Sciencemadness Discussion Board

Novelty explosives

Axt - 10-1-2006 at 19:46

So, everything from Prince Rupert's drops to mercarbide perchlorates. What are some of the other novel, fun explosive substances that have little to no practical value?

Example "Explosive Bismuth" of unknown constitution is formed by gently heating bismuth in contact with 70% perchloric acid, at about 110°C a brown layer of sensitive explosive forms on the surface that will explode with a sharp snap if tapped with a metal object.

In the pictures below a drop of 70% HClO4 was dropped onto an ingot of Bi, when the MAPP torch was lightly waved over the metal white fumes were given off a dark brown surface was created almost instantly. Tapping this layer with the edge of a knife or over heating it produced a sharp explosion, sometimes with enough force to shatter the Bismuth (which is brittle).

<center><img src="http://www.sciencemadness.org/scipics/axt/exploding-bismuth.jpg">
<a href="http://ww1.webtop100.net/~62552/xmovies.webtop100.net/banners/explosive-bismuth.mpg">MOVIE</a></center>

What the brown layer is, is not known, but the final products were shown to be:

8Bi + 24HClO<sub>4</sub> + heat --> brown stuff -BANG-> 7Bi(ClO<sub>4</sub>;)<sub>3</sub> + BiCl<sub>3</sub> + 12H<sub>2</sub>O

So considering the low surface area of above example and quantity of unused oxidiser I imagine mixing powdered Bi damp with HClO4 maybe with a fuel (acetic acid?) would be rather energetic if heated.

Sooo.. I dont care how lame it is, anyone have "Prince Ruperts drops" work for them? not me. Try keeping it to little known substances, ammonium triiodide/armstrongs/fulminating silver/yellow powder are well known... there has to be more, hydrazides, hydroxylamates...

[Edited on 11-1-2006 by Axt]

artem - 11-1-2006 at 06:51

Quote:
Originally posted by Axt
What the brown layer is, is not known, but the final products were shown to be:
8Bi + 24HClO4 + heat --> brown stuff -BANG-> 7Bi(ClO4)3 + BiCl3 + 12H2O

Very interesing, Axt, but how they were shown to be? this final products are typical for full reaction in the excess of HClO4. And the brown layer may contain Bi(II) and ClO4-=>bang=> Bi(III-IV)(for example, BiO2, Bi2O3 or BiOCl)+Cl2+O2+q
So, q is the summ of ClO4- ->Cl-(+6...+140kJ/mol for anhydrous perchlorates) and BiO->BiO1.5-2(~100-150kJ/mol).
The maximum Qexpl~0.7-0.8MJ/kg is close to NJ3.

nitro-genes - 11-1-2006 at 06:54

What about "amor complexes" never heard about any of them on any forum... Most familiar is the one formed when basic lead chlorate is dissolved in hot glycerine. It is a white powder, wich detonates even in small amounts. Its definitly more sensitive than silveracetylide/nitrate or leadazide. It has been proposed for use as a primer or initiating mixtures though...(PATR volume 2)

There is a good synthesis for chloric acid in the "Handbook of preperative inorganic chemistry"by Brauer. This was used to prepare the Leadchlorate with leadoxide. Caution is nessecary because it seems that anhydrous leadchlorate in it's self is explosive :o

There are also the organic chlorates, PATR mentions guanide chlorate and ethylenediamine dichlorate. The latter was even proposed for use in detonators, so I presume it is quite stable. Hygroscopicity could be a problem though. Unfortunately I have not yet been able to purchase ethylenediamine or guanidine to try out my self...

[Edited on 11-1-2006 by nitro-genes]

[Edited on 11-1-2006 by nitro-genes]

[Edited on 11-1-2006 by nitro-genes]

Axt - 12-1-2006 at 03:56

Quote:
Originally posted by artem
Very interesing, Axt, but how they were shown to be?


Its from this article, I've attached previously into another thread.

<a href="http://www.sciencemadness.org/scipics/axt/bismuth-perchloric.pdf">Nicholson, D. G. & Reedy, J. H. "The Explosive Reaction of Bismuth with Perchloric Acid". Journal of the American Chemical Society, vol 57, pg. 817-8, (1935).</a>

They made some attempt to analyse the explosive product, but with no definate conclusion.

Here synth for "Ethane Hexamercarbide", theres a few other references to this that dont detail the synthesis, but typical syth is to reflux HgO/EtOH/KOH. The following is more a byproduct.

<i><b>Formation of Ethane-hexamercarbide</b>: A mixture of 7.96 g. of mercuric acetate, 44.8 g. of potassium hydroxide, 35 cc. of water and 153 cc. of alcohol (mercuric acetate 1 mole, potassium hydroxide 32 moles, water 100 moles, alcohol 100 moles) was refluxed for thirty minutes. The residue on hot filtration was washed with water and dilute alkali. It was then digested with 20% nitric acid until it became white. The solid was filtered off, washed with water and digested with potassium hydroxide solution. The residue was filtered, washed with water and air dried. The product was yellowish; yield, 0.64 g. It exploded violently at 230'.</i>

Funnily I searched for "mercarbide" and this google cache come up. Imagine getting payed to do that!. Pitty the pdf is no longer avalable so no pics.

http://64.233.161.104/search?q=cache:ht8FX5msMfQJ:www.flube.com/users/jojo7/impdet.pdf+mercarbide&hl=en

Interestingly, nitro-genes, the lead chlorate/glycerine complex you mentioned is in there as well. ("amor complexes" would mean amorphous? so I think its just a description rather then a title). Thats an interesting one.

