.google.ae/url?sa=t&rct=j&q=&esrc=s&a...
(⁺N₂H₅)(N₃^-)•(N₂H₄) or empirically N7H9, contains 91.5% nitrogen by weight.

Klaptoke also synthesized moni and dihydroxylammonium 5-Nitriminotetrazolate.
http://onlinelibrary.wiley.com/doi/10.1002/zaac.201100479/ab...
All compounds in this paper has practically no use due to high sensitivity or low detonation velocity, except for 1 compound - dihydroxylammnoium 5-Nitriminotetrazolate hemihydrate.

[(⁺NH₃OH)2 (CN₄NNO₂)^-2]2•H₂O

This compound have a detonation velocity higher than HMX while having lower sensitivity. This compound is also easy to make. 5-Amino-tetrazole nitrated by 100% Nitric acid produce 5-nitriminotetrazole and upon addition of hydroxylamine solution gives this product.

_{EDIT(woelen): Fixed error in formula on request of DubaiAmateurRocketry}

[Edited on 8-5-14 by woelen]

franklyn - 19-6-2014 at 17:51

Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium Styphnate
www.google.com/url?url=http://www.mdpi.com/2073-4352/2/1/34/pdf&rct=j&frm=1&q=&esrc=s&sa=U&ei=eyijU8mPKJPLsAS8oIGIDw&ved=0CBkQFjABOCg&usg=AFQjCNG O9gQHr4qfmmqokdeKsFaMzLxC-Q

.

studie

Laboratory of Liptakov - 6-9-2014 at 00:36

Interesting post. The entire PDF file, I have translated and studied. I found information on the velocity of detonation or a detonation pressure. Maybe I missed.
LL

An oddity

franklyn - 12-9-2014 at 11:25

Attachment: Energetic cocrystals of DADP.pdf (2.6MB)
This file has been downloaded 912 times

HANP

Laboratory of Liptakov - 14-9-2014 at 12:39

Interestingly attach test results HANP 1200mg / 300mg LA. (Hexamine nickel perchlorate) R8 = ETN 650mg / 300mg LA.

TeACP and HMTA

Laboratory of Liptakov - 1-11-2014 at 11:05

I see that there are a lot of experienced chemists. Anders, PHILOU, Franklyn, Rosco, Dubai .. I have a question: TeACP (tetraminecopper(II)perchlorate) and HMTA (hexamethylene tetramine) can create complex along together? The ammonium hydroxide solution (25% in aq.) ..? What about created? Created anything? And if so: What? Laboratory test Melting points to a new (unknown) compound.
Thanks, LL

Rosco Bodine - 1-11-2014 at 15:41

I think the semicarbazide complex of nickel perchlorate may be interesting and may not have the dangerous instability of the hydrazine complex.

NHN

Laboratory of Liptakov - 7-11-2014 at 09:25

I see that the substance NHN running through thread. NHN can detonate speed of 7000 m/s. But it has several conditions. Here are my experiences. Laboratory of Liptakov do research. NHN no detonated 6 mm in diameter. Only 8 mm. Copper tube 8/10 mm. It should be progressive stamping. 1.7 g/cc 400 mg + 1.3 g/cc (400) + 1.0 g/cc + 0.6 g/cc. The following is a resistor. The following is 0.6 g/cc 400mg. The following is a seal. A total of 2 grams. That is the minimum. Better to 2.4 grams total. Hydrazine is volatile and very toxic. Further attempts LL will not be repeated.

PHILOU Zrealone - 14-11-2014 at 11:27

I see that there are a lot of experienced chemists. Anders, PHILOU, Franklyn, Rosco, Dubai .. I have a question: TeACP (tetraminecopper(II)perchlorate) and HMTA (hexamethylene tetramine) can create complex along together? The ammonium hydroxide solution (25% in aq.) ..? What about created? Created anything? And if so: What? Laboratory test Melting points to a new (unknown) compound.
Thanks, LL

Hi LL,
It seems that HMTA (C6H12N4) does form complexes (Me(HMTA)2X2) with several metals like Me=Ni, Co, Mn (and maybe Zn); X being Cl or NO3.
Those complexes are sometimes linked to water ligands.
HMTA also form a complex with silver with one HMTA unit per Ag atom.

