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Author: Subject: Diving Into the World of Fulminates
hissingnoise
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[*] posted on 28-8-2009 at 05:37


Quote: Originally posted by Hennig Brand  
Does anyone know if mercury fulminate can be purified, recrystalized from boiling water?
Does anyone know from either experience, or reading what the solubility of MF is in water?

According to Davis in COPAE, one litre of water dissolves 0.71 gm @ 12*C and 7.7 gm @ 100*C.
And MF, crystallised from water contains 1/2 H2O. . .
He mentions purifying MF by dissolving in NH4OH and precipitating by addition of 30% acetic acid.
I'd be inclined to go the NH4OH route for safety's sake!

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Hennig Brand
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[*] posted on 28-8-2009 at 08:08


Just found this link this morning, and from a little experimenting I believe it to be fairly accurate solubility information. Seems to be in the ballpark anyway, (my experiment was pretty crude).
MF solubility
http://wiki.answers.com/Q/Is_Mercury-II_Fulminate_Soluble_in...

Thank you Hissingnoise, I didn' t actually see your post till after I had posted (I refreshed the last page, but never checked for another page). I guess the solubility info for boiling water checks out nicely, between the two sources (if they are infact different sources, hard to know sometimes). I'll leave this post as it provides a little confirmation, even though your source hardly needs it. Thanks.

[Edited on 28-8-2009 by Hennig Brand]
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hissingnoise
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[*] posted on 28-8-2009 at 10:46


You're welcome! Davis's book is well worth downloading from the forum library, btw.
Urbanski it ain't, but it's quite good for its day. . .
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Hennig Brand
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[*] posted on 30-8-2009 at 06:23


I have already downloaded it, along with everything else I could find to download on the subject in the last few years. This is just a case of me trying to rely on google to do the work for me, and not doing a thorough job of my own homework using the published sources. Thanks for indulging me anyway.

By the way, in COPAE it states that MF crystallised from water contains 1/2 H2O. What is the consequences of this? Is it going to be hard to get the water out of the MF?
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[*] posted on 30-8-2009 at 06:54


Mercury fulminate can be purified by dissolving in ammonia and precipitating with acetic acid, as shown at Powerlabs:
http://www.powerlabs.org/chemlabs/fulminate.htm




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hissingnoise
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[*] posted on 30-8-2009 at 13:53


Quote: Originally posted by Hennig Brand  

By the way, in COPAE it states that MF crystallised from water contains 1/2 H2O. What is the consequences of this? Is it going to be hard to get the water out of the MF?

I'd say, guessing, it will slowly evaporate @ r.t. or in a dessicator. . .
MF is practically non-hygroscopic!
I wouldn't use H2SO4 to dry it, though.
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[*] posted on 30-8-2009 at 18:32


Quote: Originally posted by Hennig Brand  

I was just reading from the thread "Picric Acid different instructions", and in the last post there on pg 14 is a description by Rosco Bodine on recrystalizing MF from water. I am glad to see it, because the couple times that I have seen it mentioned in books, it was described as common practice at the time (late 1800' s to early 1900' s), but didn' t describe how it was done at all. Thank you Mr. Bodine.
[Edited on 27-8-2009 by Hennig Brand]


You are welcome. Now there is another thing that I have been thinking about as a kind of "virtual experiment" in the mind of Rosco, that is in that category of "thinking outside the box" which might be right down the alley for fearless and inquisitive type A personality crazyass ;) fulminate experimenters who just have to know for sure :D ......
and of course I am musing about the possible formation
of a silver fulminate / mercury fulminate double salt which
seems like a possibility that has not been mentioned or
at least I haven't seen it mentioned anywhere in the literature. It would seem like that given the recrystallization
method from NH4OH being applicable to both, that a coprecipitation scheme could be worked out which very possibly could give a double salt providing synergistic enhancement of the initiating properties and more acceptable
sensitivity than silver fulminate alone. The physical manipulation techniques for silver fulminate are exacting, risk ridden as in fraught with danger, so this is no experiment which I would recommend for inexperienced or unsophisticated pursuit. I cringe at some of the stuff I read about as "variations" of procedures where it is clear folks really don't "get it" why small changes can turn a relatively lower calculated risk of a safer procedure into a recipe for disaster. The way you do physical manipulations and reactions in chemistry and the amounts of things you are working with and the process conditions you are employing
can have definitive bearing on whether or not your next experiment is your last. Even things that would seem to be mundane can bring surprises. So have the depth to think an experiment through very well in your mind and work it out on paper before actually implementing the real thing. That way
the odds are better you will "live long and prosper" :D