From Bretherick:

Hofmann, K. A. et al., Annalen, 1899, 305, 191
A yellowish precipitate was obtained from mercury chloride and hydrazinium chlorides when basified with sodium acetate. It had N-Hg bonds and was perhaps ClHgNHNHHgCl. It exploded on heating or shock. A similar compound resulted from the bromides.

nitro-genes - 12-1-2006 at 13:50

Yes you are right of course, all those stupid abreviations in PATR make it sometimes look like some form of secret code.
And was really beginning to like the term "Amor complex" :( I mean love can be quite explosive as well can it? :D

I can imagine that there saying: "Attempts to prepare the required lead chlorates in a field manner did not meet with satisfactory results" :)
Lead chlorate is quite hygroscopic and precipitation from 96% alcohol yields the monohydrate. That has to be heated somewhere between 110 and 190 deg. C to obtain the anhydrous form.
I have no idea whether the 20% chloric acid that I used yields the basic leadchlorate or just leadchlorate. As both are to be made with solutions of chloric acid...

Axt - 13-1-2006 at 02:55

The Explosion of Chloroform with Alkali Metals
Tenney L. Davis, John O. McLean
J. Am. Chem. Soc.; 1938; 60(3); 720-722. [attached]

Attachment: chloroform-alkali-metal-explosions.pdf (320kB)
This file has been downloaded 1900 times


artem - 13-1-2006 at 04:52

Quote:
Originally posted by Axt
They made some attempt to analyse the explosive product, but with no definate conclusion...

Interesting, it seems to me, that the idea about Bi(I,II) may be correct. If the reducing of HClO4 by Bi gives us only Bi(I), for example, 8Bi+HClO4+3H2O->7BiOH*BiCl, +2HClO4->5BiOH*BiCl*2BiClO4, the ratio Bi/Cl(-) of the hydrolysed product will be 1:0.125 (exper.0.084-0.185). During the explosion Bi(I)->Bi(III): 5BiOH*BiCl*2BiClO4->3BiOCl+2.5H2O+2.5Bi2O3, the ratio Bi/Cl(-) will be 8/3, and no mettalic Bi in the exlosion products.
About lead chlorate/glycerine - probably, it is the analogue of known explosive complexes such as Pb-glyceroperchlorate (or, instead glycerine - C6H8(OH)6, C(CH2OH)4, C4H6(OH)4, NO2C(CH2OH)3) with the supposed structure C3H5(O-)3Pb2ClO4?
Quote:
Originally posted by Axt
A yellowish precipitate was obtained from mercury chloride and hydrazinium chlorides when basified with sodium acetate. It had N-Hg bonds and was perhaps ClHgNHNHHgCl. It exploded on heating or shock. A similar compound resulted from the bromides.

And what about N-N bonds? There is also yellow/also explosive [Hg2N]Cl...

Swany - 29-1-2006 at 10:43

Nitrosoguanide anyone? :P A sensitive primary explosive that produces little heat and no flash when detonated. There is a demo involving placing .5g on the back of ones hand(!!!) in a dark room, lighting a match, blow it out, and touch it to the explosive, needless to say, it explodes. The only after effects noted on Megalomania's page regarding injury is a rash and peeling skin. Clever.

Perparation is rather straight-forward once you have guanidine nitrate, or nitroguanadine. Guanidine nitrate is the real killer, as preperation of that requires dicyanodiamide. Hmmm. Once that is aquired, it is cake. I simply aquired guanidine nitrate. It should be noted that both nitroguanidine and guanidine nitrate are extremely similar to nitrourea and urea nitrate respectively.

Convert the guanidine nitrate to nitroguanidine using conc. H2SO4 and lots of stirring. Precipate, wash, recrystallise with boiling water, and let it dry.

Nitrosoguanidine requires nitroguanidine, zinc dust and ammonium chloride. 21 g of nitroguanidine, 11 g of ammonium chloride, 18 g of zinc dust, and 250 mL of water, are used in the procedure on Megalomania's page. This is all stirred with a mag. stirrer while keeping the temp ~20C with an ice bath. After 2 hours, it should be yellowish, rather than the original gray of zinc. This is due to a collection of zinc oxides, hydroxides, and basic chlorides, along with your nitrosoguanidine. This is filtered, and 4 portions of 250mls of water heated to 65C are used to extract it. All of the portions are left to sit, and nitrosoguanidine will precipate. Yeild is about 50%. It can be stored indefinitely dy in a sealed bottle.

Now I just have to get around to making some nitroguanidine. :)

DeAdFX - 30-1-2006 at 19:34

I saw one of the north american pyrotechnic stores carrying guaidine nitrate.. 12 usd a pound

Swany - 30-1-2006 at 20:22

Yes, perhaps the same source of mine.

I converted 15g of guanidine nitrate to nitroguanidine using 20mls of 93% drain opener H2SO4 and lots of stirring. The whole procedure took about 5 hours, and at that point it was totally clear with a slight, hardly noticable, cloud of crystals in it. Yeild was 9g, though some product was lost due to ineffecient washings. The product is quite feathery, and upon attempts to burn it, it will melt and then burn with a sizzling sound, rather nicely. Guanidine nitrate, when attempted to be burnt, simply coated the match with a white residue.

So, an expiremental prep. of nitrosoguanidine is being preformed.

