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Author: Subject: Mercury Fulminate from Mercury (II) Nitrate
jharmon12
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[*] posted on 17-4-2013 at 05:43
Mercury Fulminate from Mercury (II) Nitrate


Mercury fulminate is typically sythesized by reacting a solution of mercury (II) nitrate and about 65% nitric acid with a measured amount of warm ethanol. But is it possible to make mercury fulminate by taking dry, crystalline mercury (II) nitrate, dissolving it in water, and adding warm ethanol?

I ask because I am not sure that the nitric acid that is left over in solution when making your own mercury (II) nitrate is necessary for the fulminate's formation. In other words, does the left over active acid in the mercury (II) nitrate solution contribute to the formation of mercury fulminate when warm ethanol is added?

Thanks.
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[*] posted on 17-4-2013 at 09:24


I believe it is required for the oxidation of ethanol.
IIRC ... White fumes were evolved during the exothermic reaction and were flammable.
That is some partially oxidized byproduct of ethanol.
I can't get pure ethanol here. It's always denatured with methanol.
I have never tried denatured .... But would it work ?




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[*] posted on 17-4-2013 at 09:37


Hi Motherload. I have only made merc. fulm. using 95% pure ethanol/water. I have been told that anything but ethanol will not work. But if you have some mercury, try nitrating 5 grams of it to test your denatured ethanol and see if it works. Once you add the acid to the denatured, stand back and watch from a safe distance. No telling what it might do because you never really know what all they put in denatured alcohol. If it works, then great. If it doesn't work and makes nothing, then you know. If it blows up or catches fire, at least you will be safely away from it and know never to do that again....
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[*] posted on 17-4-2013 at 10:01


i can say that i have been dissapointed abit with some 93% denatured ethanol
apparently doesnt react with 62% HNO3, which is plenty concentration for the purpose..
i have accidentally purified some of this, judging i have at least 99% purity ethanol
think i will try on mL - mL scale, but i didnt see any reaction of HNO3 and denatured ethanol.. i take the 7% as being methanol and denatonium benzoate




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[*] posted on 17-4-2013 at 10:28


95% Denatured Ethanol with 70% HNO3 is guaranteed to work if you have the correct proportions. When nitrating the Hg use an excess of the nitric acid and there will be enough left over, thus not limiting the reaction. Sometimes it will start on its own, sometimes you have to add heat. What you can do to prevent having to heat the entire mixture(scary), is heat the denatured ethanol until it steams then add in the HNO3 and mercuric nitrate.

Yield is better with 100% ethanol but it seems like an expensive waste to me.




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[*] posted on 17-4-2013 at 12:34


I had the issue of the material not reacting the first time I did it. Going forward, after the mercury is dissolved in a graduated cylinder, I always pre-heat the alcohol, take it off the heat source, and then dump the acid/Hg in. I use a florence flask to hold the alcohol to heat it in, and add the acid mix directly to this flask. The reaction will start in two minutes or so, almost with 100% consistency. The yield from 10 grams of mercury is always 12.5 grams of mercury fulminate, because I always do it the same way.

But it seems that my process uses an excess of nitric, in my opinion. It uses much more nitric than is necessary to convert the mercury to mercury (II) nitrate. That is the reason I asked my original question, which is why use so much nitric if the nitric is simply used to convert the mercury? It must be used in the second part (alcohol part) of the reaction, I suppose, but noone has really said, and I cannot see any reason for what seems like excess nitric from the research I have done.

Thanks, Joel
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[*] posted on 17-4-2013 at 12:54


anyways people..
does anybody in here know what the specific gasses formed are?
i read theyre flammable, but also know theyre toxic as i read that through a few synthesis vids.
can this gas be neutralized or lead through some solution to remove it?
with NO2 it could be lead into NH4OH solution and it could easily be performed inside




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
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[*] posted on 17-4-2013 at 13:02


I read somewhere that the gasses can be vented underwater and this will eliminate most of the gas vapor, but you should still do it outside.
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[*] posted on 17-4-2013 at 13:13


Whenever I perform this reaction there is only a few seconds before it starts boiling and producing major fumes. I always hear other people saying it takes in between 2 and 10 minutes to start. What is the reason for this?

http://www.youtube.com/watch?v=zU6qgzgmyyU

Fixed broken link

[Edited on 4-18-2013 by chemcam]




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[*] posted on 17-4-2013 at 15:46


I would suspect acetaldehyde to be one of the gases/vapor in the fumes.



