Mercury Fulminate..

[inferno]

I have been working a lot with the MF in toy cap-gun caps (not blasting caps) to make simple firecrackers and the like, however, as ive read it is used in some detonators, but in my experience it wouldnt have the power to blow a metal casing? To make the firecrackers, i just get a pen lid or the end cap thing of a pen, make it about 2cm long, melt the open end so it just fits in a sparkler, empty out one ring of caps (8 caps) into the bottom, put some shaved matchheads on top, then stick in and tape in a sparkler (cut down so its about an inch long, about half an inch stick out).

They go bang and send out a lot of sparks. But my point is, that the mf only sometimes breaks the plastic. Sure theres not that much in it, but i still dont see how it could break a metal casing. Maybe the power increases dramatically with the more you use, i havent tried 5 rings in one or anything, because it takes long enough to empty out one. Thanks for any info on its power, i want to make my own caps because i cant buy them and just wanted to clear this up.

PS Are there any adverse health effects from handling MF, and secondly does anyone know whats in the party popper "charges"? I thought it was MF but its red and a hell of a lot more sensitive.
Sorry im asking so many questions, bear with me, but what are the approximate powers of detonators, eg a #1 cap to a #8 cap? Are the lowest grade about equivalent to a large commercial firecracker, or much more powerful?
Thanks

<small>[ April 24, 2002, 12:06 PM: Message edited by: inferno ]</small>

[Anthony]

Toy caps contain Armstrong's mix, it's a mixture of red phosphorus and potassium chlorate or perchlorate, it is a low explosive. Ditto for party poppers IIRC.

I recall someone posting a table showing the contents of various #'s of blasting cap, try the archives, see if it's in there.

Comercial firecrackers are filled with low explosives, like flashpowder. They cannot really be compared to a blasting cap of high explosive.

You don't seem like a bad guy, but you've made quite a few elementary mistakes. Read around some of the current and past threads here, you'll soon have the information you needed to answer your own questions and more.

I'll leave the thread open in case anyone has some useful information or experience comparing commercial and improvised blasting caps.

[andreas]

Would an mix of AN and H2SO4 work as well for fulminates.
If nobody tried it before I'll try and post the results as soon as I get some ethenol.

[Pu239 Stuchtiger]

Has anyone ever attempted to prepare lead fulminate or copper fulminate?

[inferno]

I thought that KCl03/KCl04 wouldnt "explode" like a LE, unless mixed with a fuel? Ill test tonight with a small amoutn of sugar+the powder in caps, if it makes smoke it would probably be KCl03/4. Thanks

[Bitter]

"I thought that KCl03/KCl04 wouldnt "explode" like a LE, unless mixed with a fuel ?"

What do you think the red phosphorus Anthony mentioned is for ? That's the 'fuel' in Armstrong's mixture.

[Zambosan]

Armstrong's also contains antimony trisulfide, which serves as a reducer as well.

[vonK]

The toy-caps I have contain (taken directly from the pack), no more than 0.2 grains of a pyrotechnic mixture consisting of potassium chlorate, red phosphorus, antimony trisulfide, manganese dioxide, sand and glue.
There are some things called "Wolf Packs" here in NZ which are small pea sized bundles of gravel and mercury fluminate wrapped in paper. The pack says they contain less than 0.12 grains of mercury fluminate.
These go bang with a sharp crack when you drop them on the ground and the bundle is blown apart.
On Mother's Day I get more supplies, I think I will try a few fluminates.
Do you think it would be sensible to follow Megas recipe for MF but substitute the Hg for an equimolar amount of Pb, Cu or even Zn.

[da man]

Vonk, only mercury and silver fulminate can be made by the reaction of nitric acid on the metal followed by reaction with ethanol. Other fulminates such as copper, etc, are made from the silver or mercury fulminate. So it won't work substituting other metals for the mercury.

[inferno]

Hey, thanks for the info zambosan and vonk. What i meant when i said without a fuel, was that the powder (that you said was KCl03) ignited without the red P. I understand now from the info zambosan and vonk said.
(and i think it would blow a metal cap now, ive found that 8 caps will not so much as leave a mark on the plastic, double that and it blows it apart. I did this just before in an empty plastic KNO3 container (500g) and when it went off, the propelled plastic (i assume) broke a hole through the plastic.

Please dont think im a k3wl because i use these ingredients, but especially in Australia, it is very hard to obtain nitric acid, acetone etc. And my age doesnt help that either. The only legal firework or pyrotechnic device you can buy without a licence in all but one state of Australia is sparklers. Obviously you can buy BP etc, but i find it more fun to make my own things, and learn what is in them etc, than to buy some BP and put it in a tube. And mentioning nitric acid, i saw on the news last night that a truck crashed and spilled its cargo of nitric about 20 mins from me...wish i was there.

I know one place you can buy 70% nitric, 98% sulphuric, even high conc phosphoric, also KNO3, NH4NO3 bulk, etc, but its pretty expensive, about AU$125 for 5 litres of nitric (american, about 62.50 for 1 gallon)
This topic might as well be deleted

[Anthony]

You might think it, but generally, you're no worse off for chemical sources than most other countries. Each country does have things that are easier to get or rarer than other countries, but I think it balances out somewhat.

You don't need to buy HNO3, you can substitute it for H2SO4/metal nitrate for many synthesises. Acetone you seem to can't help tripping over in America, but elsewhere you need to look a bit. Buying chemicals from lab companies isn't the answer to look for, they're usually more expensive, due to their much higher than required purity and IMO it takes some of the fun out of things. Knowing that you can make something out of everyday products is much better.

[S. Toppholzer]

Odd....
Just about a year ago I learned here at The Forum that Armstrong's mixture may be detonated as well....

[Anthony]

Yes, it can be under the right circumstances. It'd probably be similar to Ammonium Nitrate/Red Phosphorus, which is apparently sensitive to a #6 commercial blasting cap. Not much good for making a blasting cap with if it needs one itself to be initiated.

[10fingers]

Speaking of Armstrongs mix, isn't that how the infamous Kurt Saxon lost his hand?

[vulture]

Dumb question: WTF is Kurt Saxon?

[J]

Author of the 'Poor Mans James Bond' series of books.

[kingspaz]

he apparently lost 3 or 4 fingers on his left hand due to armstrongs mix. i have a 10 minute vid of him i got from here a long long time ago, really bad quality but you can see his mangled hand.

[Boob Raider]

Can anyone tell me why only 95% + ethanol works for preparing fulminates. Is it possible to use monoethanolamine, theoretically. It can be isolated from certain degreasers/oven cleaners etc.

[aster]

find 95% ethanol is easy, go to the nearest drugstore, i think they always provide this chemical, it's cheap enough i think, why we must use 95% or more? i think because it will be better to quickly reacting the metal nitrate (mercury nitrate) with this ethanol, because mercury nitrate is unstable and decompose under influence of light, if we postpone to reacting them soon they will be failed to formed mercury fulminate. so maybe this is the reason why we using a more than 95% ethanol, anyone has their own explanation?

[vulture]

What's the consistence of the toxic gases that are produced when making mercure fulminate? CO? formaldehyde?

[Boob Raider]

I don't think there is any HCOH as it definately doesn't smell like it. There are a lot of dense white fumes. Most of them are due to ethanol and H2O formed (similar to glycol+H2O fogging machines). The fumes evolved burn with a colorless flame and when I lit them .... they lit up like alcohol fumes <img border="0" title="" alt="[Eek!]" src="eek.gif" /> . Also there are no oxidizing gases present as the ignition of the fumes was not/barely audible. I have also noticed that when the reaction is almost over ... (after the fogging subsides) .... Hg(ONC)2 crystals form near the surface of the solution and then sink down. Hope someone can make use of my observations in deducing, What the fuck actually goes on in there ?
Oh yeah ... the liquor store sells 96% ethanol for use in pharmacies. 2 problems ..... 1). They only sell it in 4L cans for $200 and 2). I need a licence. :mad:

[Marvin]

Davis lists the condensable gasses produced during the fulminate reaction as mainly alcohol, acetaldehyde, ethyl nitrate and ethyl nitrite. Noncondesable gasses are probably NOx, though I didnt see much evidence for its production during the white fuming stage, and carbon dioxide.