Reactants:
3g Nitroguanidine
2.75g Zn powder
NH4Cl solution(~8mls of 31.45% HCl neutralised with NH3. Needed more NH3 soln that thought, so no additional water was added to reaction)

This ended up to be about 75mls of total volume.

Everything was mixed togeather, and this is more water than Megalomania suggests to use, by 2x. I have no magnetic stirrer, so hand stirring must be used. This is not good, as the Zn is (obviously) dense and upon stopping of stirring, drops to the bottom of the beaker. :mad: A very modest amount of heat was evolved during the first 60 mins of reaction, enough to keep the vessel *slightly* warm.

2.5 hours later, and after 10 min in a hot water bath, the water in the vessel, when it seperates out, is quite yellow/green (due to basic zinc chloride, I hope), and some milkyness has been noted. It was not like this originally, so it will be left overnight and re-assesed in the morning.

This is a very crude attempt. Any further attempts would be done according to how it is *supposed* to go, with dry NH4Cl, and the proper amount of water. No dodgy preparation of NH4Cl solution on the spot...

S.C. Wack - 31-1-2006 at 03:20

> Guanidine nitrate is the real killer, as preperation of that requires dicyanodiamide.

Surely there are other (unused, novelty) methods not using cyanamides. OTOH a patent that alleges that urea and sulfamide give the sulfate, US 2590257 and there is another patent using urea also mentioned earlier by Mephisto here

Obviously not as convenient but not that bad if they work and you have the required chemicals.

[Edited on 31-1-2006 by S.C. Wack]

DrP - 31-1-2006 at 04:26

> Guanidine nitrate is the real killer, as preperation of that requires dicyanodiamide.<


Whats wrong with dicyandiamide? MSDS says only slightly toxic (LD50 10 g/kg)
Is there something else I should know about DiCy?

Swany - 31-1-2006 at 06:33

Sorry, that was just a terrible anology by me. There is nothing *wrong* with dicyanodiamide, but rather with aquiring it.

The reduction with no magnetic stirring is taking forever, estimated at about 15 hours to completion. The amount of time stated in the procedure was 2 hours, albiet with stirring. It is nearly done though, so all ends well. Hopefully.

Swany - 31-1-2006 at 18:00

Nitrosoguanidine has been extracted and is now chilling in a yellow solution, not unlike that of picric acid or dilute urine.

We have some conflicting information, Megalomania says extract with water, and the MSDS says,'Water solubility: reacts violently'. Well, when I washed it, I think a bit of gas formed, but there was water in the reaction vessel, perhaps this is to blame the yeilds on. All of it did not react, as there was still plenty of Zn and I belive some NQ in the waste solids. Better luck with a mag stirrer.

The only thing that a google search agrees on is that it is really carcigenic(spelling).

Axt - 31-1-2006 at 20:13

Quote:
Originally posted by Swany
Megalomania says extract with water, and the MSDS says,'Water solubility: reacts violently'.


It was copied from COPAE, which gives more info on its reactions with water, in water it dearranges to nitrosamide (NH2-NO) which if heated decomposes to nitrogen and dicyanodiamide. See pg. 391 of COPAE.

Swany - 31-1-2006 at 20:45

I figured it was copied from somewhere, as is most of the stuff on his site. I will look that page up.

Very well, but does that really explain 'reacts violently'? I have my suspicions with the MSDS sheet, as it also quotes color to be pink to yellow, though other google results that talk about its cancerous effects also note this, I think.

It is currently crystallizing slowly, and it forms very beutiful spider-webbish needlelike crystals, quite like K picrate. It is not quite as yellow though, a very mild yellow at that.

Madandcrazy - 8-2-2006 at 08:04

Interrested topic with substances that have little practical value. It figured out some possibilities with some metal
salts maybe with hydrazinium.

Possibly when hydrazinium sulfate is stirred in hot anhydrous ethanol and the synthesis is continued with lead(II)nitrate, contingently a interested salt is formed with the hydrazinium sulfate, the ethanol and the nitro group.

Axt - 3-3-2006 at 16:31

Another "fulminating bismuth", this is from Fortunes in Formulas by Hiscox & Sloane in the section on "fulminates" originally printed in 1907.

<i><b>Fulminating Bismuth</b> - Take bismuth, 120 parts; carbureted cream of tartar, 60 parts; niter, 1 part.</i>

Not sure whats meant to be going on there, niter is KNO3 and cream of tartar is potassium bitartrate. But what is "carbureted cream of tartar"?

bullstrode - 3-3-2006 at 17:18

Baking powder perhaps?

The_Davster - 3-3-2006 at 17:51

Carburetted hydrogen is methane, and heavy carburetted hydrogen is ethane. perhaps it is some sort of coprecipitated potassium carbonate tartrate or coprecipitated potassium acetate tartrate?

Or perhaps even some sort of potassium methyl or ethyl tartrate?

Damn archaic nomenclature....

Marvin - 3-3-2006 at 20:49

If you strongly heat cream of tartar you end up with a very intimate mixture of potassium carbonate and carbon that 'cannot' be made mechanically. This was favoured early on for the manufacture of potassium. I suspect this is what is meant, and that a subsiquent furnace stage is missing from the description.

Axt - 6-3-2006 at 17:53

That starts to make some sense. Supposedly you can substitute K2CO3 for potassium bitartrate in yellow powder, though never tried myself.

Placed within the context of the proceeding entry in "fortunes in Formulas" the names are misleading but they now look related.

