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Author: Subject: Exotic Primaries - Complex Salts
Rosco Bodine
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[*] posted on 2-8-2010 at 07:26


Seeing the DACP, it would definitely be interesting to look also at nickel complexes and possible nickel styphnate multiple salts as a possibility.
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[*] posted on 2-8-2010 at 11:59


I also tried to make the cobalt complex. I proceeded as follows:

Take a big spatula of cobalt carbonate
Add a small amount of 60% perchloric acid and heat a little. All of the cobalt carbonate dissolves, a pink/rose solution is obtained and also quite a lot of a crystalline mass of solid cobaltous perchlorate. On cooling down a reddish brown slurry is obtained, hardly any liquid remains.
To this I added a large excess amount of 10% NH3. When this is done, a blue precipitate is formed, which is air-sensitive. Also a white crystal meal is obtained, the latter most likely is NH4ClO4. After a while, the blue color changes to pink/brown. This is not due to aerial oxidation, the precipitate just changes color, but this is a known property of many basic cobaltous compounds.
Then I added a concentrated solution of NaN3. When this is done part of the precipitate redissolves and the liquid becomes turbid and pink/purple.
Then I added some more water and some more ammonia and heated for several minutes. Most of the precipitate dissolves again, the liquid becomes beautiful deep purple/red.
On cooling down a dark purple precipitate is formed, consisting of many fine crystals. The color also shifts from deep purple/red to a much duller pink color.

I filtered this precipitate and obtained something which very much resembles what is shown in the picture of Taioseach. Next, I rinses three times with distilled water. When this is done, then the color of the precipitate becomes much darker, it becomes dark purple. Only a very faint smell of ammonia is left after the three rinses.

Now the material is drying. Even the wet material already is capable of burning somewhat, so its energetic properties look promising.

Quantities used in the experiment are not critical at all. No need to do precise measurements of chemicals, just combine them as described above. I assured that there is excess ammonia and excess azide relative to the cobalt. Enough water must be added to assure that all ammonium perchlorate formed in the process is dissolved.

----------------------------------------------------

I however have doubts about that this is a cobalt(III) compound. I hardly had the material in contact with air. I also find the purple color of the compound quite a lot like a cobalt(II) compound.




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[*] posted on 3-8-2010 at 22:37


The sample I now have has changed color considerably. It now is a green/grey solid. When the solid is ignited it quickly burns without visible flame, giving a black smoke. It burns fast with a soft hissing noise and is very easily ignited, also in tiny amounts. No need to keep it over a flame for a long time, even when it comes near a flame it already ignites. When larger pieces of the solid are ignited, then the piece of material jumps around while it is burning, leaving a trail of a very fine black powder.



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[*] posted on 3-8-2010 at 22:54


Doesn't sound like the stuff I have. No guarantee tough I have the correct stuff - the synthesis was simply an adoption of known procedure to make bis-ethylenediamine-diazido-cobalt(III)nitrate.

Whats interesting is that your solution turned purple upon addition of NaN3. In my case it retained a deep-prussian-blue like color. It only turned purple slowly while blowing in air.

I wonder how one can make sure that two azido ligands are fixed. The mono-azido-diperchlorate could form just as well. And it surely would be less energetic.
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[*] posted on 4-8-2010 at 11:29


I carefully reread what you have done. You bubbled air through the mix for 3 hours, that is what I did not do. I just boiled for a while to get all of the material dissolved and then allowed to cool down and form a precipitate. I think that is the main difference.

The compound I made also can easily be brought to explosion. I took a piece of 20 mg and folded this in a small piece of household aluminium foil. When this is put in a flame, then a fairly loud high pitched report is obtained and the aluminium foil is punched.




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[*] posted on 4-8-2010 at 12:12


>When this is put in a flame, then a fairly loud high pitched report is obtained and the aluminium foil is punched.

That means it has fixed at least 1 azido ligand I think. The ammine cobalt perchlorates dont DDT that easily.
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[*] posted on 4-8-2010 at 23:24


Yes, I also think it must have azide in it. The explosion is obtained very easily, just keeping the piece of foil with the solid in it above a flame of an alcohol burner for a few seconds, that's all what is needed.

Finally, I added the last small amount of my green/grey solid to 2M H2SO4. When this is done, the solid quickly dissolves, giving a lot of a colorless and odorless gas and the liquid becomes pink, just like plain cobalt(II). I think that the green solid contains cobalt(III) and that on addition to the sulphuric acid the azide ligands are stripped off and the free cobalt(III) probably oxidizes water to make cobalt(II) and oxygen. On heating, the liquid had the smell of HN3, which to me is exceedingly unpleasant (it gives a very weird intense feeling of fear, just as if I have witnessed something really horrible).




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[*] posted on 8-8-2010 at 10:06


Characterization and Output Testing of the Novel Primary Explosive, Bis(furoxano)nitrophenol, Potassium Salt

http://www.users.qwest.net/~m-williams/Articles_PDF/AIAA-200...