(In answer to much older points), you cant make nitric in situ becuase mercury sulphate is less soluable than the fulminate is. Formation of solid mercury (of silver) fulminate is what prevents it being destroyed as its formed, and why attempts to make other fulminates fails with this method. I didnt redistill my nitric, as a result my fulminate had a little sulphate in it, and was less sensitive to being hit than it should have been.

Soluable mercury salts are nasty very toxix things, dont put them down the drain if possible, treat the waste liquid with sodium carbonate to get it all out of solution, if nothing else this means the basic mercury carbonate can be reused. Silver salts are also a tad toxic, but the metal isnt, and Id probably have chosen to try this instead even bearing in mind its greater sensitivity.

In terms of the 95% requirement for ethanol, water isnt the main problem, though too much and the reaction wont start, but methanol is supposed to a bigger problem. Chemically dehydrating vodka would probably do at a pinch, everclear type alcohol isnt sold in a lot of countries mainly for tax reasons.

Some of the statements about low and high order in this thread seem a little 'foggy' if you dont mind me saying so. I dont know if there is a single 'official' version of the difference but I'll state the one Ive been using for some time, and that is usually used for transportation issues. Low order decomposition wave travels at or below the speed of sound in air taken as 3300fps, High order is substantially above. This sounds a bit arbitrary, but it makes sense with the physics. Speed of sound is the maximum rate gas can move from one place to another through air. If the gasses are produced at a rate much greater than the rate they can dissuptate (speed of sound in air), they build up to massive pressures and the result is an audible bang. High order explosives usually support a shock wave, but thats not always the case with high order explosives by this definition. Low order explosives usually require hot air/particals to communicate to other grains and thus the rate that grains are communicated is around the speed of sound in air, this is independent of the surface burn rate, but you all know this. Many mixtures and compounds support several discrete decomposition rates (aside from such variables as density, degree of confinement etc), some of which cover both high and low order rates, some of which classic low order mixtures will go high order given a strong enough shock wave, but arnt capable of amplifying it, and are thus arnt generally thought of as high order mixtures.

Ok, thats as clear as mud, but as a rule of thumb, if its the breaking of the container releasing high pressure gas thats causing the bang, then it has to be low order. If theres minimal confinement, and you get a bang anyway (usually much sharper sounding) it has to be high order.

RP/ClO3 mixtures detonate, theres no doubt, if this stuff is giving a bang, its detonating. Flash mixtures are often low order in small amounts, but as the size of the metal powder decreases, and the violence of the oxidiser increases nitrates, perchlorates, chlorates the minimum unconfined diameter for detonation decreases. Confined mixtures are more likely to detonate than unconfined ones and large theatrical flash pots have been used for a long time to detonate secondary epxlosives by the IRA for example. I doubt theres any good info on doing so outside fringe literature though.

If RP/ClO3 was a low explosive or a propellent then calling RP a fuel would make sense, it is burning in the resulting oxygen but my thoughts are this happens after the det wave has already moved through the mixture, being ground powders. In my experience of RP/ClO3 mixtures, using very finely ground RP is effective in rendering sodium chlorate easily detonatable in such tiny amounts that the extra energy by its burning is negligible. Id be inclined to call red phosphorous a sensitiser regardless of ratio. Id also like to add that attempting to make a secondary by sensitising large amounts of a chlorate in this way is too unsafe to be useful.

<small>[ March 25, 2003, 12:40 PM: Message edited by: Marvin ]</small>

[shooter3]

Finding useable ethanol is easy. Here's 2 places. Drug store under rubbing alcohol, there are 2 kinds, ethanol which you want and isopropol which you don't want(at least for fulminate).

In hardware stores it is called "Denatured Alcohol". It is used to thin shellac. Make sure you don't get solvent alcohol(methanol) ,unless you want to make methyl nitrate.

If part of the fumes are acetylaldehyde does anyone know what percent and are they recoverable?

[Boob Raider]

Can anyone try making some fulminate with glacial CH3COOH, (NH2C2H4OH)monoethanolamine, diethylether, Triethanolamine or other similar commonly available chems. Or if anyone knows the reason why C2H5OH can't be substituted or which C actually gets bound in the fulminate (the CH3 one or the CH2OH one)... that would also be really very helpful.
Oh and BTW ... "denatured alcohol" Normally has CH3OH in it which is not desired in fulminate synthesis. Drug stores now only have Isopropanol. C2H5OH cannot be bought without a license in Canada.

<small>[ March 26, 2003, 10:23 AM: Message edited by: Boob Raider ]</small>

[vurr]

ethanol can be distilled from vodka or whisky or wine (recomm.from liquid phase,remaining from deep frozing.. :) nb!plastic bottle!!) with common kitchen boiling devices.need only a plastic/copper tube to the output,and some cooling of that.
remained water can be removed with strongly heated copper sulphate(white powder)or silicagel (haven't tried microwaves for CuSO4*5H2O(garden chemical),which works greatly for used silicagel dessicant granules ,5 minutes,1kW,decreasing ~ 20% of weight)

[frogfot]

How sencitive is MF? I'm asking this because people on rec.pyrotechnics says that it can detonate from falling drops of water.. and this made me worry. Sounds that it's more sencitive than AP, or?

EDIT: Ouh! sorry, you're right zaibatsu, i was thinking about silver fulminate.. :o

<small>[ March 27, 2003, 11:59 AM: Message edited by: frogfot ]</small>

[zaibatsu]

I'm sorry if this is wrong, but you may be thinking about silver fulminate. It's used to coat gravel that 'snaps' when it is contained in a paper twist and thrown on the ground.

[Boob Raider]

Does Ag2C2 have the same sensitivity as AgONC. If it does .... AgONC definately wouldn't blow up from H2O drops as Ag2C2 doesn't. I would rate its (Ag2C2) sensitivity in the Armstrong mix range. Since we've talked about making other fulminates and no one seems to have experimented with substituting ethanol :confused: , Are other carbides .... like Pb etc possible to prepare (thinking along the lines of azide as far as performance goes) has anyone attempted anything in this field ? (over to the carbide section ...) :p

[kingspaz]

boob raider, i've been looking into this and the only good info i found was in federoff. it explains a fair bit <img border="0" title="" alt="[Wink]" src="wink.gif" />

[Trinitrotoluene]

For those of you who have some problems with obtaining ethonal, either if your too young or its too expensive, why not ferment you own? In small batches you only seem to need sucrose(table sugur) water, and some yeast. But for larger batches you need some nutrents.

[rikkitikkitavi]

yes, but homemade alcohol isnt exactly pure. After distillation you need to filter it through active carbon to remove most of the impurities, otherwise these will create lots of sidereactions.

/rickard

[Stone]

Inferno... You can buy acetone from any hardware store in Oz. And as far as I know, the primers in shotgun shells contains mercury fulminate, if you are still after it.

[Anthony]

Shotshells have lead styphnate primers. AFAIK, MF is/was only used in Russian ammo, where it was the only primary sensitive enough in the extremely cold weather. Caused bad barrel corrosion thought IIRC.

[Stone]

My bad, I was told they had mercury fulminate... So that yellow powder is Lead Styphnate?

[Trinitrotoluene]

Today I had a dream in my dream I prepeared mercury fulminate, this is what I did, In a 50ml erlin flask I added one gram of mercury metal then added 10ml of HNO3.It took an hour to dissolve.In another 125ml erlin flask I added 15ml of 95% ethanol(home distilled and ferminted).Then poured the nitrate/mercury soloution into it. No reaction, a little heat was applied with a hot water bath, a vigerous reaction took place alot of white fumes, after a few minutes orange fumes, the reaction thats suposed to take 15 minutes took less then 5 minutes. After that a precipitate formed white crystals with a peach colored tint. The soloution was neutralized with sodium bicarbonate soloution, the crystals changed colors from white with peach tint to gray. Its on a coffee filiter now drying.

[frogfot]

Is this color change normal? Many files on MF and SF never mentions washing with bicarbonate.. is there some obvious reason to it?