<i><b>Fulminating Antimony</b> - Tartar emetic (dried), 100 parts; lmpblack or charcoal powder, 3 parts. Triturate together, put into a crucible that it will three fourths fill (previously rubbed inside with charcoal powder). Cover it with a layer of dried charcoal powder, and lute on the cover. After 3 hours exposure to a strong heat in a reverberatory furnace, and 6 or 7 hours cooling, cautiously transfer the solid contents of the crucible, as quickly as possible without breaking to a wide mouthed stoppered phial, where after some time, it will spontaneously crumble to a powder. When the above process is properly conducted, the resulting powder contains potassium, and fulminates violently on contact with water. A piece the size of a pea introduced into a mass of gunpowder explodes it on being thrown into water, or on its being moistened in any other manner.</i>

Tartar emetic? has to be a mix of K tartrate and some form of antimony. I was thinking they screwed up the names and were refering to "explosive antimony" (electrolysis of antimony trichloride) by the title, since there was no actual reference to "antimony" in the entry.

Marvin - 9-3-2006 at 02:13

An emetic is something use medically to make people vomit, incidentally.

Quote:

Tartar emetic,
poisonous, odorless, transparent rhombic crystals or white powder with a metallic, sweetish taste. Chemically, it is potassium antimony tartrate, KSbC4H4O7·1/2H2O. It is used as a mordant in dyeing. Medically, it was formerly used as an emetic and expectorant, to produce sweating, and in the treatment of several diseases, but had frequent toxic side effects.


Just to clarify for general reading, I do not think these are yellow powder type mixtures, and the amount of nitre in the bismuth prep is far too small for a pyrotechnic mixture of any kind. It suggests more 'flux' or 'kickstart' than oxidising agent. I think this is a furnace method for potassium, combined with a material that alloys, soaking up the potassium vapour and locking it away in eutectic that is still active enough to react violently with water when finely divided.

It may just be that bismuth does not survive a cream of tartar method directly, maybe it reacts with the water produced, so a stage is needed to pyrolise to K2CO3/C and then a second to liberate potassium vapour from this in the presence of bismuth. Or it may be that you can simply do bigger batches at the very high temperature if you use 2 stages.

[Edited on 9-3-2006 by Marvin]

d010060002 - 11-7-2010 at 09:53

I recently came across a reference to the explosive nature of the ion Ag(NH4)2+. I think that would be pretty novel, only I have no idea how to make it. Do you guys have any ideas/ experiences with it?

mnick12 - 11-7-2010 at 11:20

This is not something you really want to make it is really sensitive. But I believe it is called "fulminating silver" (correct me if I am wrong) and is made by mixing silver oxide with ammonia.

quicksilver - 11-7-2010 at 11:50

This is a very old thread you guys have resurrected but the fulminating silver is the ammonia/silver nitrate combination that was a problem when making mirrors back in the 1920's. .....Very simple to make and not as powerful as silver fulminate: a curiosity. It's tough to quantify but if silver fulminate were 100; fulminating silver is a 40 in terms of over all strength. It's VoD, heat upon ignition, Tauzal level has not been examined but it is VERY similar to lead styphnate. As long as you're keeping the weight at lower than .5gr the important thing is to wear goggles. It won't knock fingers off at 1/2 gram level unless you're rubbing it within a tightly closed fist. In fact I believe that nitrogen triiodide is stronger. It's within that class of materials. It has a very short shelf-life as I remember.

EDIT:
Cream of Tarter is Tartaric Acid as used in the above examples.
>>>Correction of nitrogen triiodide


[Edited on 12-7-2010 by quicksilver]

Blasty - 11-7-2010 at 17:44

In Sidney Gernsback's A thousand and one formulas, page 103, there's the following experiment that would fall under the "novelty" (i.e. curious but basically useless) explosives/reactions category that is the subject of this thread:

"Explosion Without Heat -- Take a crystal or two of nitrate of copper and bruise them; then moisten them with water and roll them up in a piece of tin-foil, and in a minute the foil will begin to smoke and soon after will take fire and explode. Unless the crystals of copper are moistened, no heat will be produced."

[Edited on 12-7-2010 by Blasty]

Melgar - 11-7-2010 at 18:56

quicksilver - are you referring to nitrogen triiodide? That's a really easy one to make, provided you have elemental iodine. Just mix an excess of aqueous ammonia with your elemental iodine and it'll form a black sludge at the bottom. This stuff is fairly safe when wet, but as soon as it dries out, it's extremely sensitive. Once, I had a little bit dry out in a shot glass, so I poured some ammonia on it to get it wet again. Pouring the ammonia didn't set it off, but I made the stupid mistake of trying to stir it up. Yep, the crystalized stuff at the bottom exploded, sending the liquid part of the mixture right into my face.

quicksilver - 12-7-2010 at 06:14

Yes, I mis-spoke (typed). I was referring to nitrogen triiodide. Fulminating silver was accidentally made in mirror production because of the exposure of ammonia. Just as quickly & easily as you can produce nitrogen triiodide, so fulminating silver can be so mfg. But if the weight level was not significant, it would just pop with a loud displeasing ease.
I'm fairly sure it would fuck up the mirror also.

[Edited on 12-7-2010 by quicksilver]

Hoveland - 30-7-2010 at 13:47

I have read of an explosive double salt of potassium chlorate and thiosulphate, but now cannot find any information on it. Does anyone have a link?

The WiZard is In - 5-8-2010 at 12:28

Quote: Originally posted by Axt  
Another "fulminating bismuth", this is from Fortunes in Formulas by Hiscox & Sloane in the section on "fulminates" originally printed in 1907.