I haven't seen references of perchlorate anion but it is a good idea, even better would be nitroformiate anion...also as a special cyclonan variant with NH4C(NO2)3 and (if it exists?) Cu(NH3)4(C(NO2)3)2 ;-)

It is plausible that HMTA will set some NH3 (gas) free from the Cu(NH3)4(ClO4)2.

For OB reasons it might be usefull to try higher valences of Ni and Co (Ni(3+) and Co(3+) except if they are too oxydant for the NH3 and HMTA ligands (HMTA being a discrete form of methanal and amonia).
6 CH2=O + 4 NH3 <--==> C6H12N4 + 6H2O

So to try out!
Ni(HMTA)2(ClO4)3
Co(HMTA)2(ClO4)3
Ni(HMTA)2(C(NO2)3)3
Co(HMTA)2(C(NO2)3)3

Ni

Laboratory of Liptakov - 14-11-2014 at 14:37

Philou, you write too much (from my perspective) scientifically. I try to Ni(HMTA)2(ClO4)3
Thank you for the advice. Maybe arises LL-PHIL / supercyklonan...........

PHILOU Zrealone - 15-11-2014 at 08:22

I see that the substance NHN running through thread. NHN can detonate speed of 7000 m/s. But it has several conditions. Here are my experiences. Laboratory of Liptakov do research. NHN no detonated 6 mm in diameter. Only 8 mm. Copper tube 8/10 mm. It should be progressive stamping. 1.7 g/cc 400 mg + 1.3 g/cc (400) + 1.0 g/cc + 0.6 g/cc. The following is a resistor. The following is 0.6 g/cc 400mg. The following is a seal. A total of 2 grams. That is the minimum. Better to 2.4 grams total. Hydrazine is volatile and very toxic. Further attempts LL will not be repeated.

Nice work LL!

It is a long time I play with Ni(N2H4)3(NO3)2.
I have tested also Co(N2H4)3(NO3)2 (stable pale Brown/amber powder with comparable properties to pink lilac NiHN) and Cu(N2H4)2(NO3)2 (turquoise blue precipitate)...
This last one is highly unstable probably owing to oxydoredox potential of Cu(2+) vs hydrazine just like Ag(+) and takes fire spontaneously while drying...most of the hydrazine being destroyed during process.

@LL and others,
I highly do not recommand the use of copper detonator in direct contact with NiHN (better use a plastic straw interface)...I suspect a Cu detonator containing NiHN/SANC was involved in an unwished detonation of a N2H5NO3 pipe firework that occured at home. It is possible that NiHN exchanged partially for Cu metal or that the mildly acidic N2H5NO3 reacted on its side of the detonator with the Cu oxyd-hydroxyd layer to make transient Cu(N2H4)2(NO3)2, heating and detonation.

I have improved the performances of NiHN by admixture of silver acetylide nitrato complex (from neutral proces AgNO3/C2H2/water). Both dry precipitate do mix nicely and are stable towards each other.
Ni(N2H4)3(NO3)2 + Ag-C#C-Ag.xHNO3.yAgNO3 : Mix by weight 2/1 to 3/1.
That way the flame/impact sensitivity of SANC and short D2D distance benefits from the high VOD and power of NiHN while SACN increases synergetically the sensitivity and reliability to detonation of NiHN --> reduction of the critical mass of detonation.

Never try Ni(N2H4)3(ClO4)2 it is very sensitive explosive even in water solution a glass rod hit onto the surface of the container can set it off!

Use extreme caution with unknown explosive metal-oxoanion complexes of the kind and always start small and make heat and confinement testing (flame test in open and in Aluminium foil wrapping).
NiHN burn like nitrocellulose in the open and minute amount but same amount in Al foil will detonate very strongly...