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[*] posted on 18-4-2013 at 05:25


If you start with warm alcohol, it will start immediately. The friends of mine that have done it always started with room temp alcohol so they had to wait around for it to start. I warmed my alcohol and that makes all the difference in the world.
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[*] posted on 18-4-2013 at 07:21


Drop a few tiny crystals of sodium or potassium nitrite into the mixture and the reaction will start, regardless of the temperature of the alcohol.


[Edited on 18-4-2013 by Bert]




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[*] posted on 24-2-2014 at 14:10


I have heard that dropping a tiny bit of starch in the reaction mixture will also initiate the reaction. The bit of starch reacts with the HNO3 resulting in the formation of nitric oxides, which is what facilitates the reaction. I know if the alcohol is added right after the mercury has dissolved the reaction is usually almost immediate and very violent and fast. This is because the nitric oxides are still present from the Hg & HNO3 reaction. If, however, one waits a while for the nitric oxides to dissipate, the reaction can be very sluggish to start and take a long time to complete. I had a 5g batch one day jump right out of the beaker at me, because I added the mercury nitrate-HNO3 mixture to the ethanol right after the mercury had finished dissolving and there was a lot of nitric oxides present in the mixture. I think sunlight will also cause nitric oxides to form, in the mixture, by decomposing HNO3, but sunlight should be avoided for obvious reasons.




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[*] posted on 26-9-2015 at 18:03


Not sure, but one time I had a small quantity of pure mercury nitrate in distilled water (excess nitric removed by by repeated evaporations with distilled water), then added ethanol and heated.

Two substances were generated. One was a crystal clear, needle shaped salt (around 0.5cm length). This material, when heated on a hot plate, simply decomposed into an orange red powder. I never thought to expose it to shock or friction at the time because I was attempting to make something else.
https://upload.wikimedia.org/wikipedia/commons/d/d3/Mercuryf... It looked like this stuff so I'm guessing it was mercury fulminate. Oops.

The other substance was a chalky, off white looking material. I'm not sure what this was since oxides of Hg are red or orange. If you take elemental Hg and add H2O2, you get a material which looks identical, but I'm not sure if it's the same stuff. Might be a result of a reaction limited by the amount of nitrate, but I'm not sure.

[Edited on 27-9-2015 by crestind]
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[*] posted on 15-11-2015 at 07:38


Does anyone here know a critical diameter value for mercury fulminate?
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[*] posted on 16-11-2015 at 15:36


Lately I have retried Hg fulminate synthesis from Hg/ HNO3 and denaturated alcohol (and with 96% pure ethanol also).

I did observe the special NxOy cloud above my Hg/HNO3 and the foaming/sparkling with apple smell like in my memories of first trials but less strong and this time running too smoothly I had a sudden crash out of heavy and voluminous needle like white cristals...like crestind exposed hereabove...I suspect that if heat doesn't go high enough then Hg(NO3)2 will precipitate from the ethanol...

This crash out also happened from my Hg/HNO3 mix (5N and then 69%) ...while bubbling NxOy red fumes suddently I ended up with big square cristals floating into my HNO3 above my Hg and some bubbles trapped inside a yellow crust.

I will use the Hg(NO3)2 to make some Hg carbide by bubbling acetylen through it, some Hg fulminate and some Hg nitranilate ...because I also did some chloranile from hydroquinone, HNO3 and HCl...the later when boiled with NaNO2 and concentrated do form easily Na nitranilate (disodium salt of 2,5-dihydroxy-3,6-dinitro-paraquinone) that forms sensitive primary heavy salts (Pb, Ag, Hg)




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[*] posted on 10-1-2016 at 19:33


Quote: Originally posted by Bert  
Drop a few tiny crystals of sodium or potassium nitrite into the mixture and the reaction will start, regardless of the temperature of the alcohol.