<i><b>Fulminating Bismuth</b> - Take bismuth, 120 parts; carbureted cream of tartar, 60 parts; niter, 1 part.</i>

Not sure whats meant to be going on there, niter is KNO3 and cream of tartar is potassium bitartrate. But what is "carbureted cream of tartar"?



A cyclopaedia of six thousand practical receipts, and collateral information ...
By Arnold James Cooley 1854

II. Triturate together, very carefully, 100 parts of antimony, 75
parts of carbureted (roasted to blackness) cream of tartar, and 12
parts of lampblack : preserve it in vials. (Ann. de Chim., Oct.
1822.)

Remarks. When the above processes are properly conducted, the
resulting powders fulminate violently on contact with water. It is
to the presence of the very inflammable metal potassium that
they owe this property. Another compound, made with 60 parts of
carbureted cream of tartar, 120 bismuth, and 1 of nitre, treated
as above, contains an alloy very rich in potassium. A piece the
size of a pea introduced into a mass of gunpowder explodes it on
being thrown into water. Use. For making some kind of fireworks.
It is very probable that this is the preparation used by Capt
Warner.

The London encyclopaedia: or, Universal dictionary of science ..., Volume 18 1829
edited by Thomas Curtis

A fulminating antimonic powder has been prepared by M. Serullas
in the following manner :—Grind carefully together 100 parts of
tartar emetic and three parts of lamp-black, or ordinary charcoal
powder. Crucibles capable of holding about three ounces of water,
to be only three-fourths filled, are to be ground smooth on their
edges, and rubbed inside with powdered charcoal, so as to dust
lightly their surface, and prevent the subsequent adherence of the
carbonaceous cone which remains after the calcination. The
above mixture, being introduced into the crucible, is to be covered
with a layer of powdered charcoal; and the joinings of the cover
must be luted. After exposure for three hours to a good heat in a
reverberatory furnace, the crucible must be removed, and left to
cool for six or seven hours. This interval of time is necessary to
allow the air, which always penetrates a little way into the
crucibles, to burn the exterior coat of the fulminating mass;
otherwise, if it be taken out too recently, there is always an
explosion. We must then hastily enclose it, without breaking, into
a glass with a wide opening. After some time, it spontaneously
breaks down into fragments of different sizes, retaining all its
properties for years. When the calcination has been conducted as
above, the product is excessively fulminating, so that, without the
least compression, it gives rise to a violent detonation on contact
with water. 100 parts of antimony, severity-five of carbureted
cream of tartar, and twelve of lamp black, triturated together,
form also an excellent mixture. A piece of the size of a pea of this
fulminating compound introduced into a mass of gunpowder
explodes it when thrown into water. It is to the presence of
potassium that the above explosive property is due. Sixty parts of
carbureted cream of tartar, 120 of bismuth, and one of nitre,
treated as above, yield an alloy very rich irf potassium, of which
the smallest portion cut with scissors sparkles. When bruised it
melts and burns.—An. de. Chim. Oct. 1822.



franklyn - 6-10-2010 at 12:26

Sodium Hyponitrite
http://jupiter.chem.uoa.gr/pchem/lab/pubs/XX_24A(1959)147.pdf

An antique thread on this here _
http://www.sciencemadness.org/talk/viewthread.php?tid=147#pi...

.

Exploding Antimony

franklyn - 22-12-2010 at 02:59

http://antimonyproperties.blogspot.com/2009/03/yellow-antimo...

Ttwo unstable allotropic forms of antimony are yellow and explosive.

Much like its arsenic and phosphorus analogs, yellow antimony exhibits mostly nonmetal properties. The oxidization, either by air or oxygen, of liquid antimony hydride produces yellow antimony and black antimony. Yellow antimony is only stable below -90° C. At temperatures between -90° C and -50° C, the yellow allotrope will degrade into its black counterpart. At temperatures above -50° C, yellow antimony rapidly converts into regular metallic antimony.

Explosive antimony is produced by the electrolysis of the aqueous solution of antimony halide. It is believed that this is because of the presence high concentrations of antimony ions in the solution. Explosive antimony deposits on the cathode at a current density of 200 A/m2 in a hydrochloric acid solution containing 17 - 33% SbCl3. Explosive antimony has a steel-gray color and a smooth, soft surface. Its density is 5.64 -5.97 g/cm3. It will produce a vigorous explosion when it is gently struck, rubbed, treated with thermal radiation, or heated to 125° C. The explosion is the result of instant liberation of crystalline heat when a foreign force is applied and will occur even under water.

Attachment: Antimony - Dictionary of Applied Chemistry I A-C , pg 360 .pdf (375kB)
This file has been downloaded 647 times

Exploding Bismuth this thread
http://www.sciencemadness.org/talk/viewthread.php?tid=5112#p...

.


quicksilver - 22-12-2010 at 06:57

I don't want to go too far off topic but where I live there is a great deal of arsenic naturally occurring near two mines. It is very beautiful stuff. If not for it's toxicity I would pile it up a great deal of it and sell if off. Many elements can be gathered if you know where to look.

Hydrazinium - 7-1-2011 at 11:06

Would, for example, nitrosyl fulminate (NOONC) count as a novelty (and probably highly unstable) explosive?
I would assume that a simple synthesis would consist of a very small quantity of saturate silver fulminate solution through which a steady stream of nitrosyl chloride could be passed. The reaction would precipitate AgCl. Hopefully the product would not be destroyed by the solvent, so something as passive as possible should be used.
I would also advise that anyone who tried it keep temperatures just above freezing as no information seems to be available on it.

