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[*] posted on 27-10-2011 at 17:46


Quote: Originally posted by Rosco Bodine  
Interesting. Did you try conversion of the tris(hydrazine)zinc nitrate (ZHN) to a perchlorate derivative by mixing with 2 mole equivalents of ammonium perchlorate. I am thinking that a double decomposition may result leaving ammonium nitrate in solution while precipitating tris(hydrazine)zinc perchlorate (ZHP) but I have no solubility or other data to confirm the validity of this idea.


No, I haven't. It is insoluble in water, and hot water decomposes it (hot water also slowly decomposes NHN). It is soluble in conc. aq. NH3 though. But I would be weary of forming any kind of perchlorate here considering instability of the copper perchlorate complex and dangerous sensitivity described above on the nickel perchlorate complex. I've seen no data on it.
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[*] posted on 27-10-2011 at 17:57


@AndersHoveland
What is the basis for NHN - AgN3 to be characterized as a clathrate?
There are a lot of coprecipitates that are definitely not clathrates, and
that would seem to be the case here .



[Edited on 28-10-2011 by Rosco Bodine]
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[*] posted on 27-10-2011 at 18:03


Quote: Originally posted by AndersHoveland  
Another advantage, small amounts of the compound do not need confinement to detonate.


Try that for yourself and see if it's true. I couldn't even get it to detonate under confinement.

Note: yes it can explode when heated but these are likely in what I would call at least larger amounts. Probably gram amounts. It has likely a higher critical mass than many other primaries.

[Edited on 28-10-2011 by Formatik]
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[*] posted on 27-10-2011 at 18:10


Quote: Originally posted by Formatik  
Recently made tris(hydrazine)zinc nitrate (ZHN). It is a very shiny, glittering compound (every crystal glitters) with a beige tint. I made it by mixing Zn(NO3)2 aqueous from zinc and nitric acid, with conc. aq. NH3 which was added until the Zn(OH)2 precipitate redissolved and the liquid took on a light yellow color to form a clear solution, then added about the same volume of 55% N2H5OH and boiled it on low boil until crystals started appearing where the boiling was stopped. Then let it crystallize, washed it several times with alcohol. The compound is also mentioned in Gmelin.

It is an insensitive initiator, it hasn't exploded in any heating tests done on small amounts, like over a flame, in flame directly, etc. It doesn't even flash like tris(hydrazine)nickel nitrate (NHN) does. But it does burn very fiercely, very nicely actually even though it leaves behind a lot of white ZnO. It burns splendid with an interesting bluish-white-orange flame. Sprinkling it onto aluminum foil and wrapping this up into a fuse caused it to burn completely to the end when one end was lit. It does have some energetic properties, but needs to basically be blasted itself.


Please attach that Gmelin excerpt if you have it.

You describe boiling the solution on a low boil until crystals begin to appear. What I was thinking was to add a boiling hot solution of ammonium perchlorate before the point where a low boil would make crystals begin to appear, seeking possible precipitation of a less soluble perchlorate derivative via double decomposition of the nitrate.

The reaction mixture you describe is already a solution of ammonium nitrate and probably diamminezinc nitrate or diamminezinc hydroxide, so the presence of ammonium perchlorate may cause the perchlorate salt to precipitate.
I know this works for tetramminecopper perchlorate, but haven't tried the hydrazine complex for any of these.
Generally though not always, the perchlorate salt will be less soluble so that will be what precipitates.

[Edited on 28-10-2011 by Rosco Bodine]
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[*] posted on 27-10-2011 at 18:18


Perchlorate complex salts of hydrazine are dangerously friction sensitive. Hydroxylamine perchlorate is very sensitive, having a drop height value of only 2cm. Hydrazine perchlorate is also much more sensitive than hydrazine nitrate, although I do not know exactly how much. Woelen has demonstrated that it can at be heated over a flame in a metal spoon without detonation, but I would not want to risk trying this. It seems that compounds that contain perchlorate together with either hydrazine or hydroxylamine (which are reducing agents) are dangerously friction sensitive. I would wonder about nitroformate salts instead of perchlorate, since hydrazinium nitroformate is apparently stable enough for use as a rocket oxidizer. Nitroformates are more powerful than nitrates, and almost as powerful as perchlorate. However, the sensitivity and stability of complex transition metal salts (especially Cu, Ag, Hg, Pb) of nitroformate may be completely different, due to the unique chemistry of the nitroformate anion.