.
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Rosco Bodine
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[*] posted on 15-8-2010 at 07:27


Treating a hot nickel perchlorate solution with three equivalents of semicarbazide
solution might be interesting.

It might also be interesting to see if anything interesting may further result from treatment with sodium nitrite.
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[*] posted on 15-8-2010 at 07:43


How about Hg and Fe complexes?

[Edited on 16-8-2010 by Mildronate]
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[*] posted on 27-8-2010 at 21:14


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...

[Edited on 28-8-2010 by Chainhit222]




The practice of storing bottles of milk or beer in laboratory refrigerators is to be strongly condemned encouraged
-Vogels Textbook of Practical Organic Chemistry
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[*] posted on 29-8-2010 at 10:29


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.

Attachment: Gmelin, Ni, Tl. C, 110.pdf (1.9MB)
This file has been downloaded 1197 times

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[*] posted on 30-8-2010 at 04:30


Quote:
what the fuck was he thinking


It's pretty clear if you read the whole article that the guy was pretty much advice-proof. Adviser tells him to make no more than a few hundred mg, he scales it up to 10g. He had numerous unlabeled bottles. He used all of 14 pages of his notebook to describe 3 months of lab work (!!!). Lots of bottles and stuff out in the open, in the photo it looks like his workspace was a mess even before the explosion. And I would bet that his claim of just taking off his safety goggles right at the end was probably BS too.
Still much of the blame has to go to the uni... the existence of sloppy and inexplicably self-destructive people is well-known and there are (or should be) rules and enforcement measures that would have stopped this guy a long time ago.
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Rosco Bodine
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biggrin.gif posted on 17-9-2010 at 06:25
basic lead guanyl azide styphnate , (exist ?) , theoretical compound


A hypothetical compound which may or may not exist has occurred to me, basic lead - guanyl azide styphnate, a possible compound which may be of interest by itself and may further be of interest as a possible substrate for a series of clathrate compounds having higher energy than the already known series of clathrates which are possible using basic lead picrate as the substrate. There has been from time to time mention made of what other possible substrates for clathrates may exist, and may be an improvement over the basic lead picrate, and this purely hypothetical compound, basic lead - guanyl azide styphnate seems a possibility, so I thought I would share this idea, for the entirely speculated compound, which at this point I truly have no idea if it even exists beyond the idea that it seems possible. I offer here my pure speculation for the hypothetical compound, for whatever it may be worth as a possibility or interest for experimentation. :D

[Edited on 17-9-2010 by Rosco Bodine]
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[*] posted on 18-12-2010 at 22:26


Rosco,

To your best knowledge, which is the most friction/impact/heat stable primary that is practical to make? I've read a thread on azo-clathrates, lead azide and its properties, and heard plenty good about silver acetylide. Btw, silver acetylide has only hobbyist-derived information, so annoying.

Which one has the best overall stability?



[Edited on 19-12-2010 by holmes1880]
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Rosco Bodine
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[*] posted on 19-12-2010 at 03:19


There are several pages in Fedoroff PATR regarding silver acetylide and its double salts, and there are patents and other references, so you are incorrect that there is only hobbyist derived information.

Your question I can only answer in part. I haven't studied or tested to identify one which one would have an average of different properties that represents highest overall stability. Generally with primaries there is a tradeoff of one good property for another and you can't have everything great at the same time for what properties are most desirable. That being true generally leads to binary compositions that are mixtures where the properties of one compound complement another. My experiments are incomplete even concerning my own ideas of things to test. I spend a hundred times as much time reading as actually doing any experimenting. So I have a substantial backlog of ideas to test, most of them having already been posted in case anyone else wants to followup before I get to it. Earlier in this thread I mentioned a binary primary that is unusual in its reported property of low sensitivity to impact, a lead azide - barium styphnate mixture. There are probably several other binary compositions.
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...
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[*] posted on 19-12-2010 at 21:42


You're right, DS have been discussed in scientific literature, but they seem to overlook specifics on sensitivity. "Very sensitive to shock and friction" is about all they state. 1kp can be considered very sensitive, but 0.1kp is a whole lot more sensitive.

Powerlabs has shock sensitivity of 2kg--3.4cm, more than TATP, which doesn't seem right.

[Edited on 20-12-2010 by holmes1880]
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[*] posted on 9-1-2011 at 05:20


Can make primary explosive from caseine nitrate. I search information about acsein nitrate from internet but I don`t fiind more information.
I remeber from book from an primary explosive made from milk.
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[*] posted on 9-1-2011 at 07:26


Casein nitrate is energetic but I don't think it's a primary explosive.
I might be wrong though!

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[*] posted on 18-1-2011 at 03:54


@otonel : That book was probably KIBC ? Remove it from your pc.
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[*] posted on 18-1-2011 at 05:21


I didn't want to start a new topic about this single question so I thought it would be best suited here.
I made lead azide according to the method described on the megalomania website.
I made a blasting cap with it as follows:
Drinking straw which is closed on one end with hot glue.
Pb(N3)2 is pressed in the drinking straw and a little bit of blackpowder is placed on top with a fuse in it, and a little bit of tissue paper to hold it in place.
Then some tape was put over the top (over the tissuepaper).
When the fuse was lit it only burned with a bit of sound, like pressed blackpowder would burn....