God grant that mortal men may no be so ingenious at their own cost, as to pervert a profitable science any longer to such horrible uses

The WiZard is In - 7-1-2011 at 13:35

I send you two small phials of nitrated sulphuret of potash, or
yellow powder, as it is usually called in this country....I have made
some hundred pounds of it, which were eagerly bough up by
hunters and sportsman for priming fire arms, a purpose
which it answered most admirably; and, but for the happy
introduction of powder for priming, which is ignited by percussion,
it would long since have gone into extensive use.

With this preparation I have had much to do, and I doubt whether,
in the whole circle of experimental philosophy, many cases can be
ound involving dangers more difficult to be overcome, than
melting fulminating powder and saving the product, and reducing
he process to a business operation. I have had with it some eight
or the tremendous explosions, and in one of them I received, full in
my face and eyes, the flame of a quarter of a pound of the
omposition, just as it had become thoroughly melted.

I shall but just mention a fatal event which lately happen'd in
Germany, from an experiment made with balsam of sulphur
terebinthinated, and confined in a close chemical vessel, and thus
exploded by fire; God grant that mortal men may no be
so ingenious at their own cost, as to pervert a profitable science
any longer to such horrible uses. For this reason I forbear to
mention several other matters far more horrible and destructive,
than any of those rehearsed.

Benjamin Silliman, 1831. In Tenney Davis, The Chemistry of Powder &
Explosives. p. 30-32

The WiZard is In - 7-1-2011 at 14:25

Quote: Originally posted by quicksilver  
I don't want to go too far off topic but where I live there is a great deal of arsenic naturally occurring near two mines. It is very beautiful stuff. If not for it's toxicity I would pile it up a great deal of it and sell if off. Many elements can be gathered if you know where to look.


Realgar occurs in rose-red, orange-red, or orange-yellow prismatic crystals ; in coarse or fine granule, in compact masses or as an incrustation. Strabo, in the first century of our era, in his Geographia (12, iii, 40), said that there sandarach mines at Pompeiopolis, in Paphlagonia ; and added :


The mountain is hollowed out by large trenches made by workmen in the process of mining. The work is always carried on at the public charge, and slaves were employed in the mine who had been sold on account of their crimes. Besides the great labour of the employment, the air is said to be destructive of life, and scarcely endurable in consequence of the strong odour issuing from the masses of mineral : hence tile slaves are short lived. The mining is frequently suspended from its becoming, unprofitable, for great expense is incurred by the employment, of more than two hundred workmen, whose number is con¬tinually diminishing by disease and fatal accidents.


JW Mellor
A Comprehensive Treatise on Inorganic and Theoretical Chemistry
9:267-8

Asthana —
NC Asthana & A Nirmal
The Ultimate Book of Explosives and IED's
2008

Brock —
A St H Brock
A History of Fireworks
1949


For the fireworks fiends - trivia — What was Alan Saint Hill
Brock's occupation?

Ex-plosive-coconuts-Asthana-800.jpg - 296kB Explosive-Coconut-Brock-800.jpg - 744kB

The WiZard is In - 7-1-2011 at 14:35

Quote: Originally posted by The_Davster  
Carburetted hydrogen is methane, and heavy carburetted hydrogen is ethane. perhaps it is some sort of coprecipitated potassium carbonate tartrate or coprecipitated potassium acetate tartrate?

Or perhaps even some sort of potassium methyl or ethyl tartrate?

Damn archaic nomenclature....


I did-id this some time ago when I had spare time upon my
hands. As always - corrections/additions welcome. U2U works
for me.

Attachment: Chem Chemold.doc (126kB)
This file has been downloaded 2320 times

The WiZard is In - 7-1-2011 at 14:38

Quote: Originally posted by quicksilver  
This is a very old thread you guys have resurrected but the fulminating silver is the ammonia/silver nitrate combination that was a problem when making mirrors back in the 1920's. .....



Fair use ... or “The Morality of Convenience” (If it’s convenient ... it’s moral!)
From: Mirrors: A Guide to Manufacture of Mirrors and Reflecting Surfaces
Dr. Bruno Schweig
Pelham Books - London 1973

Danger of Explosions

Unexpected explosions have frequently occurred in silvering shops, to the surprise of the
operators and their employers. The people concerned were rarely in a position to account
for the cause. The present author was repeatedly asked in court cases to explain what
happened, and why. On one occasion an experienced silverer received severe eye
injuries, on another the silvering equipment was destroyed by a night-time explosion, and
on a third a schoolboy lost the sight of one eye when he to make a mirror for his physics
teacher. In all these cases fulminating silver was formed.

Fulminating Silver and its formation was first detected and named after the French chemist
Count Claude Berthollet in about 1770. Crell describes Berthollet's experience in 1788 in
Annalen, der Chemie Pharmacie 2, p. 390. F. Raschig, in Liebig's Ann., 1886 (233), p. 93 e
a full study of it. Dr. W. Friedel in Centralzeitungfor Optik und hanik, March 20th, 1928,
published a good report on the dangers xplosions when silvering, and concluded that the
danger of formation of fulminating silver only exists if concentrated solutions of silver nitrate
and ammonia come together, and that the probability that fulminating silver precipitates is
greatly enhanced by the presence of strong sodium or potassium hydroxide solutions.