A double fulminate of zinc and silver has been reported and details are needed. Evidently boiling silver fulminate with powdered zinc replaces exactly half the silver and no more
to produce the double fulminate. This may be an interesting material for experimental investigation of its properties.

Reportedly contacting zinc fulminate with mercuric chloride will displace the zinc and give mercury fulminate, and possibly
likewise contacting the double fulminate of zinc and silver
with mercuric chloride or perhaps better with mercuric nitrate
will displace the zinc portion of the double salt of the fulminate of zinc and silver, to produce the double fulminate
of mercury and silver. I do not know what may be the reaction dynamic there and if it would be favorable or not, these are preliminary speculations.

http://www.youtube.com/watch?v=zLZysDhVmD4&fmt=18 Alkaemy - The Merlin Mystery - Legend of the Stone

http://www.youtube.com/watch?v=lYNTDx6fJoU&fmt=18 Alkaemy - Nimue's Lament (with lyrics)

http://www.youtube.com/watch?v=Yw0RcKaL6Hs&fmt=18 Himalayan Sky

http://www.youtube.com/watch?v=m40wcqlt1Uo&fmt=18 Orchid Potion

http://www.youtube.com/watch?v=RGWH9md3Grc&fmt=18 Gregorian Chill Out Music

Attached is an excerpt from an old chemistry textbook circa 1903 which shows some reported experiments parallel to what I have been speculating, and indeed the double fulminate of silver and mercury has been prepared, though no properties for it are reported. Thorpe 1922 has some more general information that is fulminate related, see second file attached. My own idea is that Bridges 1869 text
identifying that fulminic acid is a dimer and bibasic acid and polymeric rather than mono isomeric with regards to cyanic acid is probably correct in spite of other more modern references to the contrary.

Attachment: Pages from Chemistry__inorganic_and_organic 706-708.pdf (314kB)
This file has been downloaded 707 times


Attachment: Pages from A_dictionary_of_applied_chemistry Thorpe 1922.pdf (313kB)
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[Edited on 31-8-2009 by Rosco Bodine]

Attachment: Pages from A_manual_of_elementary_chemistry 1869.pdf (204kB)
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[*] posted on 1-9-2009 at 14:27


Finally made some mercury fulminate this past weekend.

Previously I had tried to make silver fulminate without success - could never get the reaction to start. I believe this is because I used AgNO3 and HNO3 instead of dissolving silver in the HNO3. Apparently there must be dissolved nitrogen oxides present for the reaction to start reliably.

I took a small drop (about 0.2g) of Hg metal and dissolved it in about 1.5ml of 70% HNO3. This was pretty slow for some reason (took about 30 minutes). I then added about 1.5ml of EtOH. This resulted in an immediate runaway reaction, with dense, heavy clouds of vapor being produced. Based on smell (I was carefull not to smell too much), I'm pretty sure the heavy vapor is acetaldehyde. Acetaldehyde boils around room temperature and is very soluble in water so I'm guessing that is what the white vapor is. Bubbling continued for about a half hour, at a slower rate. It looked like the solution was boiling slowly the whole time.

The mercury fulminate precipitate was light gray in color. I washed it several times in water and allowed it to dry in a small plastic cup. When dry, small amounts deflagrate with a "whump" sound, similar to TATP. However, I was not able to set this off with a blow from a hammer. Probably was not completely dry.

It seems the final product contains some free Hg. I put a small amount on a piece of aluminum foil to dry and it ate a hole through the foil, leaving a large volume of Al(OH)3.

Sometime I will try the silver fulminate, now that I think I know what was wrong before.