[rooster]

Maybe some of the peach-coloured stuff reaacted with the bicarb, so that it left you a grey product? Anyways, I have never heard of peach coloured fulminate. I suppose it depends on purity of chems and so on. It is used to be gray right from the reaction. You can dissolve it in ammonia or something to get a white product. Also I heard something about adding some copper before adding the Hg. What is this about?

[Trinitrotoluene]

I just thought that neutralizing it will yield a more stable product. I find it strange to find my mercury fulminate a preach color. But again after neutralization, the color went to gray which is normally how unpurified mercury fulminate looks like. The precursers use are rather fair.Mercury metal technical grade, ethanol, from fermination, then distillation 3 times to yield 95%, nitric acid distilled from NaNO3, and H2SO4. I forgot to mention my HNO3 contained NO2, after adding the Hg metal into the HNO3, the soloution didin't turn green it remained the same color as the HNO3, after adding the mixture to the ethanol, the color disappeared and the whole soloution became clear, then a little heat was applied the reaction started.

[Trinitrotoluene]

Does anyone know the senistivity of mercury fulmiate compaired to HTMD and AP? In my searches I had found that mercury fulminate detonates form a .25cm drop from a 2kg weight, and HMTD 3cm from a 2kg weight, that seems very senistive. Are those figures accerate?
Thanks.

[Boob Raider]

I came across a page which shows 3 possible structures for the fulminate ion. Here is what they are >
http://bilbo.chm.uri.edu/CHM501/oldproblemsets/DMA2_2.htm
The Hg(ONC)2 we make contains all three of these forms presumably. Does anyone know of ways to tilt the reaction in forming the stabler version. Similar to the alpha - PbN3 and beta - PbN3.

[frogfot]

I assume the electron cloud moves freely and takes the most stable form itself.. don't see why it should lock on other two less stable forms.

[Boob Raider]

Does anyone know what happens if iso-propanol is added to the Hg(NO3)2/HNO3 mix. I tried a very small amount in a test tube and as soon as I add iso to the warm NO3 mix ..... a very vigorous reaction (exothermic too) takes place and the volume increases almost 30 times and the mixture turns yellow from green. On the other hand when I added a mix of 90% ethOH/ 5%Isopropanol/ 5%methanol the reaction some what spurted out of the tube in one shot. Later on I did notice some greyish-white crystals in the tube, presumably of Hg(ONC)2.

[IPN]

SWIM had his first experience in mercury fulminate last night.

SWIM used 10ml HNO3 (65%), 1g pure mercury and 15ml ethanol (99%). SWIM put the 10ml HNO3 into a 100ml beaker and added the mercury in, the reaction took few minutes and a green solution was left.
SWIM then put the 15ml of ethanol into 100ml erlenmeyer flask and added the HNO3/Hg mix, reaction was vigorous and took approx. 7min.
50ml distilled water was added, mixture was filtered, and the precipitate washed 3 times with distilled water and once with ethanol. A slightly gray precipitate was left in the filter paper.
Product was dried over night in a desiccator.
A 0,25g sample was placed on a metal plate and struck with a hammer, detonation occurred with a loud bang and formation of mercury.

SWIM thinks that MF will be he's new primary because of the ease and speed of manufacture, although HMTD seems like a more powerful and stable one..

[al93535]

Well I was making Hg fulminate and it went bad! Everything went fine until I started heating the solution after the addition of alcohol. It began to emit white smoke as normal, then when I picked the flask up out of the bath to set it down it happened. I looked at the Hg fulminate crystals, they were floating to the top and decomposing! It looked as if they were boiling. As soon as I could set the flask down huge amounts of NOx, red smoke, was billowing out of the flask! There was tremendous amounts of it, and it was accelerating more and more coming out incredibly fast. I dumped water into it fast and it stopped. Just make sure not to heat the solution too much! ;) I just dumped the shit, just to be sure! What a waste of Hg and nitric. Have to try again. :)

[pdb]

Hg & Ag fulminates synthesis must be watched after as milk on fire...

You must be prepared to warm the mixture if the reaction seems to take a long time before starting (temperature should increase slowly), and to slow the reaction down when it becomes too tumultuous, by addind a few ml of cold alcohol... As a matter of fact, I always noticed the reaction is always more violent and irregular, hence unpredictable, with Ag than with Hg. However, making AgONC is not a good idea given its extreme sensitivity.

[Bert]

How close to theoretical is the yield from the classic Hg/HNO3/ethanol technique of fulminate production?

How seriously would the methanol denaturent in "hardware store" variety denatured alcohol affect the procedure?

[al93535]

Bert:

I always used the denatured alcohol with no problems. Except the once overheating it :) Yield seems okay, my first try I got 2.35 grams from one gram Hg.

[Bert]

Bert:
Yield seems okay, my first try I got 2.35 grams from one gram Hg.

That yield is a lot better than OK-

Mercury metal: Mol weight = 200.59 aprox.

Mercury fulminate: HG(ONC)2 Mol weight: 284.59 aprox.

By my calculations, 1 gram of Hg should at most be capable of producing only about 1.418 grams of fulminate- Are you sure it was dry?

[al93535]

Bert:
I did use .1 ml of mercury, its density being 13.something, so actually I used 1.3 grams. I am pretty sure it was dry, although it was crude, not recrystalized. So some impurities were present. Although I thought more could be obtained from 1 gram. Take a look at powerlabs.org, he synthesized 1.1 grams Hg to about 2.5 grams after recrystalization! I thought my yield was just okay, being crude. I think I will recrystalize it and re-weigh and will post what I get back.

[Bert]

Bert:
I did use .1 ml of mercury, its density being 13.something, so actually I used 1.3 grams.

It sounds like you didn't weigh the mercury? You tried to measure it by volume? Considering the behavior of small ammounts of mercury, volume measure of such a small quantity isn't likely to be too accurate.

(quote from powerlabs)
Yield here is estimated at about 2.5 grams (one cc)

- Sounds like he just guessed.

[al93535]

Bert:
I didn't want to get any mercury on/in my scale. I know that small amount is hard to measure. I got close though, I used a 1 cc medical syringe with .1 cc increments. So I would guess it was pretty accurate. My powder is drying from recrystalization now, will let you know the yield when it's dry. I will also be trying about half a gram of silver fulminate in the near future. :D

[Bert]

Bert:
I didn't want to get any mercury on/in my scale.

Some have been known to weigh the reaction vessel empty and then weigh an ammount of a reactant desired directly into the reaction vessel, eliminating loss, errors, and haveing to clean extra containers.

[al93535]

I use a reloading scale which goes to 500 grains and it's quite small, and very accurate, but I can't fit much onto it. Otherwise I would have done just that. For other substances I use a coffee filter and subtract that from the final weight. I just don't like messing with mercury, and won't be making any more of this stuff. I will stick with hmtd/rdx detonators. I weighed the recrystalized product and got 1.983 grams of pure white Hg fulminate. I would say I got a good yield. The crude product was grey/yellow. It deflagrates nicely and is quite bright. For others who can't get mercury, a good source is in abandonded houses, in the air conditioning temerature setting device is a mercury switch.

[Bert]

Which nitrate of Mercury is formed by the reaction with nitric acid, mercurous nitrate Hg2(NO3)2
or mercuric nitrate Hg(NO3)2 ?

[Sarevok]

al93535: When heated, mercurous oxide is decomposed to mercury and oxygen. Mercurous oxide itself can be bought from chemical supply stores. That's much better than stealing garbage from abandoned houses, isn't it?

Bert: With hot nitric acid, it forms mercuric nitrate, Hg(NO3)2. If there is an excess of mercury, however, it forms mercurous nitrate, HgNO3.

[Bert]

With hot nitric acid, it forms mercuric nitrate, Hg(NO3)2. If there is an excess of mercury, however, it forms mercurous nitrate, HgNO3.

I'd then assume an excess of HNO3 is present in the classic Hg fulminate synthesis, and the intermediate "greenish" solution is mercuric nitrate in nitric acid-

BTW, from US patent #4093623:

A Hg(NO3)2 solution was prepared by dissolving 54.0 grams of red mercuric oxide in 200 ml of 35 percent nitric acid
If this is correct, no need to decompose the red mercury oxide to metalic Mercury prior to reacting with nitric acid?