These observations tally to a great extent with those of the present author. As far as his
experiences go, over a period of thirty-five years, there was never an explosion from
fulminating silver when silver nitrate and ammonia alone were mixed, independent of their
strength. He has, however, read that such explosions occurred when the mixture was
heated on a water bath.

But fulminating silver was formed and explosions took place when strong alkali
hydroxides were present, or when the solution became concentrated through evaporation.
A similar conclusion was reached by the Pittsburgh Plate Glass Co. of U.S.A. in 1955, i.e.
that:

(1) Explosions are not produced by adding concentrated ammonium hydroxide (ammonia)
to solid silver nitrate.
(2) Addition of sodium or potassium hydroxide to the silver-ammonia complex definitely
increases the tendency to form explosive material. The action of the alkali hydroxides is not
quite clear, but may be explained by their tendency to displace ammonia.
(3) A very high alkalinity of pH 15 appears to favour formation of explosive. The pH of
usual silvering solutions is about 13-4. The dangerous pH region starts at about 14-5.
(4) Although the concentrated silver-ammonia complex appears not to form fulminating
silver, it is recommended to dissolve silver nitrate in water before adding ammonia.
(5) Therefore, silvering solutions should not be stored, and under no circumstances over
longer periods such as weekends.

Dr. Eduard Lohmann had already expressed the same opinion in 1931, in the Journal
Diamant, No. 33. And the British Ministry of Labour Factory Department is even more
cautious. It postulates that the silver ammonia solution must not contain more than 6%
silver nitrate.

Fulminating silver is a black precipitate. It consists mainly of silver nitride (Ag3N) and
silver imide (Ag2NH) and possibly also of silver amide (AgNH2). It is often mixed with
metallic silver. When left alone for a few months, it tends to lose its nitrogen component
and to change completely into harmless silver powder. Fulminating silver can be regarded
as an ammonia whose hydrogen is wholly or partially replaced by silver. It is not silver
azide (AgN3) a white precipitate which is also explosive; it forms under different
circumstances to this.

The danger of bringing these exploisves substances to a weighing machine makes their
analysis difficult. According to Dr. W. Friedel, Centralzeitung fur Optik und Mechanik,
Berlin, March 3rd, 1928, the formation of fulminating silver from silver nitrate and ammonia
may take place in this fashion, as earlier formulated by F. Raschig in 1886 (Liebigs
Annalen, 233, p. 93).

3 Ag(NH3)2-NO3 = Ag3N + 3NH4NO3 + 2NH3

Silver Ammonia Silver Ammonium Ammonia
Nitrate Nitride Nitrate

and

2 Ag(NH3)2-NO3 = Ag2NH + 2NH4-NO3 + NH3
Silver Ammonia Silver Ammonium Ammonia
Nitrate Imide Nitrate

and

Ag(NH3)2-NO3 = AgNH2 + NH4-NO3
Silver Ammonia Silver Ammonium
Nitrate Amide Nitrate


To conclude, it may be pointed out once more that diluted solutions of silver nitrate with
ammonia and alkali hydroxides are harmless, but they must not be allowed to become
concentrated. They no longer present a danger when the reducer is added and the silver is
precipitated as a mirror or as silver powder.

The black precipitate of fulminating silver must not be confused with the harmless
dark-brown-to-black silver oxide [Ag2O] which forms when insufficient ammonia is added to
the silver nitrate solution.

If, however, any suspicion of the presence of fulminating silver is aroused, extreme
caution is imperative. Under no circumstances must the vessel be moved or shaken.
Fulminating silver, whether dry or wet, explodes at the slightest touch.

In order to eliminate the danger, diluted hydrochloric acid should be added until the
solution becomes acidic, and the fulminating silver is converted into silver chloride. The
operator should approach the suspected vessel behind a screen of thick glass, protect his
eyes and hands, and add the acid carefully. It is better to destroy and discard the ful-
minating silver than to run an often underestimated risk.

AndersHoveland - 7-4-2012 at 17:30

There is also diazomethane, which is more commonly thought of as a precursor in organic chemistry. It is a very toxic, extremely unstable, dangerously sensitive explosive gas.
http://www.sciencemadness.org/talk/viewthread.php?tid=2273

killswitch - 7-4-2012 at 20:23

No amateur will ever synthesize that in its pure form, even if purification is possible via practical methods.

Lithium - 7-4-2012 at 20:33

what about potassium nitrosocarbamate ,NONKCOOK.

here is the only reference i can find is this, and it is on this thread:

quote:

Potassium Nitrosocarbaminate
Author: Lagen
Procedure: Place 38 ml of methanol in a 100 ml beaker. Add 10 g of dry potassium hydroxide, in several small portions and with stirring. Wait for each portion to dissolve, then let the solution cool down. Pour off some of the resulting solution in another container, keep approx. 30 ml of solution in the beaker. Place the beaker in a salted ice bath. In another container liquefy 1g of nitrosourethane with a few drops of methanol and add 4 ml distilled water. Add the solution in one portion into the potassium hydroxide solution and let it react for 10 minutes. If nothing precipitates, add 5 ml of the spare potassium hydroxide solution and wait for another 10 minutes, then add the remainder of the KOH solution. Let the mixture stand for one hour, keep replacing the ice bath if it melts. Quickly vacuum filter the precipitate, wash several times with absolute alcohol and place immediately in a desiccator. Try to avoid unnecessary contact of the product with moist air. Yield: approx. 1 g of a pale yellow powder.
Properties: Potassium nitrosocarbaminate - NONKCOOK. Very sensitive. Detonates violently, even in small amounts, on contact with water or sulfuric acid. May detonate at slightly elevated temperatures (below 100°C). Decomposes in the presence of moisture. It can be temporarily rendered nonexplosive by the addition of ether followed by addition of alcohol. When treated in this way it can be decomposed safely by water or H2SO4.


google gets 2 results!