Anyone got an idea what is wrong with it?

[Edited on 18-1-2011 by DNA]
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[*] posted on 9-10-2011 at 12:01


Dextrinated LA under slightly alkaline conditions alters crystal size and shape to produce a 92-97% pure material that is less sensitive to static, friction and impact, but unfortunately also less prone to make DDT.

There are 3 solutions:

1. Provide better confinement. It is inadvisable to use a drinking straw anyway, since it can easily deform while manipulating it with a sensitive primary inside.
2. Use a hotter burning pyrotechnic composition to cook it off.
3. Use a very small amount of an initiator like the silver acetylide/nitrate double salt. (Commercially lead styphnate has been used.)

A fourth option is to use collodial LA, by instantly precipitating LA from solutions of a lead salt and NaN3, but this is rather sensitive material. Better improve your cap design...
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[*] posted on 27-10-2011 at 17:02


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.

Also tried out tris(hydrazine) nickel nitrate: when exposed to open flame it flashes like mercury fulminate, but this compound didn't explode if heated over flame in small amounts, the best detonators like silver azide and tetrazolates detonate and blow holes through aluminium sheets. Not even under confinement could I get a detonation in small amounts despite how it flashes.

Tetrazole detonators can easily initiate both of these insensitive materials. 0.02g mercury diazoaminotetrazolate (HgDTZ) initiated 0.08g both NHN and ZHN when underneath them and unconfined, in both cases a small amount of complex powders spread since it was unconfined. But the tests showed the holes these two made against aluminium sheets were far larger than the 0.02g HgDTZ made alone. The two holes were close in size to one another.

Both hydrazinate compounds would be good for demonstrations, the nickel salt for its unique color and flashes, and the zinc salt for its glitter and fierce burning and interesting flame.
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[*] posted on 27-10-2011 at 17:19


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.
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[*] posted on 27-10-2011 at 17:39
Primary resistant to impact


Nickel hydrazine nitrate is a potential primary explosive that shows good resistance to impact, while still being easily initiated by flame. This means that the complex salt may likely be safer to handle than other primaries. The sensitivity to impact (the hammer drop height value at which the sample has a 50% chance of detonation) is 84cm. It is resistant to friction up to 10N, resistant against electrostatic discharge, but is sensitive to flame and will explode in contact with a red hot wire.

Another advantage, small amounts of the compound do not need confinement to detonate. Nickel hydrazine nitrate shows excellent initiating power for a primary. The detonation velocity 7km/s.

One note of warning, nickel hydrazine perchlorate is dangerously sensitive to friction. An accident involving only 5 grams cracked a fragment off a laboratory table and resulted in severe injury.

Here is a video:
http://wn.com/Nickel_Hydrazine_Nitrate

Procedure:
An aqueous solution of nickel nitrate was prepared, containing 8% Ni(NO3)2 by weight. 50mL of the solution was poured into a steel container, which was then heated to 65degC. Separately, 100mL of distilled water was warmed and maintained at around 60degC. Gradually over the period of 30 minutes, 7cm3 of hydrazine hydrate was added into the steel container, simultaneously together with 50mL of the water that had been separately prepared, the remaining water was discarded. The hydrazine hydrate used was somewhat wet to begin with. The color of the reactants in the steel container changed from a bluish tint to purple over the course of the reaction. The reaction was stirred for an addition 10 minutes, maintaining the temperature at 60degC. After cooling to 20degC, the purple colored product was filtered out over two layers of coffee filter paper, washed once with 50cm3 distilled water. The moist caked solid was then partially dissolved in >98% alcohol (50mL ethanol was used), then the alcohol was allowed to evaporate out on an electric hot plate set to only 60degC. The evaporation should be carried out in the dark, but with plenty of ventilation. About 5 hours are required for complete evaporation. From this procedure, about 11 grams of nickel hydrazinium nitrate is obtained, which is a 90% yield. Heating of the reactants/reaction is not in any way necessary, as similar yields were obtained at room temperature, but the product obtained from heating shows better physical properties, as the salt is of a more crystalline form. The crystalline form has a density of about 0.89 g/cm3. The nickel hydrazinium nitrate thus obtained, when gradually heated, explodes at 219degC. The compound appears thermally stable even up to 200degC. Sensitivity (50% probability of explosion using 2kg drop hammer from variable heights) value of 84cm. Velocity of detonation: about 7km/sec.

The co-crystallization of NHN with silver azide, such that the resulting clathrate contains 10% by weight of AgN3, increases the drop height sensitivity to a value of 66cm. Even such a clathrate containing only 2% silver azide is not much less sensitive, having a drop height value of 68cm. As a side note, cobalt hydrazinium nitrate, which can be similarly prepared, is even more sensitive, having a sensitivity drop height value of 59cm. The cobalt salt also explodes at a lower temperature, 188degC. Interestingly, however, the cobalt salt is actually somewhat less sensitive to friction than NHN.




I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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