[Sarevok]

The patent's information is probably correct. HgO is easily decomposed to its constituents; it probably undergoes decomposition when being dissolved in nitric acid too.

[Myrol]

Has Mercury fulminate a better Initiating effect than AP? Or is it just wasting time to make MF contra AP? I have here around 25ml Hg left from my University and have no real use for it!

[metafractal]

AP has a higher explosive power (det. velocity, brisance) than mercury fulminate and therefore is a better initiator. However, mercury fulminate is storage stable where AP is not. Whilst of similar sensitivites, mercury fulminate's activity is generally predictable whereas AP might withstand a 3kg anvil drop one day, and detonate from a feather the next. So it has its upsides.

[Rosco Bodine]

AP has a higher explosive power (det. velocity, brisance)
than mercury fulminate and therefore is a better initiator.

It is admittedly counterintuitive , but such properties are not absolutely
definitive about what will be the efficiency of an initiating explosive ,
and that anomaly applies in this case , because AP is a *poorer* initiator
than MF , in spite of the numbers for AP which would indicate the opposite
expectation to be realized .


However, mercury fulminate is storage stable where AP is not.

The reverse is actually true , if chemical stability is what you are describing .
The instability of AP is a *physical* problem related to volatility , where
smaller crystals sublime and recrystallize in situ , forming larger and larger
crystals over some weeks or months time , the continual process produces
an unpredictable physical form for the charge , even a "self-grinding" effect
for compressed crystals is conceivable , which could result in spontaneous
detonation . What are the odds of this happening with AP , and the charge
geometries / quantities which would be vulnerable , I don't know .

Using AP as an unreenforced top charge initiator in attempts to detonate
picric acid , I have had no experiments produce detonations of picric acid ,
whereas similar quantities of HMTD always produced complete detonations
of the picric acid base charge in compound detonators . From such experiments
it is evident that in unreenforced caps where relatively insensitive base charges
are to be used , AP is not useful , but within its limited shelf life , HMTD is
useful as an initiating explosive . These experiments involved lightly pressed
charges of 9 mm column diameter in 1.5 mm wall thickness polypropylene tubes .


Whilst of similar sensitivites, mercury fulminate's activity is generally predictable
whereas AP might withstand a 3kg anvil drop one day, and detonate from a feather
the next. So it has its upsides.

Von Herz reported that the performance of mercury fulminate could
be greatly enhanced by its mixture with lead styphnate , or by use
of mercury fulminate as a cover charge for lead styphnate , as an
initiating means for a base charge of pressed crystalline TNT .

GB142823

More dubious information as follows :

A curious patent of interest related to a "modified" mercury fulminate
in a mixture with an unspecified basic lead picrate double salt is

GB199489

And by the same inventor a mercury fulminate "substitute" based
upon the same sort of basic lead picrate double salt wetted with
a small percentage of nitroglycerine

US1398098

Details of Chandelon's warm process batch method for mercury fulminate
is briefly described on the first page of

US1523338

[Bert]

The patent's information is probably correct. HgO is easily decomposed to its constituents; it probably undergoes decomposition when being dissolved in nitric acid too.

Sadly, it doesn't appear to work. At least not as when substituted directly into the classical procedure in an ammount suitable to provide an equimolar ammount of Mercury. It does dissolve in the Nitric acid producing a clear solution ,which has no reaction with ethanol even on heating other than the evolution of what I assume to be ethyl nitrate fumes.

[Rosco Bodine]

Try dropping a pinch of starch , paraformaldehyde , or sodium nitrite
into the reaction mixture and see if that doesn't initiate the reaction .

[Bert]

Try dropping a pinch of starch , paraformaldehyde , or sodium nitrite
into the reaction mixture

5.4 g of red mercury oxide (HgO) was dissolved in 50 ml of room temperature 70% HNO3 in a 500 ml beaker, resulting in a clear solution with no visible fuming and only a mild warming.

50 ml of denatured ethanol was measured out, 25 ml of which was quickly added to the Mercury nitrate solution. After about 5 minutes, no visible reaction was noted. At this time, .25 g of Sodium nitrite (NaNo2) was added to the beaker. A mild effervescence and a change of the solution to a slightly yellowish color was noted after a few moments. The effervescence accelerated, with self heating and development of heavy white fumes. When the reaction seemed in need of moderation to prevent bubbling over, the remaining 25 ml of alcohol was added to the mix in several small portions. An additional 20 ml of alcohol was also added for purposes of reaction moderation after the initial 50 ml was expended, bringing the total to 70 ml.

About 30 minutes after the onset of effervescence, the reaction had subsided and a considerable amount of a light grayish precipitate had settled out. The contents of the beaker was added to about 200 ml of distilled water and the solids filtered out in a Buchner funnel. The retained solids were washed with several portions of water and then given a final wash with alcohol.

The first obtained solids weighed 5.1 g after drying, and were of a yellowish/grayish color and needle like crystal shape.
These solids were dissolved in 80 ml of 30% ammonia and the liquid filtered. The filtered liquid was carefully neutralized with glacial acetic acid, the resulting precipitate filtered out, washed with water and then alcohol and dried. The precipitate weighed 3.65 g after drying and was a dense sparkly white powder consisting of small crystals, quite different in shape from the crystals of the initial product.

The product displayed the characteristics of mercury fulminate, deflagrating in small quantities in the open and detonating violently in larger quantities or if confined. The entire remaining batch was mixed in 80:20 ratio with KClO3and detonated, as dry storage seemed inadvisable and no use was anticipated for a primary explosive... "It made a jolly bang"

[Rosco Bodine]

It was an educated guess that nitric oxides present in the acid
as a byproduct from the formation of nitrates from the metals ,
would be the thing missing from the system if you made the nitrate
from the oxide of the metal instead of using the free metal .

Anything which would cause decomposition of the nitric acid
and produce nitric oxides would probably initiate the reaction .
The materials which I mentioned above would cause the missing
nitric oxide to be formed .

[ikbendirk]

Why bother trying to dissolve the mercury in nitric acid?
I know mercuric/-ous nitrate isn't a very common salt, but for example, in the silver fulminate synthesis, instead of dissolving silver in nitric acid, why wouldn't you just dissolve AgNO3, one of the most common silver salts...?

I know that for some of you this isn't the best way to do it, because of the availability of chemicals, but as my father is a teacher in chemics, he can easily get me some AgNO3, where HNO3 seems to be too dangerous to him.
So is it technically possible to substitute the Hg/HNO3 solution by Hg(NO3)2?
Or the Ag/HNO3 solution by AgNO3?

[K9]

I'm fairly certain that for the synthesis you want a solution of the nitrate in an excess of the acid, and thus even with the nitrate salt you would still want to dissolve it in the acid before the reaction with the ethanol.

[Rosco Bodine]

Surely you can use oxides or nitrates or other compounds of the metals
as the starting material for the fulminates , but these would need to
be dissolved in nitric acid to supply the excess nitric needed for optimum
yields of the fulminate . Less added nitric acid would be needed if the
metal source being supplied was already a nitrate .

As Bert observed above , the presence of some nitric oxides is also
needed in the reaction mixture to initiate the oxidation of the ethanol ,
and this complicates the process slightly if you are using a metal nitrate
as the starting material . If you start by dissolving the metal directly
in excess nitric acid , the byproduct nitric oxides are present in the
residual acid solution of the metal nitrate just formed , and the reaction
begins on contact with ethanol , with no added catalyst needed .

Economy is the principal reason for simply dissolving the metal in
nitric acid for the synthesis of fulminate . For the market cost of
silver nitrate is easily twenty times the cost of the silver contained ,
at six dollars for an ounce of silver , it is evident that is far cheaper
to dissolve a one ounce bullion coin in nitric acid and evaporate the
solution on a *mildly warm* water bath to obtain your silver nitrate .
( The nitrates are heat sensitive and will decompose to the oxides if
a boiling water bath is used )
For mercury , the story is similar .