Whereas trinitromethane, even and especially when dissolved in an organic solvent is dangerously sensitive, its nitroformate salts, including even those of hydrazine, are much more stable. One difficulty of synthesis may arise in the fact that trinitromethane itself will oxidize hydrazine (or its salts). The trinitromethane must be added in the form of its nitroformate salt.

[Edited on 28-10-2011 by AndersHoveland]
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[*] posted on 27-10-2011 at 18:33


@AndersHoveland
Zinc diammine Perchlorate is actually used as a phase stabilizer at 1.8% content in NH4NO3 oxidizer based solid rocket propellants, according to US5071630

You often make generalizations or even specific statements about things which are simply inaccurate, the dubious clathrate is a recent example, and you continue opining here about the hydrazinium complexes, making generalizations which are somewhat or altogether dubious generalizations.

You go through these threads with a broad brush pseudointellectualizing about things you really don't know, and I for one wish you would stop it with the pretended knowledge, and qualify what you think by just saying, "I think" ...but it may not be so, as a kind of disclaimer :D

Attachment: US5071630 Zinc diammine Nitrate.pdf (489kB)
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[*] posted on 27-10-2011 at 18:40


Quote: Originally posted by Rosco Bodine  
Zinc diammine Perchlorate is actually used as a phase stabilizer at 1.8% content in NH4NO3 oxidizer based solid rocket propellants,


Zinc diammine Perchlorate is an ammonium complex, not a hydrazine complex. There are no compatibility problems between perchlorate and ammonia. Indeed, ammonium perchlorate is very stable, virtually impossible to detonate by itself.
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[*] posted on 27-10-2011 at 18:46


Do you have specific information on the hydrazinium complex of zinc perchlorate?

It is possible it could be unacceptably sensitive and it is possible it may not be unacceptably sensitive. Unless there is a specific reference for it, then why make such generalizations ? The hydrazinium zinc perchlorate is described in the following references, which may provide some reliable information.

W. Friederich and P. Vervoorst, SS 21, 49 (1926)

SS = Z. ges. Schiess-Sprengstoffw.

CA 21, 1184, 1927

Semicarbazide perchlorate complexes could also be interesting ....but there is nothing I can find about them.

[Edited on 28-10-2011 by Rosco Bodine]
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[*] posted on 27-10-2011 at 19:55


Quote: Originally posted by Rosco Bodine  
Please attach that Gmelin excerpt if you have it.


It's attached below. The original description goes: a clear solution of Zn(NO3)2 in NH3 and N2H5OH is heated on the water bath, causing a brown coloration and separation of a skin of black metal particles (I didn't see that). Upon cooling the compound separates as a white crystalline powder (it's whitish). The Franzen and Mayer reference also mentions it burns with a green flame, I suppose there is some green in its flame also. It burns brilliantly once ignited.

Quote:
You describe boiling the solution on a low boil until crystals begin to appear. What I was thinking was to add a boiling hot solution of ammonium perchlorate before the point where a low boil would make crystals begin to appear, seeking possible precipitation of a less soluble perchlorate derivative via double decomposition of the nitrate.


Maybe it could work, but I wouldn't be willing to risk the glassware on it.

Attachment: Gmelin, Zn, 156.pdf (386kB)
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[*] posted on 27-10-2011 at 20:19


Thanks for the Gmelin page.

You could put your hot NH4ClO4 solution in a foam coffee cup and dribble in the other hot component solution .....no glass at risk.