Li



[Edited on 8-4-2012 by Lithium]

AndersHoveland - 9-4-2012 at 04:53

2-Iodoxybenzoic acid can be prepared by the slow addition, over a half hour, of potassium bromate (76.0 g, 0.45 mol) to a vigorously stirred sulfuric acid mixture (0.73 M, 730 mL) containing 2-iodobenzoic acid (85.2 g, 0.34 mol).
While 2-Iodoxybenzoic acid is usually used as a regent to selectively oxidize alcohols to aldehydes in organic chemistry, the substance is also an explosive.

Adas - 9-4-2012 at 10:24

What about PETN derivate, but with just -NO2 groups?

It can probably be easily made by reacting NaCH2NO2 (sodium nitronate) and CCl4.

AndersHoveland - 10-4-2012 at 21:53

So why exactly did you post this idea here?
For better organisation, you could have posted in one of these threads:
http://www.sciencemadness.org/talk/viewthread.php?tid=14003
http://www.sciencemadness.org/talk/viewthread.php?tid=18920 (not sure why this thread is not in the "Energetic Materials" section)

Quote: Originally posted by Adas  
What about PETN derivate, but with just -NO2 groups?

It can probably be easily made by reacting NaCH2NO2 (sodium nitronate) and CCl4.


You may be on to a good idea. But certain things need to be considered. First, the sodium salt is only chemically stable in the absence of water, in pure ethanol for example. It can be made by reacting solid NaOH with nitromethane in ethanol. But the compound irreversibly hydrolyses in water, which is indicated by the solution turning a redish-brown color. (you might see this thread for more information about the reaction: http://www.sciencemadness.org/talk/viewthread.php?tid=1089 ) Second, chlorine does not substitute readily off of carbon atoms under normal conditions. More realistically one would need CBr4 or CI4. This forum also has a good thread on the preparation of iodoform, CHI3.

The compound you are describing, C(CH2NO2)4, would no doubt be very insensitive, like nitromethane. Nitromethane is actually a fairly energetic explosive, and one of the main reasons for its relatively low detonation velocity is its low density. C(CH2NO2)4 would have the advantage of having a higher density, because of larger molecular size.

PHILOU Zrealone - 25-5-2012 at 06:26

CCl4, CBr4 or CI4 are not good candidates for such reactions because it is apolar and all Cl atoms are equivalent...

Much better would be the use of activated halogens... like in dangerous chloropicrin, bromopicrin or iodopicrin...
CCl3-NO2 -(NaO)(O)N=CH2-> O2N-CH2-CCl2-NO2 + CH2=N(O)-O-CCl2-NO2 + NaCl

You obviously see that sodium nitronate might give C bonding or O bonding but the question is in what proportion?

Once a first linkage is done...the remaining halogen atoms are even more activated by the electron withdrawing effect of the NO2 and CH2-NO2 groups and so further substitution might occure faster...

The final step should (amongst other reaction products) give the putative O2N-C(-CH2-NO2)3 (Tetranitroisobutane) which should be denser than Tetranitropentaerythritol C(CH2-NO2)4 and display more power owing to a better OB and higher density.

From comparative studies between molecular families I have done: Like it is the case for other related Carbon skeleton molecules Tetranitropentaerythritol (thus the nitrocarbon and not the nitrate ester!) must display higher density than 1,2,3-trinitropropane but a lower one than tetranitroisobutane.
So d(X-C(CH2X)3) > d(C(CH2X)4) > d(XCH2-CHX-CH2X)


[Edited on 25-5-2012 by PHILOU Zrealone]

[Edited on 25-5-2012 by PHILOU Zrealone]

AndersHoveland - 25-5-2012 at 23:04

Quote: Originally posted by PHILOU Zrealone  
O2N-C(-CH2-NO2)3 (Tetranitroisobutane)

Unfortunately, such a compound would have thermal stability problems, since it has nitro groups on adjacent carbon atoms (vicinal).

see the eleventh post down in this thread, with the section "Geminal Nitro Groups":
http://www.sciencemadness.org/talk/viewthread.php?tid=17012
Quote: Originally posted by AndersHoveland  

Although such compounds still tend not to be very sensitive to initiation, there exists the problem of thermal stability, where there is slow decomposition in storage under warm conditions, or rapid degredation if the explosive becomes subjected to the heat from flames outside the metal casing.

The examples of stable gem-nitro molecules seem to have one thing in common. In all cases, elimination of HNO2 and resultant formation of an unsaturated C=C bond, is not possible. In other words, the molecules lack an (R)2CHC(NO2)2CH(R)2 segment, or if such a segment does exist, the carbon-carbon bonds are under a high degree of strain. ...

Dinitropropanes that do not have a hydrogen atom on the same carbon as the dinitro group require a higher temperature for thermal decomposition than those that have such a hydrogen. P. S. DeCarli, D.S. Ross, Robert Shaw, E. L. Lee, H. D.Stromberg. For example, the solid compound 2,2-dinitro propane is thermally unstable when warmed. At 75degC, it partially decomposes, losing two thirds of its weight after two days. There are, however, several conditions under which gem-dinitro compounds can be thermally stable. ...


[Edited on 26-5-2012 by AndersHoveland]