[palpy]

It's not nitric oxides, but HNO2 what is crucial for the initiation of the reaction (it converts acetaldehyde into isonitrosoaldehyde). That's why HNO2 free nitric acid can't be used for the production of fulminates. Ordinary commercial grade HNO3 contains trace amounts of HNO2, which starts the reaction, is consumed, but then recycled as a byproduct in the final stage (creation of fulminic acid) of the reaction chain.

[Rosco Bodine]

An assortment of nitrogen oxides and their corresponding acids
and intermediates and reaction products is going to be present
in the complex reaction mixture . Which one is definitively essential
for the reaction to start is probably not even possible to determine
since many or all of those nitrogen oxides are going to be present
as the reaction proceeds along many possible paths simultaneously .
HNO2 will evidently initiate the reaction , but so should other
radicals reactive with HNO3 or with each other and water leading
to the HNO2 . The solution of a freshly made heavy metal nitrate
in excess acid would be well polluted with HNO2 and NO2 and NO ,
but all such nitric oxides are going to be present in some mix of
proportions depending upon temperature . Simply heating the
nitric acid solution of the metal nitrate derived from whatever source
would eventually lead to the presence of these compounds from
the thermal decomposition of the nitric acid and/or the metal nitrate .
Likewise , leaving the flask sitting in direct sunlight would probably
get the reaction started . It is a murky matter to identify precisely
which species in such a mixture is the key reactant , when several
oxidizing compounds are present simultaneously , and any one of those
interrelated nitrogen oxides could catalyze the reaction . Berts experiment
confirms that adding a nitrite will cause a sluggish reaction to initiate ,
but that doesn't necessarily mean that is the only way to do that trick
or that HNO2 is the only possible starting point for the reaction .
Anyway , we generally agree about the HNO2 being an initiator of the
reaction , but its origin is more from the solution of a heavy metal
being dissolved in nitric acid to produce the nitrate , than is it present
in any substantial amount in ordinary concentrated nitric acid of commerce .

Consider the different equations below for the formation of the nitrate
from silver and mercury dissolved in nitric acid , understanding that
both reaction mixtures will self initiate on contact with ethanol to
form the fulminates .

mercury in concentrated nitric acid
Hg + 4 HNO3 -------> Hg (NO3) 2 + 2 NO2 + 2 H2O

mercury in dilute nitric acid
3 Hg + 8 HNO3 ------> 3 Hg (NO3) 2 + 2 NO + 4 H2O


3Ag + 4 HNO3 -------> 3 AgNO3 + NO + 2 H2O

You see the variations in byproducts confound the identification ,
before you even look at the possible reaction products of the
nitrogen oxides with water which further complicates the matter .

[Bert]

These solids were dissolved in 80 ml of 30% ammonia and the liquid filtered. The filtered liquid was carefully neutralized with glacial acetic acid, the resulting precipitate filtered out, washed with water and then alcohol and dried.

Household ammonia water sold around here is 3%.

The strongest "janitor grade" ammonia water I can buy OTC is 10%.

Lab grade concentrated ammonia at nearby chemical suppliers is 29.4%.

On looking up solubility data, I find that maximum solubility is supposed to be around 31% at STP, and at 0* C around 42%. I have prepared a more concentrated solution from the OTC 10% by heating a 3X volume and bubbling the ammonia that comes out of solution through a single volume of 10% in a salt/ice bath-

Does anyone have a chart of specific gravity vs. % concentration for ammonia? It's a reverse of the one for acid- it gets LESS dense the more concentrated it is. Experimentally, I found 30% be .927 g/ml and 10% to be .963 g/ml at room temperature.

What is the minimum concentration needed to dissolve Mercury fulminate? Is there solubility information (grams per liter @ concentration @ temperature) available? COPAE just says "strong ammonia water"... 30% works, but is this excessive?

In regards to acetic acid, how strong a solution could be prepared by distillation from the commercially available 5% "white vinegar"? What would be the parameters for temperature?

And lastly, what ARE the impurities removed by purification of the yellow/tan crude fulminate?! I actually saw a few tiny beads of METALLIC Mercury on the bottom of the beaker after dissolving- I also wonder what kind of yield is technicaly possible, I find it unlikely that even in the "good old days" a 50% of theory yield from expensive Mercury would have been acceptable!

[Marvin]

Normal lab ammonia is traditionally 880, which is around 35% w/w.
Try,
http://www.terraindustries.com/our_products/ammonia/ammonia_tech_manual_2002.pdf
I'm unaware of any problems making glacial acetic acid by distillation, but its a hell of a job in terms of volume. Glacial acetic acid can usually be bought from photographic suppliers.

I only tried mercury fulminate once, for obvios reasons, and I didnt purify it as Davis says the grey product is (was) commercial grade anyway.

[Rosco Bodine]

http://chemdat.merck.de/cdrl/services/labtools/en/tools_body.html

An assortment of very useful printable tables are here ,
including a density table for aqueous ammonia solutions .

The best OTC source for concentrated ammonium hydroxide
is at drafting and blueprint supply stores where gallon jugs
are sold cheaply as blueprint developer for the diazo process .

Seven or eight dollars per gallon for 28-30 percent .

[Bert]

Thanks, Rosco, Marvin-

From the Merck table, I would judge that either my graduate or my scale is inaccurate. I used a 5cc graduate, perhaps I will try again with a larger volume in hopes of reducing measurement errors. (Or my lab supplier may be watering the goods!)

I was looking at this from the viewpoint of OTC from grocery store, auto supply store and a few salvaged Mercury switches. With photography supply and blueprint supply thrown in, you don't have to waste time concentrating solutions, making Nitric acid from battery electrolyte and fertilizer is certainly enough effort without that on top! I understand that the the commercial product was not purified back in the day- Did that contribute to a short storage life? I have seen in COPAE that a fulminate cap was rendered inert by a couple of years storage in the tropics-

Another issue I've wondered about is the 80:20 fulminate/chlorate mix used in the original Copper blasting caps. I've been taught to not handle chlorates with copper or brass tools- Could that have contributed to shortening the storage life?

[Rosco Bodine]

There is a patent about the usefulness of vacuum drying
mercury fulminate at a slightly elevated temperature in
order to remove traces of volatile free metallic mercury
trapped in the material during manufacture , so it is
reasonable to expect that without recrystallization
the presence of traces of free mercury in unpurified fulminate
indeed does occur and has been a problem also observed by others .
US1718371

[0EZ0]

Free Hg metal is most certainly aparrent in the unpurified end product. I presume the mercury metal is present from the thermal decomposition of Hg(NO3)2 starting material and of the intermediate salts during the reaction process. Also the crude Hg fulminate could contain various compounds and oxidation products of ethanol and any contaminants in the starting precursors. I think there is some discussion earlier in this thread and others pertaining to the same subject that contain info on the by-products of the fulminate reaction.

As I understand it, Hg(ONC)2 is not thermally stable, like many other Hg salts and will decompose at a fast rate under heat. It will also decompose on long term storage where the ambient temperature is high (just as in the tropics). COPAE has alot of info on Hg fulminate if you wish to find further information.

As for Acetic Acid, well there are a few different routes to preparing it. Distillation of common 'white vinegar' is not the the most attractive option but should be possible. Keep in mind that Acetic acid distills over at a higher temperature than water (at something like 120 degress C) and that azeotropes of the two components are said not to form.

The better method for the preparation of Acetic acid is through first creating an Acetate salt either with Sodium Hydroxide or some other hydroxide. Then you can either dry distill the anhydrous salt to produce Acetic acid fumes or alternatively combine the salt with Sulfuric acid and then distill. Of course if you can get a large amount of food grade Sodium Acetate then it would be much cheaper and more efficient than starting from vinegar.

Sodium Acetate is a component in reusable hot packs that incorporate a supersaturated solution of the salt which produces heat upon crystallising with a metal disk. Sodium Acetate is hardly going to arouse suspicion if bought from a bulk commercial/industrial supplier. Food grade Sodium Acetate is sold to caterers and other food preparation businesses as a flavouring(salt & vinegar) and preservative. It also finds wide use in industry for many other applications.

Medicinal hot packs and Sulfuric acid drain opener or battery electrolyte are both found quite easily OTC. It should not be too hard with this information in mind, to produce Glacial Acetic acid in the home without too much fuss.