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[*] posted on 2-9-2009 at 20:22


Would you consider the tin foil experiment with other sample metals?Say tin copper,bronze brass, steel ,anything on hand?if really in an experimental mood coated with something like polyurethane,parafinn.shellac.For the life of me I havent been able to find what was used for detonator shells using Hg fulminate prior to bakelite in the early 20th centrury.

as for the reaction of hg and nitric acid of 68-70% I rarely saw any reaction even on heating but stirring made the hg react and dissolve in the Nitric, the remainder of the lab as described.The whys and wherefores are far beyond me
But even a a small whiff isnt advisable if you value your CNS.HG vapor!I think it best to wash with ethanol,drys quicker etc.[Edited on 3-9-2009 by grndpndr]


[Edited on 3-9-2009 by grndpndr]

[Edited on 3-9-2009 by grndpndr]
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[*] posted on 3-9-2009 at 17:35


I could try some other metals next time - I don't have any mercury fulminate left this time though. I'm guessing that steel would be okay since mercury does not react with steel.

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Rosco Bodine
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[*] posted on 4-9-2009 at 23:31


Here's another old reference circa 1870 which lists many different fulminates and provides a bit more information about preparation and properties

Attachment: Pages from A_dictionary_of_chemistry 1870.pdf (692kB)
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[*] posted on 6-9-2009 at 07:52


Here is still more detail on fulminates, preparations and properties from Gmelin circa 1855, more is here concerning
the lead zinc double fulminate and other substituted fulminates. These reactions and compounds are interesting
in particular to me because of the possibility of forming double salts or clathrates between the fulminates and
basic or normal picrates or styphnates, which could represent novel energetic materials having desirable properties as initiators.

Attachment: Pages from Hand_book_of_chemistry Gmelin 1855.pdf (835kB)
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[*] posted on 6-9-2009 at 15:46


Quote: Originally posted by Rosco Bodine  
Here's another old reference circa 1870 which lists many different fulminates and provides a bit more information about preparation and properties


Thanks Rosco.



The main smell I detected when making mercury fulminate was acetaldehyde. I doubt there is much mercury vapor present given the temperatures involved, although of course there might be small mercury particles carried into the air by the bubbles. Either way, sounds like this is something to avoid breathing.

I did have some very limited success creating silver fulminate, after two more tries. On the first try, I let about 0.1g of silver dissolve in about 2ml of HNO3, waited for it to cool, and then added 2ml EtOH. Although I did see some small bubbles, kind of like the solution was slowly boiling, I did not see any vapor cloud. The bubbling continued for about 30 minutes, and no product precipitated. I suspect the vapor was just plain aldehyde from the reaction of the alcohol with the nitric acid. I tried a second time, this time adding the alcohol while the silver was still reacting. This resulted in much faster bubbling, along with NO2 vapors. After a couple of minutes, the reaction became so vigorous that it boiled out of the small plastic cup I was doing the preparation in (which was about 10 times taller than the depth of the liquid in it). This time I got a tiny amount of precipitate, as fine as dust. So fine that I could still see the bottom of the cup through them. From the residue from the boilover I found a speck about the size of a crystal of salt. I dried this and it detonated with a definite snap from the flame of a lighter. Tried washing the fine powder at the bottom of the cup but yield was so low there was practically nothing left after the washing.

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[*] posted on 6-9-2009 at 17:22


These "ancient arts" always intrigue me because of the obscurity of what could be very good pertinent information on which possible followup experiments of interest were never done. I especially like the analysis
of old time chemists who did the "mental virtual and logical analysis" of structures by experimental observations and deduction, scientifically sleuthing to get the lowdown on how unknown compounds are probably structured, as compared with already well known compounds. Everyone should admire the abstract thinking of these perceptive scientists of old who had none of the modern instruments as helpers, and no great body of prior art on which to rely, but were doing good basic scientific investigation, using what little information and theory they had to advance the art.
I especially like the nitro-acetonitrile and the bibasic acid
and dimer analytical hypotheses concerning fulminic acid.
Modern references, at least those I have seen are not comprehensive in describing or resolving the obvious issues raised by the perspicacious observations of the ancient experimental chemists who do have an obvious point in what they are saying about the legitimacy of conclusions which their experimental results would seem to indicate.