[Edited on 15-11-2014 by PHILOU Zrealone]

Ni/Ag

Laboratory of Liptakov - 15-11-2014 at 11:24

Thank you for yourself and for others for pointing out NiHN + Cu tube. This is important. I read many times about 2 parts NiHN and 1 parts Mixture of nitrate of silver acetylide complex. This is a good choice. Question for Philou: Diameter 6 or 8 mm? Weighed 0.6 or 1 or 1.5 grams? Thanks, LL...... :cool:

PHILOU Zrealone - 16-11-2014 at 08:52

Thank you for yourself and for others for pointing out NiHN + Cu tube. This is important. I read many times about 2 parts NiHN and 1 parts Mixture of nitrate of silver acetylide complex. This is a good choice. Question for Philou: Diameter 6 or 8 mm? Weighed 0.6 or 1 or 1.5 grams? Thanks, LL...... :cool:

@LL,
I must confess that I use almost always too much initiator and too big detonators

:
*5-8mm internal diameter
*2.5-4 cm long
*max density by vibration of clay-like consistency initiator powder and pressing by small powder increments via tooth-pick point
*so 1-3g

Why? Everybody has its own financial and practical limitations

I prefer to waste 1 or 2g too much comparatively cheap initiator(*) (with 100% efficient detonation) than 100g (or more) valuable rare or labour intensive HE main charge (TNB or N2H5NO3)...

(*)To me Ag, AgNO3 and CaC2 are very cheap; at that time was Ni, Ni(NO3)2 and HNO3 also cheap and easily accessible (I stil have a lot of Ni nitrate).Nickel is less used in coin factories (allergies, environemental aspects, euro-legislation)...I remember not so long ago 50 belgian franc coin was 7g of nearly pure Nickel (50BF = 1.25 Euros = approx 1.5$)...there is stil some Nickel Inside Euro-coins but not a lot

.
I had also access to 80% hydrazine but 500ml was quite expensive (I stil have a few ml left...but I found a new provider and I own 5L 25% hydrazine for a decent price and I have about 2kg of N2H5HSO4 in my personnal stock).

So I have never pursued the goal of optimum detonation quantity limit vs efficiency to spare money and allow me to make as much detonator from a given quantity of initiator.
This would have been an interesting perspective and study...but it would have costed me time and money at a time I was looking for quick fun and results...
--> yeah young people are usually impatient...
--> I do not escape to the rule

--> I'm only human after all

[Edited on 16-11-2014 by PHILOU Zrealone]

NHN/Ag

Laboratory of Liptakov - 17-11-2014 at 03:08

Thank you for the perfect answer. Pity that ended Belgian coins. 8 mm cavity will be good. The content of 3 g too. Hydrazine is a problem. It is more expensive and toxic. This is not the best way for amateurs. But the way it is. 3 g refill, that's pretty firing charge. I have the same opinion. Rather large detonator (3), before spreading expensive charge. (100 and more). If the detonator safe, almost like NPED may need 4 grams in it. No fear ...... :cool:

Monte Carlo - 2-1-2015 at 18:58

Canadian nickels from 1981 or earlier are essentially pure nickel and are still in circulation.

http://en.wikipedia.org/wiki/Nickel_%28Canadian_coin%29

franklyn - 30-1-2015 at 09:03

Analogous to the inorganic coordination cyanide anion ,
K3[Fe(CN)6] , Potassium Ferricyanide ( Potassium Hexacyanoferrate III )
there is an inorganic coordination anion of Nitrogen Dioxide
K3[Co(NO2)6] , Potassium Cobaltinitrite ( Potassium Hexanitrocobaltate III )

The two could be co-precipitated from solution forming an oxygen balanced blend very close to a 2 : 3 molar ratio.
38 K3[Fe(CN)6] + 60 K3[Co(NO2)6] => 147 K2O + 60 CoO + 19 Fe2O3 + 228 CO2 + 294 N2
1.25 parts by weight of Ferricyanide to 2.71 parts by weight of Hexanitrocobaltate

In solution with an Ammonium salt it can undergo metathetical double replacement to become _
(NH4)3[Co(NO2)6] , Ammonium Hexanitrocobaltate III
mentioned in Explosive Properties of Metal Ammines here
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

Ammonium Hexanitrocobaltate III can be further reacted with hydrazine to replace Ammonia.
(NH4)3[Co(NO2)6] + 3 H2NNH2 => (H2NNH2•H)3[Co(NO2)6] + 3 NH3 ^
The result is a more energetic compound which also has excess oxygen.
4 (H2NNH2•H)3[Co(NO2)6] => 4 CoO + 30 H2O + 24 N2 + 7 O2

It occurs to me that formaldehyde will condense with the Ammonium and Hydrazonium cation of these complexes.
This would add carbon fuel to the oxygen rich compound.