[Rosco Bodine]

There may be a different and more economical simpler
method for isolating pure mercury fulminate , which also
provides the option for making other fulminates from
the sodium fulminate intermediate . Davis reports in
COPAE that mercury fulminate crystallizes from water
with a half molecule of water of cystallization , or one
molecule of water bound with two molecules of mercury
fulminate , but gives no temperature associated for the
formation of that hydrate . He also reports that the
anhydrous salt is obtained by crystallization from alcohol .
The solubility of mercury fulminate in a liter of water is
.71 grams @ 12 C , 1.74 grams @ 49 C , 7.7 grams @ 100 C .
Given the significant solubility in hot water of mercury fulminate ,
it would seem that seven grams per liter of water could easily
be purified by making a saturated solution in boiling water ,
and then pouring that into a large shallow tray for rapid cooling .

It has been reported by the early researchers that digesting
mercury fulminate in water with sodium chloride will lead
to a solution of sodium fulminate . Given the solubility of
mercury fulminate in water , perhaps it would be better
to add a solution of sodium carbonate or sodium bicarbonate
dropwise to a rapidly stirred suspension of mercury fulminate ,
which should react with the dissolved mercury fulminate to
precipitate the relatively insoluble mercury carbonate , as
additional mercury fulminate dissolves to continue the reaction
to completion . The result would be a solution of sodium fulminate
and an insoluble precipitate of mercury carbonate which can be
recycled in mercury fulminate synthesis . By this method it should
be possible to produce a relatively concentrated solution of
sodium fulminate , which could be used to precipitate many
different fulminates by a cold process , simply by mixing with
a solution of the metal nitrate , acetate , ect. of the metal fulminate
desired . The precipitated fulminates could then be controlled
in crystalline size , precipitated as mixed or double salts , or
given coatings and other treatments by the same strategies as
are used for producing metal azides . If workable , this method
might be of particular interest for silver azide , which could be
made in extremely small particles and then perhaps coated with
two or three per cent of its weight , of an adherent film of bright
red silver chromate , from a finish treatment with sodium dichromate .
This would provide an insensitive coating upon the microcrystals
and also greatly diminish or eliminate photosensitivity by the opacity
of the silver chromate coating . This is all purely theoretical .
I have done no experiments at all to test this proposed scheme ,
or to identify any potential dangers .

However , there may be some usefulness in the strategy for producing
sodium fulminate by the above proposed method , which could
then be used by a cold process to make purified metal fulminates
of interest , including a purified mercury fulminate itself , by an
alternate method which requires only aqueous solutions , and
does not require ammonia nor acetic acid .

[Rosco Bodine]

Being curious about the above theory/theories ,
I have decided to do an experiment to attempt to
confirm or disprove the ideas . A small batch of
fulminate is precipitating now as I am writing this post .
The method that I am using is a slight variation on
megalomanias method for mercury fulminate , using
one and one half times the amounts and using denatured
alcohol instead of pure ethanol . When I mixed the
still slightly warm green solution of mercury nitrate
in nitric acid , all at once with the alcohol , there was
only a slight warming and the reaction did not proceed
further . I tried adding a tenth gram of sodium nitrite
and the reaction mixture warmed slightly , then cooled
again . So I set the beaker in a pan of very hot water ,
to kickstart the reaction . The heat did the trick , and
the reaction is feeble enough for these quantities that
I am leaving the beaker in the hot water to maintain the heat
of reaction . There is a steady effervescence in the solution
with a smoky dense white vapor above the liquid . In the opening
at the top of the beaker I have placed a small pyrex bowl
of the sort used to serve sauces in restaurants , a custard cup
as some call it , and there are three ice cubes melting in this
improvised "cold finger" which is working nicely to return any
alcohol to the reaction by drips from its cold underside .
There is a pungent odor of fresh cut apples in the vicinity
of the reaction outdoors , indicating the escaping acetaldehyde .
And a layer of fine sand like crystals , very pale yellowish , almost
white in color is accumulating steadily on the bottom of the beaker .
There is no violence at all about the reaction , the reaction is
a steady effervescence of very fine small bubbles with no boiling
of the liquid or larger bubbles or foaming problems at all .
It looks like a reaction time of about one to two hours
is what will be the duration , even with the supplemental heat .
I did not check using a thermometer , but my estimate is that
the reaction runs steadily at about 80 C , and slows below that .
If the fulminate is still very light in color and evidently reasonably
pure , I may skip the boiling water recrystallization , and go
straight to an attempt to convert the mercury fulminate to
sodium fulminate .

Edit : The crystals are dried and weighed . The color is a light tan
with no gray at all , so the purity looks good , but the yield of the
process is shit , only four grams from 7.5 grams of mercury ,
a yield of only 37 per cent of theory . 10.64 grams would have been
100 per cent yield , based on anhydrous mercury fulminate . The
yield for commercial manufacture of large batches is about 88 per cent ,
or about 1.25 grams of mercury fulminate from each gram of mercury .
In the commercial process the reactants are prewarmed to 55 C ,
so that the heat of reaction is sufficient from there to maintain the reaction .
For small batches , it is probably even more important that the reactants
be sufficiently warm before mixing , and in future procedures I will
use more heat early in the reaction in an effort to improve yields .

Update: The four grams of mercury fulminate were suspended in
40 ml water and to the well stirred suspension was slowly added by drops
a solution of 2.3 grams sodium bicarbonate in 30 ml water . There was
only a very slight cloudiness observed and no effervescence of carbon dioxide ,
indicating that the reaction to produce sodium fulminate failed .
If sodium fulminate had been produced , there would have been free
carbon dioxide produced as a byproduct , and this did not occur .
A later experiment will be done to see if sodium hydroxide will produce
the desired sodium fulminate . It may be that the early researchers use
of sodium chloride is because other sodium compounds don't work .

[pdb]

Rosco: you bad yield comes most likely from the fact you left the reaction run too long... I have noticed on numerous occasions that the MF precipitate would reduce when left overtime, leading me to limit the reaction to 30 minutes only, which implies you have to start it straightly by heating the mix if bubbling has not started in the first 5 minutes. Another experimental statement I noted is what I would condense in "the more violent, the better", i.e. contrary to what you did, quiet bubbling is not an omen for a good yield. On the opposite, a tumultuous reaction generally gives an higher crop. However, in my best trials, I never exceeded 82%... but 100% or close is out of reach with this method.

[Rosco Bodine]

Yeah , I agree that the reaction needs to start quick ,
and run to completion quickly . I searched a lot of
old usenet postings and read every patent I could find
for any clues about details that are important to getting
better yields . One thing that was mentioned several times
is that many denatured alcohols will contain methanol which
will cause a sluggish starting reaction and poor or no yield ,
as methanol tends to poison the reaction for fulminate .
That is probably what crippled the reaction for me because
I did use an ordinary paint thinner grade of denatured alcohol .
There is a medical grade of 70 per cent ethanol "rubbing alcohol" ,
that is denatured with something else which may give better results .
Beverage grade "everclear grain alcohol" is supposed to give the
best results . So the purity of the alcohol and the type denaturant
are reported factors .

The temperature of the nitric acid solution of mercuric nitrate
and the alcohol should *both* be *very warm* when the initial mixing
is done , so that the "induction period" for the reaction to reach
the boiling point is shortened , and the reaction begins quickly .
I saw one post that mentioned the reaction for fulminate proceeds
best within a temperature range of 80 to 90 C in the reacting mixture .
A lot of unreacted alcohol is likely boiling away during the reaction ,
and perhaps carrying away some other volatile byproducts along
with the alcohol vapor , so it may actually impair the reaction to condense and
return any of this vapor as I was doing . I don't really know what the
story is on this possible variable . There is a lot of acetaldehyde
produced by the reaction , and the well rinsed and dried crystals
in my sample still have a slight residual odor of acetaldehyde when
they are wetted again with water . The color is very light tan , and
not gray at all . The crystals were almost white in the reaction mixture
when they first formed , but darkened slightly to a tan color on standing
in the spent mixture , and remained a tan color after rinsing and drying .
The reaction mixture and the crystals themselves are about the same
color as a light ale .