Another possible way of doing this would be to react Calcium Hydroxide in slight excess with Ammonium Perchlorate and heat to boiling to drive off the ammonia, filtering the residual solution of Calcium Perchlorate. React that solution of Calcium Perchlorate with Hydrazine Sulfate and filter out the Calcium Sulfate to leave a solution of Hydrazine Perchlorate. Then you could add your metal complex candidate as an ammonia solution of the metal nitrate.
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[*] posted on 9-11-2011 at 21:14


Here are a few deflagrations of the aforementioned hydrazine compounds:

Tris(hydrazine)nickel nitrate (NHN):


nhnpic.png - 495kB


Deflagration to heat and flame:




Tris(hydrazine)zinc nitrate (ZHN):

zhnpic.png - 600kB


Deflagration to heat and flame:


zhndef.png - 358kB



The same aforementioned fuse of ZHN is also in one of the videos above. It burned to the end. I'm not sure how reliable it is yet though. And around 30mg of the ZHN intermixed with about 30mg Ag2C2.AgNO3 into a small pile on an iron plate gave a very loud report on contact with a long wooden match flame (originally Philou's idea to mix the nickel salt with acetylide complex).

Concerning hydrazine toxicity, this works by inhibiting vitamin B6. Hydrazine drugs also inhibit vitamin B6. Vitamin B6 ingestion can offset some hydrazine toxicity, however too much vitamin B6 ingestion can cause permanent nerve damage so it has to be very carefully dosed. Respirators work pretty good against vapor. But they do nothing to protect the eyes, which hydrazine damages.

Below is the aforementioned reference claiming spontaneous deflagration and detonation of the nickel complex. It sounds to me like they had some kind of nasty contaminant, perhaps in their nickel source (copper maybe) in their lab. I had it sit around for about three weeks and it never misbehaved. Copper would not be readily discernible in their original nickel but would impart a green color to the lilac salt (their impurity maybe more bogus than copper). I've ignited 1.0g in the open and it only flashed, yet they had a violent spontaneous detonation with only 1.5g of the unconfined salt. That's not the NHN I know.

Attachment: J. Chem. Educ. 32 [1955] 24.pdf (1MB)
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[Edited on 10-11-2011 by Formatik]
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[*] posted on 19-12-2011 at 21:01


Studies of Complex Perchlorates
http://www.dtic.mil/dtic/tr/fulltext/u2/607947.pdf

Studies of Complex Perchlorates (final)
http://www.dtic.mil/dtic/tr/fulltext/u2/634105.pdf


Chlorates & Perchlorates their Characteristics & Uses
http://www.dtic.mil/dtic/tr/fulltext/u2/318741.pdf

Chlorates & Perchlorates Their Manufacture Properties & Uses
http://www.dtic.mil/dtic/tr/fulltext/u2/242192.pdf


Related Post _
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...


[Edited on 20-12-2011 by franklyn]
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[*] posted on 27-12-2011 at 21:51


Some more thoughts on the previous nickel hydrazine nitrate:

The spontaneous explosion of the previous nickel hydrazine nitrate is a complete mystery. Rather than admit the possibility of having impure material in the facility, they speculate the presence of some kind of higher complex, noting an excess of hydrazine, or that residual N2H5OH did some kind of funky stuff. I think I may have read Franzen and Mayer explicitly doubting any higher complex possible. Mine also smelled of hydrazine for a few days, but I doubt the presence of a higher complex. It's just excess hydrazine, hydrazine being hydrazine and lingers around for a few days.