One can also react Ammonium Hexanitrocobaltate III with an organic amine base to replace Ammonia.
(NH4)3[Co(NO2)6] + 3 CH3NH2 => (CH3NH2•H)3[Co(NO2)6] + 3 NH3 ^
This results in an energetic compound with a negative oxygen balance.
2 (CH3NH2•H)3[Co(NO2)6] => 2 CoO + 6 CO + 16 H2O + 9 N2 + 2 H2

Instead of Methylamine, using Dimethylamine yields a compound having poor oxygen balance but a very large molar gas volume.
2 [(CH3)2NH•H]3[Co(NO2)6] => 2 CoO + 12 CO + 10 H2O + 9 N2 + 14 H2

Here I thought I was on to something new and it turns out all this had been investigated back in 1909 !
Attachment: Studies on the Cobaltinitrites , Jnl of The Chem Soc (Transactions) 1909 - pg 1562.rtf (23kB)
This file has been downloaded 682 times
From here ( in .djvu , .pdf , and various other formats )
http://ia902608.us.archive.org/31/items/journalpt295chemuoft

I've written before that judicious blending of two compounds can remedy the shortcomings of either.
Combining a compound deficit of oxygen with one having a surplus yields an oxygen balanced composition.

7 (CH3NH2•H)3[Co(NO2)6] + 8 (H2NNH2•H)3[Co(NO2)6] => 15 CoO + 21 CO2 + 123 H2O + 79 1/2 N2
Nearly in the ratio of 5.4 parts by weight of the methylamine to 6.2 parts by weight of the hydrazine variant.

14 [(CH3)2NH•H]3[Co(NO2)6] + 52 (H2NNH2•H)3[Co(NO2)6] => 66 CoO + 84 CO2 + 558 H2O + 375 N2
Nearly in the ratio of 4.7 parts by weight of the dimethylamine to 6.1 parts by weight of the hydrazine variant.

These other coordination compounds are unstudied with regard to substitution with organic amine bases. Those in which the ammonia comprises the complex anion itself cannot be so simply substituted. Formaldehyde will condense with a coordinated metal amine complex. Providing coordination is not completely destroyed releasing the metal oxide, this will introduce carbon fuel in the compound.
Found in The Metal Ammines in the forum library here
http://library.sciencemadness.org/library/books/ATBOIC/atboi...
• Hexammino Cobaltic Nitrate , [Co(NH3)6](NO3)3 , pg 136
• Nitrato Pentammino Cobaltic Nitrate , [Co(NH3)5NO3](NO3)2 , pg 145
•1,6-DinitroTertaamminoCobaltic Nitrate , [Co(NH3)4(NO2)2]NO3 , pg 155
( it is also mentioned in Inorganic Synthesis vol 18 , pg 70 - 71 )
( both the cis & trans forms of [TetraammineDinitroCobalt III] Nitrate , [Co(NH3)4(NO2)2]NO3 )
• Hexammino Cobalt Nitrite , Co2(NH3)6(NO2)6 , pg 161
• Trinitro Triammino Cobalt , Co(NH3)3(NO2)3 , pg 162
• Ammonium Tetranitrito Diammino Cobaltate , NH4[Co(NH3)2(NO2)4] , pg 163
• Potassium Cobaltinitrite , K3[Co(NO2)6] , pg 164

Description
Fischer's salt (also called Fischer's yellow), Potassium Cobaltinitrite ( Potassium HexanitroCobaltate III ) a pigment known historically as Aureolin, a.k.a. Cobalt yellow
http://www.jstor.org/discover/10.2307/1506479?sid=2110519426...
Sodium HexanitroCobaltate(III) reagent is used to test for Potassium and Ammonium ions, also forms the basis of quantitative determination of Potassium.
http://cameo.mfa.org/wiki/Cobalt_yellow

http://en.wikipedia.org/wiki/Sodium_cobaltinitrite
http://en.wikipedia.org/wiki/Potassium_cobaltinitrite

Properties of Potassium Hexanitritocobaltate(III)
http://books.google.com/books?id=PpTi_JAx7PgC&lpg=PA759&...
http://books.google.com/books?id=IDsXBQAAQBAJ&lpg=PA473&...

Properties of Sodium Hexanitritocobaltate(III)
http://pubchem.ncbi.nlm.nih.gov/compound/159748#section=Chem...
http://www.lookchem.com/Potassium-hexanitrocobaltate-III-/
http://www.caslab.com/Sodium_cobaltinitrite_CAS_13600-98-1/

Preparation
http://chemistryfanatics.wordpress.com/2013/07/02/experiment...
http://www.studymode.com/essays/Preparation-Of-Sodium-Hexani...