One post I read mentioned using acetone with the ethanol in a 1 to 3 ratio
when making silver fulminate , and I do not know what is the reason for
that unless perhaps to help moderate the temperature for the more heat
sensitive silver salt .

[pdb]

I think I have read a lot along the years about MF and SF, and I never came across any information reporting adjunction of acetone... As I said in another post, the only difference I noted between MF and SF synthesis is that the latter is more violent and more irregular than the former. I really do not see a need for moderating temperature because of SF's great sensitivity: I had several unwanted explosions with SF, in dry and damp states, but never when it wall still soaking in the rest of the acid-alcool mix, where anyway the temperature cannot raise higher than the boiling point.

I have an interesting monograph on MF of different colors (white to grey and tan), but unfortunately for you it's in French. My MF always comes as a grey or tan product, that you can later purify to get the white flavour.

[Rosco Bodine]

That reference to use of acetone with ethanol was something
I first read about on the russian page I have mentioned before .
Here is a link to an outline of the process also containing a link
to the Russian page itself , which is a difficult page , UTF-8 encoding ,
cyrillic characters , and thereafter difficult to translate using a
chemistry specific translation engine , the translation is muddy
and barely understandable .

http://groups.google.com/groups?hl=en&lr=&ie=UTF-8&th=18dc68903a7ee3eb&rnum=7

About silver fulminate , yeah the sensitivity of the usual product
is indeed the problem . Trying to tame it is precisely the interest
of my experiment to produce the silver fulminate by a cold process
from sodium fulminate and silver nitrate solutions .

[pdb]

Looking at my lab notes, I found that I have never prepared sodium fulminate. However, I did make some Cd(ONC)2 by moderately heating a mix of CdCl2 & Hg(ONC)2 in water. I obtain a tiny precipitate of a fine white powder, which deflagrates when lit by flame. I never got enough to study DDT.

I also prepared Pb fulminate by leaving in presence Hg(ONC)2 and an Pb amalgam for a few days: it's a grey powder which also deflagrates.

Last, I also succeeded to prepare Copper Fulminate from the metal and Hg(ONC)2 in water, with or without NH4OH. Varying the conditions, I obtain products of different appearance, among which a green fine powder which would deflagrate with a green flame. But again, I couldn't study DDT.

[Rosco Bodine]

In COPAE there is a table showing comparisons
of the minimum charges of various fulminates and azides
required for initiating various common base charges .

According to that table , silver , copper , and cadmium fulminates
are roughly comparable with the azides in their initiating ability ,
when loaded in a detonator capsule and fired .

Update : After not getting any reaction with sodium bicarbonate solution
added to a stirred suspension of mercury fulminate , I tried the same
procedure with sodium hydroxide solution and no joy with it either .
One benefit that did occur from the treatment with dilute sodium hydroxide
is a change in the crystalline form to a much finer mesh . There was
probably some slight erosion of the thinner ends of any needle form crystals ,
or the larger crystals were fractured into smaller fragments during the
extended stirring , to produce a more desirable fine mesh of crystals
than was obtained directly from the original synthesis . It is evident
now that the fulminate salt of mercury has little reactivity with dilute bases
even when both are in solution . Chemically its behavior resembles that
of a relatively stable carbonate or basic carbonate or oxide in reacting
very little or not at all with dilute bases . It is becoming clear why a
chloride is the compound found to be useful by the early researchers ,
but I do not like the prospect of having calomel as the byproduct , which
would complicate recycling the mercury in the process . Another idea
has occurred to me which intends to exploit the solubility difference
between mercury fulminate and silver fulminate . A liter of water at
100 C will dissolve 7.7 grams of mercury fulminate , but only .1 gram
of silver fulminate , a very drastic difference in solubility . So it may be
possible to simply make a near saturated , near boiling solution of mercury fulminate ,
and add to this a slight excess of theory of a similarly hot and saturated solution of silver nitrate .
Silver fulminate should immediately precipitate , and the mercury nitrate byproduct
remain in solution , from which it can be recovered by evaporation of the water ,
and easily recycled . I will do an experiment to see if this idea works .

[Rosco Bodine]

So far , not everything that works out on paper holds true in the beaker .

The mercury fulminate did dissolve when sprinkled into well stirred
very hot water which was just at the boiling point . The fulminate
solubility agreed with the figure of 7.7 grams per liter @ 100 C .
The saturated solution was allowed to cool again to 80 C to see
if the fulminate would begin crystallizing back out , which it did ,
confirming that the mercury fulminate was in solution intact , and
not decomposed by the boiling water . The crystals appeared to
be white cubes about the granulation size of table salt . Whether
this is the hemihydrate or the anhydrous salt is unknown . It could
be the anhydrous salt crystallizes at above a certain temperature ,
and the hemihydrate is formed at below a certain temperature , as
is true for many hydrates . Making a determination or finding a reference
about the hydration states of mercury fulminate would provide useful
information for use of the boiling water recrystallization and purification
of mercury fulminate , which appears upon first examination to be practical .

However , upon adding silver nitrate solution to a hot nearly saturated
solution of mercury fulminate , the atempt to produce silver fulminate
by metathesis failed . Instead of the solution turning milky and giving
silver fulminate , the solution turned black and precipitated what appears
to be silver oxide . A perfect example of how in chemistry 1 + 1 is not 2 .
Many of these type outcomes occur , but you never know until you try
to see exactly what will be the actual result as compared with what is
guessed may occur . A different silver salt like the acetate may work ,
or the reaction may be pH sensitive , or the reaction may not work
under any conditions .

Edit: I obtained a pint bottle of the medical grade ethanol "rubbing alcohol"
70 per cent ethanol by volume , and it lists the minor ingredients as
acetone , denatonium benzoate ? , methyl isobutyl ketone , and water ,
a specially denatured alcohol formulation SDA-43-640 . There is probably
a reference somewhere as to what percentages of the denaturants are
used . I am going to shake up this alcohol with an excess of anhydrous
sodium carbonate to tie up the water , and then agitate the anhydrous
alcohol with activated charcoal powder to purify it further , hoping
this will be a sufficiently pure ethanol for fulminate synthesis , from a
cheap source , aside from going the moonshine route , or paying the
cost for expensive beverage alcohol .

The solubility of the mercury fulminate in hot water is something I keep thinking about
in terms of how this could be useful . One idea that has occurred to me is that perhaps
mercury fulminate may form a double salt with mercury or basic mercury picrate and
if it does , then this material could have useful properties .

[rasputin_ecuador]

When I tried making MF... the first time I put 5g of Hg in 35ml of 70% Nitric and for some reason alot of NO2 was released and the mercury dissolved in seconds, when I added 30ml of 96% ethyl alcohol NO2 was also released in great quantities and after 10 minutes white fumes started appearing and it formed a yellow precipitate that floated in the solution, I filtered and washed with distilled water, after drying i tried detonating with no success. The second time, same exact ingredients were used but this time Hg didn't dissolve quite as quickly and released no NO2 gases. When mixed with alcohol the same reaction as the first time took place and again yellow precipitate floated in the solution. Both times after filtering washing and drying the MF did not detonate. Has anyone had the same disappointing results? What could have possibly gone wrong?

[tintinteslacoil]

I tried purifying some mercury fulminate by the ammonium hydroxide/acetic acid method as mentioned, and it ruined it. I got a fluffy grey ball that wouldn't explode. I had made it by the Army's Improvised Munitions handbook, and should have used it as-is. What a waste of Mg.

[truonggiang_male90]

This's my video i cacthed at home, MF synthesis, I used Hg metal. 68% HNO3 and 98% alcohol, it worked very well, U can see the reaction in my video
http://www.youtube.com/watch?v=c2OWP4pTCog

[The_Duke]

Your making MF on a chair, in your house, with no fume hood, while not wearing socks and shoes... :eek:

I'll bet your mother wasn't too happy about all the acid splashes on her floor and good dinner chair. :p

Next time use a flask outside while wearing shoes and pants (not shorts!) or someday you will regret not doing so, this much is certain.

[Charles Owlen Picket]

You won't get a quality result if you do not use ethyl alcohol......the consumable variety.