Excerpts are attached for an 1844 Lancet article by Justus Liebig and a later 1876 article by Edmund Davy, cousin of Humphry Davy, doing followup experiments concerning some of his father's earlier work with fulminates.

Attachment: Justus Liebig circa 1844 The_Lancet.pdf (468kB)
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Attachment: Davy_The_American_Chemist circa 1876.pdf (893kB)
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[Edited on 7-9-2009 by Rosco Bodine]
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[*] posted on 7-9-2009 at 13:54
fulminate complexes


I know of the patent by Hurst to stabilize silver fulminate to make it only temporarily relatively insensitive, but would it be possible to prepare a fulminate complex like silver-zinc fulminate or potassium-silver fulminate without having to isolate and form silver fulminate first?
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[*] posted on 8-9-2009 at 06:31


I'm not sure what sort of manipulations may be workable
for an indirect route to the silver double salts. The zinc lead double fulminate was one that caught my notice as interesting.
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[*] posted on 8-9-2009 at 16:18


I have made silver fulminate probably more than 20 times, and am no where near to having it all figured out. Sometimes it works out pretty well, and sometimes it does not. I first started experimenting with it about 3 years ago, at that time I couldn' t even get the reaction to start with the ethanol, silver nitrate(made from silver + HNO3) and HNO3. I was using crappy 95% ethanol from the drugstore which had all sorts of other crap in it, which I don' t believe really added anything to my experiment if you know what I mean. I found if I heated it on a sand or water bath to somewhere between 40-60C the reaction would start, but petered out quickly leaving little SF (using the rubbing ethanol). I was reading a silver fulminate thread at the time from this site, and there I learned that acetone could also be used to provide the methyl group (I think thats correct), and fascilitate the reaction. I found the acetone to be much more reactive and could easily lead to a runaway, so I mixed it with the rubbing ethanol and used careful heating. I got a very explosive product that was fun to play with, but my yeild where nothing to brag about. I also soon noticed some batches were much more powerful and destructive in small amounts than others. That was when I learned how easy it was to make very contaminated SF. I believe the heating is necessary to start the reaction, or at least that is how it has been for me, and how I have seen it written in many sources. However when the reaction starts(sometimes pretty close to 60C) the reaction quickly generates much more heat(exothermic), and much higher than 60 or 70C silver oxide is produced quite readily. I have had batches that proceeded too vigorously, with too much heat, and all I got was silver oxide, no SF at all. At the time I was brewing, but hadn' t yet the skills to make high concentration and purity ethanol. I should try a batch of SF with my home made ethanol of 90% or higher, I bet it works much better than the rubbing ethanol. Maybe I wouldn' t need the acetone at all. What I did the last couple of times I made SF, was use heat (carefully) to get the reaction going, watching a thermometer all the time. Once the reaction got started I would put the flask in cool water as much as was needed to keep the temperature well down below where the oxide is formed. As the reaction proceeds at some point heat will probably be needed to keep it going (hot water/sand bath). I don' t think even then that much over 60C is desirable though. SF is much trickier than MF in my humble opinion.
This was posted by Axt in the thread called Silver fulminate synthesis- Attachment: A Reappraisal of Silver Fulminate as a Detonant .pdf
I found it very useful and informative, at the time and still now.

[Edited on 9-9-2009 by Hennig Brand]
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[*] posted on 10-9-2009 at 06:19


SF certainly sounds as though its the more difficult, if its available to you I have heard everclear is a good source of 180 proof
ethanol just dont drink it!:oLikely more toxic than the mercury,or rather youll think so next AM!Thanks for the links everyone!