Potassium Cobaltinitrite
Russian Journal of Inorganic Chemistry 04/2011; 56(4):501-505.
DOI: 10.1134/S0036023611040267
http://www.researchgate.net/publication/225112209_Potassium_...
Highest yield, smallest particle size, and highest purity of the product are attained by reacting Potassium Nitrite with Cobalt Nitrate in an acid medium in the same way as in the synthesis of Sodium Cobaltinitrite:
2CH3COOH + Co(NO3)2 + 7KNO2 => K3[Co(NO2)6] + 2KNO3 + 2CH3COOK + NO^ + H2O.
All of the resulting Potassium Cobaltinitrite samples are hygroscopic.

The following reference found in Federov PATR-2700 , C-386
Cobalt Nitrite Complexes
When KNO2 is added in excess to a solution of Co(NO2)2 , acidified with AcOH, a yellow precipitate of potassium hexanitrocobaltiate ( potassium cobaltinitrite ), K3[Co(NO2)6] forms. This compound is also known as Fischer's Salt or as a pigment Cobalt Yellow, formation of above complex can serve as the basis of a volumetric determination of Co ion. When a solution potassium salt is added to sodium cobaltinitrite a yellow crystalline precipitate potassium-sodium cobaltinitrite K2Na[Co(NO2)6]•H2 0 is formed. This complex, being practically insoluble in water, can be used as the basis for detection of potassium ion.
References :
1)Gmelin, Syst Nr 58, Teil A (1932) , 400, 409 & 411
2)Kirk & Othmer 4 (1949) , 210-11
3)Gmelin, Syst Nr 58, Teil A, Ergänzungsband (1961), 513-15
4)CondChemDict (1961), 288

According to this , these complexes can serve as propellants.
Gas Generant Complex Oxidizers patent US 5962808
http://www.sciencemadness.org/talk/files.php?pid=91285&a...

Related posts
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

.

PHILOU Zrealone - 31-1-2015 at 13:00

Very nice Franklyn!

Just one remark on stability...
Nitrite/Nitro anion and ammonium or hydrazino ligands on a metal core might be very unstable.

NH4NO2 (ammonium nitrite) is already not stable.
NH2NH3NO2 (hydrazinium nitrite) turns into HN3 (hydrazoic acid)...this is observed when AgNO2 is mixed with N2H4...sensitive AgN3 results.

One may expect primary amine to be quite unstable too
R-NH2 + HNO2 --> R-OH + N2 + H2O

Secondary amines may transform into nitrosamine compounds
R2NH + HNO2 --> R2N-N=O + H2O

Tertiary amines may be stable

[Edited on 31-1-2015 by PHILOU Zrealone]

TeACP velocity

Laboratory of Liptakov - 2-2-2015 at 02:12

The my patent process is on a good way. Therefore, I can give important insights into the double salt TeACP. Measured by dent plate. Pure TeACP also loses ammonia from the molecule. In the dry powder state very soon, during 3 days. In the pressed state at 1.8 g / cm3 as well. After 20 days (at 20C) begin to fall explosive properties. This can be prevented, in other words, importance to limit the loss of NHx.
With plasticizer PIB 2% + 2% oil 5W40. This is key. This mixture is safe for compression. This mixture has a zero oxygen balance. Detonation velocity is very high. (graph) It is possible constructions SC or EFP devices. It is here in threads. Everything device (LL produce) is just filled with this mixture. TeACP grain fraction is 0.05 -0.2 mm. Wet 5% H2O/NH3. Then mixed with a plasticizer, dry heptane, and pressed of 1.75 to 1.85 g / cm3. Production TeACP is very easy, video here: https://www.youtube.com/watch?v=MDPa0Od3jws
Proven stability of 4.5 g pellet is 30 days / 20C. The power/VoD/ is the same as tetryl pellet. Detonation pressure at 1,7 - 1.8 g / cm3 is 20 - 25 GPa. (RDX 28 GPa). Initiation No.8.
For more details, I will discuss later. According questions.
...LL... :cool:

PHILOU Zrealone - 3-2-2015 at 12:45