The previous crude test of initiation using HgDTZ may not have worked well at all, because I didn't think of the action of a powder on top of another simulating the effect of confinement, but it does. Initiation of ZHN and NHN was done with 0.3g PbN6 in the Journal of Hazardous Materials 171 (2009) 1175–1177, which showed maximum pressure generation of 86.9% and 105.0% of TNT for the zinc and nickel salts respectively.
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[*] posted on 28-12-2011 at 14:32


Random Idea

Hypofluorous Acid (HOF) CAS 14034-79-8
Formed much the same as the Chlorination of water H2O + Cl2 => HOCl + HCl
except it only forms on ice and is only barely stable at cryogenic temperature.
If mixed with Nitrogen Trifluoride may perhaps reform as
TetraFluoroAmmoniumoxyhydride (NF4OH)
The Lewis structure is perfectly satisfied manifesting a TetrafluoroAmmoniumoxy
cation and hydride anion.

Tetrafluoroammoniumoxyhydride.GIF - 2kB

http://en.wikipedia.org/wiki/Hypofluorous_acid
http://accessscience.com/content/Hypohalous-acid/334300
http://pubs.acs.org/doi/abs/10.1021/ja00327a016
http://www.sciencedirect.com/science/article/pii/00404020778...
http://www.ncbi.nlm.nih.gov/pubmed/18355062
Properties
http://www.chemeo.com/cid/26-601-5

.
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[*] posted on 29-12-2011 at 03:34


Formatik, please, upload your videos on MediaFire next time if you can. It is free and I must not wait for download and all that crap. Thanks :)

Nice videos, btw.

[Edited on 29-12-2011 by Adas]




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[*] posted on 29-12-2011 at 09:05


Thanks. Ah yes, mediafire is much better.
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[*] posted on 3-1-2012 at 17:56
double salt lead bromate acetate


Here is an obscure explosive double salt. It is doubtful that it has any practical applications, probably having poor chemical stability in storage because of the bromate.

http://www.youtube.com/watch?v=_Xx-zhALHjM

Quote:

lead acetato-bromate Pb2(C2H3O2)2(BrO3)2 precipitate deflagrates with a yellowish-white puff of smoke. hammer drop height sensitivity: 15-20cm. 175 g of KBrO3 are dissolved in 1.5 L hot water, and mixed with a solution of 175 g acetic acid (100%) and 260 g lead acetate hydrate in 2 L water. The solution remains clear initially. It is then filtered, cooled down and seeded with a few crystals of lead bromate while rubbing the side of the glass vessel with a glass rod. Soon after, the solution becomes turbid, and yields a heavy crystalline precipitate, which does not increase anymore after 12 hours in the cold. The solution above the precipitate is decanted off or extracted out, and discarded (possibly add some Na2CO3 to salvage the remaining lead in the waste solution, in the form of PbCO3). The crystalline precipitate is washed with cold water until it is free of acetic acid and Na/K acetate/bromate, then is hot dry air is passed over until free from moisture. Yield is only 123 g


[Edited on 4-1-2012 by AndersHoveland]
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[*] posted on 14-1-2012 at 16:19


Making that large of an amount of a primary is never a good idea. This lead salt complex also has a thread on here.

Below is the original reference of Franzen and Mayer mentioned above and some references of similar salts.

Über die Hydrazinate einiger Metallsalze. Franzen, Mayer. Z. Anorg. Chem. 60, 247 (1908).

Verbindungen von Hydrazin mit Quecksilbersalzen. K.A. Hofmann, E.C. Marburg. Ber. 30, 2019 (1897).

Zur Kenntniss der Stickstoffquecksilberverbindungen. K.A.Hofmann, E.C. Marburg. Annalen, 305, 214 (1899).
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[*] posted on 5-2-2012 at 09:11


Co-ordination Compounds as Sensitizers for Percussion Cap Compositions
http://www.dtic.mil/dtic/tr/fulltext/u2/a492392.pdf

Most notable, less known compounds:

Thiourea cuprous perchlorate - cuprous cyanamide complex
Behavior on ignition: Deflagrates fiercely with a dark red flame and little smoke.