If you are using other types of supposed EtOH then you will be disappointed every time. Use REAL ethyl alcohol such as EverClear.

[tranquillity]

I recently made some MF. For some reason the 2.9g of mercury took almost an hour to dissolve. After the synth proceeded as normal. I got 2.4g of very fine grey crystals after recrystallization which is a somewhat dissapointing 58% yeild. This could be attributed to the fact i used methylated spirits instead of pure ethanol or a large amount of product remained in solution after recrystallization.

[Charles Owlen Picket]

Here are some time honored facts about MF from industrial sources within the US when production was a daily affair...*

1.) -=Ethanol=-, the consumable variety, was used. NOT rubbing alcohol or methanol or even denatured alcohol....but ethanol at the standard 95%.

2.) The Hg was left to stand in the acid at minimum 18 hours to achieve a degree of free mercuric nitrate; this is very important for yield volume as it's the level of that precursor that determines what is actually acted upon in the fulmination process.

3.) The actual shape of the reaction vessel has a bearing on the process and the foaming should be encouraged to wash into itself (refluxing) so as to maintain a consistent level of free mercury while the reaction takes place.

Those are the hard basics; if they are maintained the reaction and yield level is both consistent and high quality. Fulminates have a sort of "art" to their lab..... It's a rather finicky synthesis & those are pivotal areas....

* A.G. Griffin & Sons. 1903, Austin Powder Co.

[sagv]

I was thinking of making mercury fulminate however obtaining sufficient mercury was impossible.
However I managed to pick 1/2 kg of mercuric chloride and 1 kg of silver nitrate from my college lab. Now considering the low solubility of silver chloride, it seems to be very simple to obtain mercury nitrate from them by a simple double decomposition. But can this mercuric nitrate be used to make the fulminate by adding it to ethanol and nitric acid or is it necessary that the mercury nitrate be generated in situ ?
Also even after the silver chloride precipitates some amount of silver will be present in the solution. So will any silver fulminate form and make the mercury fulminate unstable or will the synthesis work ?

[tranquillity]

Any silver remaining will form incredibly unstable silver fulminate which you obviously dont want. Instead try reacting your mercuric chloride with sodium carbonate in solution and mercuric carbonate should precipitate this can then be dissolved in nitric acid releasing CO2 and giving you Hg(NO3)2.

Take care with all that mercury as it is incredibly toxic made even worse by how soluble the chloride is.

[Charles Owlen Picket]

The mercuric nitrate may actually be ideal for your efforts. As I am sure you know of the toxicity issues I won't belabor them at all. The methods to utilize an existing nitrate is so simple that the resultant fulminate will be of a very high quality.

Through a molar ratio dissolve the HgNO3 in a 1:3 level of 70% HNO3, allow this to remain in solution for at least 6 hours with no shaking (there are reasons for this that are involved in the precipitating-fulminating process). Introduce your ethanol at a level of 240ml:200ml acid to ethanol. Make sure your reaction vessel (under a hood or out of doors) is large enough and "tall walled" enough to cope with the vigorous reaction.

Realistically, if you do use a hood make sure that the thing is strong enough to pull all the smoke from a burning newspaper.....as the level of reactants in the atmosphere are heavy and the majority of hoods just aren't up to the task. Out-of-doors may be best.

I have seen the HgNO3 process work quite well.The resultant product is quite clean & well formed.
Silver fulminate is not unstable. It is sensitive. If you have an understanding for the level of sensitivity evolved silver fulminate is akin to any other primary of that level of sensitivity. [...If you do not fully appreciate the issues with ANY energetic material: then the inherent dangers are more acute.] And I'm pretty sure you know all of this.

[lucas]

It wouldn't hurt for me to state that it is best, nay essential, to add the concentrated nitric acid solution to the concentrated ethanol solution. Concentrated nitric can oxidise ethanol so quickly it can boil over nastily if ethanol is poured into it under the wrong conditions.

It's analogous to adding concentrated acids to water and vice versa.

The only time I have witnessed immediate violence of this reaction was when ethanol, 90 - 95% was added to nitric acid, 70%. The same batch of nitric and ethanol combined the other way were much better behaved.

[al93535]

In my attempts to produce MF I found a few strange things.

I did 4 synthesis's, two of which failed and I obtained a white fluffy semi-sparkling powder, and two of which succeeded with low yields.

I used commercial triple distilled Mercury, freshly distilled HNO3 that was diluted with distilled water, and a new bottle of everclear.

The two times the batch failed I see from my notes that the mercury dissolved rapidly within 3 minutes. Also the mercury nitrate acid solution sat for some time. The first time for about 3 hours, and the second about 12. Even with strong heating the batch failed and I obtained the white powder, which I assume is either mercurous or mercuric nitrate.

I followed the same set up and procedure each time with only the above mentioned differences, except for slight differences in amounts.

When I did get the proper reaction it proceeded exactly as Rosco's did above. A steady effervescence and a calm reaction.

Here is my latest batch:

3.6 grams mercury
25.2 ml HNO3 - 7.5 ml distilled H2O and 17.6 ml 95-99% HNO3.
Diluting the acid warmed it to 36 degrees. I chilled the acid to 15 degrees before adding the Hg.

1:30- adding the Hg to the acid.

1:40- Heated to 20 degrees to speed the dissolving of the mercury.

1:52- All Hg dissolved. 52.5 ml everclear heated to 55 degrees.

1:57- Hg nitrate/acid poured into alcohol.

2:00- Placed the beaker on the hotplate to help kickstart the reaction.

2:02- heavy dense white fumes noticed.

2:06- Steady light boiling and dense white fumes, more of an effervescence like Rosco mentioned. There is nothing violent and no frothing at all. Solution turns grayish.

2:10- Tan precipitate accumulating at the bottom of the beaker. It seems like the crystals are the seeds for the boiling. Solution clears up, and appears a very light tan.

2:26- Reaction stops.

I decanted, filtered washed and dried the MF. I got a yield of 47.9%, 2.45 grams of light tan product. This seems like a bad yield, my first yield was 38%.

I would have thought a better yield was due after reading your guys comments about heating the vessel quickly, pre-warming the reactants and using pure ethanol.

Does anyone have information of how to improve the yield? I suppose I can leave the beaker on the hotplate and try to drive it hotter.

Also, does anyone have any ideas about the failed reactions, and what the white powder might be.

Picture of .5 grams of the MF http://www.roguesci.org/theforum/attachment.php?attachmentid=990&d=1226802359

[al93535]

I cannot edit my previous post, so I add another for a question.

I have searched and searched for incompatibilities with fulminate. The best I have found is:

http://cameochemicals.noaa.gov/chemical/2020

It says nothing about aluminum. Seeing as how I am using aluminum for my caps I would like to know. It also states copper is incompatible, yet Nobel used copper caps!

So does anyone have any reliable information about fulminates and metal incompatibilities? Specifically aluminum.

[Lewis]

Any unreacted mercury in your fulminate will form an amalgam with the Al. May not be a problem if you use them soon enough, but small amounts of Hg have been known to "eat through" large amounts of aluminum.

Probably won't have an effect on the stability of the explosive, but something to keep in mind regardless.

[Alexires]

You could prevent this by using an excess of everything but Hg to try and ensure the reaction is pushed to the products side.

Otherwise just wrap the inside of the container with something inert (Gladwrap would do) to prevent contact.

[Hinckleyforpresident]

Unreacted Hg (and many other contaminants) could be removed by recrystallization.

[al93535]

Yes, I did read about the mercury going though a lot of aluminum.
I would like them to be storage stable for at least 6 months. Perhaps I can coat the inside with a thin layer of NC lacquer or some other varnish or lacquer.
I tried a drinking straw, but they were either slightly too small in diameter or way too large. I think a coating is the best way to go.

I am going to order some 35% ammonia solution from a chem supplier as soon as I get my first order through. When I do get some, I just might have to go that route Hinckley. Its always better to be safe, and have a pure product to boot.

[FUTI]

No NC lacquer won't work. Plastic film coated or lacquered tubes made of Al are usually tested for coating uniformity by pouring mercury-chloride solution inside, and if that tube don't look good after some set time you don't wish to use that lot of tubes for some purposes.