[Edited on 10-9-2009 by grndpndr]
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[*] posted on 16-9-2009 at 07:50


The double fulminate will work as energetic materials to a degree. I have a Pb/Hg & Zn/+ paper somewhere. However if one does not have the proper glassware and some way of keeping clear of the fumes (personal opinion here) Hg Fulminate might be the most insidious toxin in this hobby. I think hydrazine gives more warning. What Hg does to the CNS is no joke. Lungs can recover from scaring, livers can recover from fatty deposit, but what mercury does to one's CNS - you will not know until either you get seizures or some other ugly outward issues.....please be serious with Hg.
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[*] posted on 16-9-2009 at 11:42


What are the best way to "save" our nervous systheme with the mercury, the mercury fulminate synthesis and the burning of mercury fulminate???
Will it be safe enough to use glasses, smock, gaz mask and nitril gloves for the use of mercury metal and the synthesis of the MF???
And for the burning test of MF, will it be safer to make test outside??? I have a fume hood, but i am not sure that all of the fume will be going oustide...
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[*] posted on 16-9-2009 at 22:34


@Hennig Brand

in one of those excerpts Rosco posted above, it says that moist SF when dried in direct sunlight will become so sensitive that it goes off from merely touching it. Can you confirm this? Whats your take on its stability?



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[*] posted on 18-9-2009 at 00:27
HG fulminate toxicity


I knew a person very well who used a full lb of dist merc in HG fulminate labs over a period of perhaps a year over 10years ago
using normal precautions during the labs as well as whenever working with the substance.He was still tremor free as well as free of any cns effects i noticed or his Drs noted over 10 years later.Certainly not the mad hatter effect in his case although thats no reasons not to be very cautious with this or any lab involving any # of precursors.Those who work with nitric acid
in labs also risk instant death or a slower death from pulmonary edema a week later.Is that sufficient reason to stop all labs where the possibility of noxious fumes are likely?I dont think so,I do think its an obvious decision to use the proper protective equipment just as one would in sports or any risky endeavor.Unfortuneately my friend the lab rat died from a head on collision not CNS deterioration at the age of 40.



No one I know is out to win the darwin award despite what some unfamiliar with the hobby may think .

[Edited on 18-9-2009 by grndpndr]
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[*] posted on 18-9-2009 at 06:19


In an old Gmelin handbook from 1857 is reported a double styphnate of nickel and potassium, a brown crystalline and probably anhydrous salt which detonates with "tremendous violence" on heating. This may be worth an experiment as a candidate material for admixture with a fulminate, which could have a synergistic effect even beyond the already known synergistic mixture of mercury fulminate and lead styphnate. Such compositions could occupy a niche between the performance of mercury fulminate and lead azide and could have value as initiators. A zinc fulminate - lead fulminate double salt in admixture with the nickel styphnate - potassium styphnate double salt could be a synergistic mixture .....but whether or not the mixture is compatable or would be reactive is unknown. Some of these hypothetical mixtures may work or may not, and I find no references to such experiments having already been done, although it could be that such mixtures have already been investigated, and the references are obscure.

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[Edited on 18-9-2009 by Rosco Bodine]
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[*] posted on 20-9-2009 at 17:32


@Taoiseach
I have never dried it in direct sunlight, so I don' t know. I do find however that its sensitivity for most samples is much less than what we hear about (at least for me). I can say that the sensitivity varies with the batch, and that for my samples very little friction or percussion was needed to initiate detonation, but it still always took much more than simply touching it. Touching is kind of a relative term though I guess. The sharp sand in those little bang snaps is definately needed to make them reliable. I have even found that if I didn' t use sharp sand and used round sand, from say a beach, that they had to be thrown quite hard. I do find that it seems to darken up and lose a certain amount of power over time, which I have been attributing to sunlight(I had a few small samples that sat out in dishes indoors, not in direct sunlight but even reflected light seemed to cause breakdown). I haven' t done a lot of testing and I think my Silver Fulminate samples have all been quite impure. I have only had a couple batches where I actually saw good crystal formation to. The other thing to remember is I have only been playing with tiny amounts, the more of an explosive you have especially a sensitive one, the greater the danger. There is more potential energy of course, but also the potential for an accident is greater for various reasons. I think reproducability is probably one of the biggest problems with SF, and who knows maybe I have just been lucky and never hit one of those super sensitive batches. I may test the sunlight thing with a small batch, and see if I can get an observable result. I am curious now.
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[*] posted on 23-4-2010 at 12:46


I think that assuming silver fulminate can be used reliably is a big mistake. There are much safer ways to detonate ETN. Flash powder can do it, or mixing the ETN with aluminum powder can make it so you can detonate it with a nichrome wire.
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