Basic triethanolamine lead perchlorate
On ignition deflagrated vigorously.
:cool:
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[*] posted on 6-2-2012 at 14:36


BTW, German patent DE922216 says about the heavily oxygen deficient basic triethanolamine lead perchlorate that "unter Einschluß detonierende Substanz" - detonating substance under confinement.
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[*] posted on 12-2-2012 at 17:44
Tetramine Zinc Permanganate


Do not know if this complex salt has been mentioned before, here is a translation from http://www.pirotek.info/Vv2/TeAZM.htm

Quote:

Tetramine Zinc Permanganate - [Zn (NH3) 4] (MnO4) 2 – is an ammonia complex salt, which is a relatively weak but also sensitive initiating explosive. It has an oxygen balance of -4.3 - 8 6% (since the reaction products contain a mixture of both MnO and Mn2O3), and the volume of detonation gases about 483 l / kg.


Tetramine Zinc Permanganate is unstable in storage, gradually decomposing with the loss of ammonia, resulting in a characteristic odor, accompanied by self oxidation-reduction. The latter reaction is accompanied by the release of nitrogen, water and ammonia and, because this reaction is autocatalytic, if not properly stored it can lead to an explosion, both because of the ignition, and just because of the increase of pressure in a sealed vessel. Keep substance preferably at low temperature in a dry atmosphere, as in the presence of moisture it is less stable than ammonium permanganate.

The solubility of Tetramine Zinc Permanganate in water is very small - the reaction of its formation is used in analytical chemistry (microcrystalline microscopy) for the detection of zinc (with a detection limit of 1:7000 ). As a consequence, from a solution of salt precipitated in the form of fine black powder, shiny needle crystals are formed only with careful crystallization from relatively dilute solutions. In general, due to low solubility, synthesis of Tetramine Zinc Permanganate is simple.

Required equipment: chemical glasses (or better disposable plastic) , refridgerator (or freezer), and desirable but optional, an electric mixer and filter.

Materials needed: potassium permanganate, zinc oxide and zinc chloride (or nitrate), ammonium chloride (or nitrate), 10 - 30% aqueous ammonia (ammonia), distilled water.


Stages of Preparation:

1) In 100 ml of distilled water dissolve 4g KMnO4; to accelerate the dissolution it is recommended to use an electric mixer;

2) to 8 ml 20% aqueous ammonia is added 1.1 g ZnO, and 1.4 g NH4Cl (or NH4NO3); zinc oxide should dissolve completely, instead of zinc oxide and ammonium salts can take an equimolar amount of the corresponding zinc salts;

3) The prepared solutions were mixed and rapidly cooled before freezing;

Note: The precipitation of Tetramine Zinc Permanganate takes place during mixing of solutions, cooling slows the recovery of permanganate ion and free ammonia yields a relatively pure product.

4) The bulk of the cold solution is poured, and the residue washed precipitate on the filter, the solution to further remove the filter with the precipitate on the stack of filter paper sheets, after which the product is loosened as soon as possible and dried at low temperature (optionally under reduced pressure).

The result is a 4 – 4.5 g of fine black powder (yield of permanganate 85 - 95%), the presence in it a brown powder of manganese oxides indicates that the product is partially decomposed by high temperature or duration of precipitation and drying.

In principle, the use of dilute (and not contaminated colloidal particles), the starting solution can be precipitated more pure Tetramine Zinc Permanganate in the form of small brilliant needles, but in this case the output drops sharply.
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[*] posted on 13-2-2012 at 00:25


There are some salts of salts of azotetrazole likely ammines which hold more potential I would think. Adding tetraamminecopper(II) nitrate powder to aq. sodium azotetrazole under stirring affords a bright green solid which is uncomparably mechanically far less sensitive than the extremely sensitive copper azotetrazole, but also less brisant.

Quote: Originally posted by NatashaJurievna  
BTW, German patent DE922216 says about the heavily oxygen deficient basic triethanolamine lead perchlorate that "unter Einschluß detonierende Substanz" - detonating substance under confinement.


