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Axt
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Novelty explosives
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]
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artem
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| 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. |
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nitro-genes
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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 
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]
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Axt
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| 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.
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nitro-genes
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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? 
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...
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Axt
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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
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artem
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| Quote: | Originally posted by Axt
They made some attempt to analyse the explosive product, but with no definate conclusion...
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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...
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Swany
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Nitrosoguanide anyone?  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.
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DeAdFX
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I saw one of the north american pyrotechnic stores carrying guaidine nitrate.. 12 usd a pound
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Swany
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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.  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...
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S.C. Wack
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> 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]
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DrP
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> 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?
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Swany
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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.
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Swany
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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).
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Axt
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| 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.
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Swany
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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.
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Madandcrazy
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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.
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Axt
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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"?
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bullstrode
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Baking powder perhaps?
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The_Davster
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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....
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Marvin
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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.
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Axt
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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.
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Marvin
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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.
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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]
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d010060002
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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?
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mnick12
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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.
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