The copper salt appears to hold energetic properties also. It was obtained from addition of perchloric acid onto aq. triethanolamine-copper complex and drying the liquid over H2SO4, left a deep blue solid which flashed violently with a wonderful blue light when heated over a flame. The experiment was done several years ago and perchloric acid may have been present in excess.
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[*] posted on 14-2-2012 at 00:42


Quote: Originally posted by Taoiseach  
DACP supposedly stands for "double azido cobalt perchlorate", the correct formula is trans-tetraamminediazido-cobalt(III) perchlorate [(NH3)4(N3-)2Co(3+)](ClO4-). Whats interesting about this complex is the fact that it contains azide ligands, fuel and an oxidizer in a single compound.

It is briefly investigated in a freely available paper "Lead Azide Replacement Program NDIA Fuze Conference" by Bichay and Hirlinger. It is also discussed in more depth in several Chinese publications. I cannot download nor understand these papers but the google translation of the abstracts gives some valuable hints. 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.

tetraminecobaltazideperchlorate.jpg - 12kB

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.


This has to be the most interesting complex salt that has been mentioned in this thread.

There must be variation of this compound that is even better.
Perhaps hydrazine instead of ammonia? I would be hesitant to make a perchlorate complex hydrazine salt after reading about the accident with cobalt hydrazine perchlorate, which suggests dangerous friction sensitivity.
http://www.sciencemadness.org/talk/viewthread.php?tid=14587
It is not just complex salts, because hydroxylamine perchlorate is very sensitive (drop height 2cm). But hydrazinium nitroformate apparently is not very sensitive, as it has been researched as a solid rocket fuel oxidizer. But nitroformate probably has different compatibility issues than perchlorate. Ammonium nitroformate appears to be the most stable nitroformate salt.
Quote:

Silver nitroformate slowly decomposes at room temperature, and is a very sensitive explosive. The potassium salt, KC(NO2)3 is a lemon yellow crystalline solid that decomposes slowly at room temperatures and explodes above 95 °C. Ammonium nitroformate deflagrates or explodes above 200 °C. Hydrazinium nitroformate is thermally stable to above 125 °C. Most salts of trinitromethane derive from the aci-form. However, the silver and mercuric salts exist in two forms: colourless and yellow. This may indicate that two forms of these salts - nitro and aci - can exist.

So it would seem nitroformate would be stable in the presence of hydrazine, but not with certain metals (probably including copper).

Quote: Originally posted by Formatik  
Adding tetraamminecopper(II) nitrate powder to aq. sodium azotetrazole under stirring affords a bright green solid which is uncomparably mechanically far less sensitive than the extremely sensitive copper azotetrazole, but also less brisant.

This is good to know. I would have been a little concerned about whether nitroformate would be ligand towards Co+3, as this could result in dangerous sensitivity (nitroformate is stabilized by being an anion). But apparently complexed ammonia molecules make the transition metal ion less "noble" in character. (difficult to explain, hopefully you understand what I mean)

Nitroformate salts are usually bright yellow in color, but might not contribute a any color if the nitroformate acts as a ligand rather than anion, which would also presumably make it more sensitive.

Perhaps...
Hydrazine-diazido-cobalt nitroformate ?
(N2H4)2(N3)2Co[+] C(NO2)3[-]

Not sure what color it would be, but probably would have a grayish tone from being a mix of yellow and light purple. But difficult to speculate, as complex cobalt salts can take a range of colors.

Complex cobalt nitroformate salts have already been prepared:

Journal of Structural Chemistry
Volume 32, Number 3, 339-344, DOI: 10.1007/BF00745741
Crystal structure of (4-amino-1,2,4-triazole)pentaamminecobalt(III) nitroformate [Co(NH3)5 (C2H4N4)][C(NO2)3]3
N. V. Podberezskaya, N. V. Pervukhina and V. P. Doronina
http://www.springerlink.com/content/q50434k7334m1wt6/

ethylenediamine copper(II) nitroformate
[C2H8N2]2Cu[C(NO2)3]2
Li Yang, Jin Zhang, Tonglai Zhang, Jianguo Zhang, Yan Cui
Beijing Institute of Technology, China


A quick note about the chemistry of cobalt, solutions of Cobalt(II) salts in water are not oxidized chlorine, but the presence of ammonia renders the cobalt much more vulnerable to oxidation, even by air.

It might actually be fairly complicated to prepare a hydrazine cobalt(III) salt, since non-complexed cobalt(III) salts generally do not exist. Oxidizing the cobalt(II) with hydrazine already in the solution would also likely lead to oxidation of the hydrazine. Perhaps Co2O3 reacted with a solution of hydrazinium nitroformate, hydrazinium azide, and some additional hydrazoic acid would work.


Here is what the decomposition formula for the compound would be:

(N2H4)2[N3]2Co[C(NO2)3] --> CoO + 4 H2O + CO2 + 6½ N2

[Edited on 14-2-2012 by AndersHoveland]
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Formatik
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[*] posted on 15-2-2012 at 20:39


Yes, the ammine does desensitize the original energetic compound, though it will also take away from its power unless an oxidizer or high nitrogen is present. Another example of large sensitivity reduction is the complex of tetraamminecopper(II) nitrotetrazolate, a fairly soluble blue solid with impact sensitivity of manyfold less than copper (II) nitrotetrazolate. Copper nitrotetrazolate is a frightening material to work with anywhere near the dry state.

Speaking of cobalt salts, cobalt diazoaminotetrazole has very low sensitivity to mechanical action (in strong contrast to Hg, Cu, Ag, Pb salts which are highly sensitive), cobalt azotetrazole is also of relatively low sensitivity (again in contrast to the same metals). Though both salts are not that brisant, the latter probably more than the former. There is good potential of forming low sensitive salts with cobalt.

Thinking on the perchlorate above, how about a polyamminecobalt-azido-azotetrazolate, or nickel hydrazininium azotetrazolate. :P Maybe a question too general, what is better for an energetic then, to have an oxidizing moiety or high nitrogen content?
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[*] posted on 16-2-2012 at 19:01


Yes, I was thinking about the compound with nitrotetrazolate ligands instead of azide.

(N2H4)2[N3]2Co[C(NO2)3]

(N2H4)2[N4CNO2]2Co[C(NO2)3]

But I am not sure if nitrotetrazolate can act as a suitable ligand to replace the azide. This is important because if the two anions have near the same ability to act as a ligand, a double salt would be unlikely to form, and the ions would just precipitate out as separate crystals of two different compounds. There is also nitrotetrazole-2-oxide that exists. So I suppose this would be possible,

(N2H4)2Co[CN5O3]3

One of the advantages of cobalt is that it would bind to the hydrazine very strongly. For example, the ammonia complexed in tetramine cobalt chloride do not come off even if the compound is dissolved in hydrochloric acid, and indeed the complex salt can be crystallized out of a solution of hydrochloric acid. The Co+3 ion is very acidic, one of the reasons that Co(II) salts will not be oxidized in the absence of ammonia. So no worries about hydrazine decomposing out from the complex salt.

Hydrazine is much more energetic than ammonia, I was just thinking about how to combine several strategies together into one compound: a complex double salt with hydrazine, azide, and nitroformate.


Quote: Originally posted by Formatik  

cobalt diazoaminotetrazole has very low sensitivity to mechanical action (in strong contrast to Hg, Cu, Ag, Pb salts which are highly sensitive), cobalt azotetrazole is also of relatively low sensitivity. There is good potential of forming low sensitive salts with cobalt.


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?
That would be amazing if it were just plain azotetrazole that only was not especially sensitive. Would that not mean that the ammonia complex of that compound would be even less sensitive? Or would there be no room for the ammonia to complex?


Quote: Originally posted by Formatik  

what is better for an energetic then, to have an oxidizing moiety or high nitrogen content?


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

[Edited on 17-2-2012 by AndersHoveland]
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