[Edited on 18-4-2013 by Bert]


Great tip. Works out very well.

Little off topic, Im thinking in recover any Hg2+ left in all used liquids, combining it, neutralizing the acid then treating with some salt to ppt out the Hg as a insoluble salt. I was wondering if treating the basified expent liquids with sodium polysulfide solution (made from NaOH and sulfur) would result in HgS. Does anyone knows if that could work?




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[*] posted on 11-1-2016 at 03:36


I used room temp. 98% EtOH, brought from a Liquor Store. The HNO3 was varm from the reaction with the one gram of Hg. The reaction started in about 10-20 sec. and the smell was rather sweet. The whole reaction was very exothermic and quite scary.
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[*] posted on 11-1-2016 at 04:26


Sorry to introduce a discordant note . . . I 'went off' MF quite a few years ago ─ I used to make small pyro squibs for the garden (about half a gram in duct-tape with visco), which went with a satisfying "thump" and flash, visible in full sunlight.

The children loved them but the large quantities of mercuric residues on the grass bothered me greatly as I have cats and many other animals visit from time to time . . .

I'd later find myself carefully (and tediously) brushing all residues off the grass into the soil beneath!

And fuck it, silver azide, greener though it is, never just deflagrates at all.

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[*] posted on 11-1-2016 at 09:06


Quote: Originally posted by Aqua_Fortis_100%  

Little off topic, Im thinking in recover any Hg2+ left in all used liquids, combining it, neutralizing the acid then treating with some salt to ppt out the Hg as a insoluble salt. I was wondering if treating the basified expent liquids with sodium polysulfide solution (made from NaOH and sulfur) would result in HgS. Does anyone knows if that could work?

If you use basified liquids, you will first have precipitation of Hg oxydes and hydroxydes...
With polysulfide, you may get complexation see tread by Magpie to extract Hg from Hg ores...

This document may help you: solubility of Hg and Hg salts in water and aqueous solutions http://www.nist.gov/data/PDFfiles/jpcrd274.pdf
I would choose Na2CO3 to precipitate HgCO3...more convernient for further use to avoid anionic polution...since H2CO3 goes out of the system upon contact with an acid...




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[*] posted on 11-1-2016 at 09:58


Quote: Originally posted by hissingnoise  
Sorry to introduce a discordant note . . . I 'went off' MF quite a few years ago ─ I used to make small pyro squibs for the garden (about half a gram in duct-tape with visco), which went with a satisfying "thump" and flash, visible in full sunlight.

The children loved them but the large quantities of mercuric residues on the grass bothered me greatly as I have cats and many other animals visit from time to time . . .

I'd later find myself carefully (and tediously) brushing all residues off the grass into the soil beneath!

And fuck it, silver azide, greener though it is, never just deflagrates at all.



I like his back yard... It's exciting! (done in voice of the new "Scotty")

Whoa. There are safer flash mixes, both in handling and as far as residual contamination. Silver azide is the only primary which I have had an accidental explosion from during handling due to static electricity. Not a great choice for quiet back yard enjoyment there either.

Some decades back, I found a 4oz bottle of reagent grade red Mercuric oxide in my dad's office while cleaning out after he died. Thanks dad... I think he was doing something less spectacular with it, related to doping a glaze on ceramics for cathode use? A 100 gram bottle of photographic grade Silver nitrate came out of that box of goodies too, I can barely remember him painting various mixes on ceramics and kiln firing. He let US make and glaze a few small clay projects too, before returning the kiln to the university shop. Good times.

The HgO digested slowly in 65% nitric acid with little heat, no fuss, muss or NOx, requiring the addition of a pinch of nitrite (or starch) to kick off the reaction with ethanol. The fulminate produced did not release visible tiny beads of metallic Mercury when dissolved in 30% ammonia for filtering and purification as the fulminate produced from mercury metal often did. Can't find the lab notes on relative efficiency.




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2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.

Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).

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[*] posted on 11-1-2016 at 11:49


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I like his back yard... It's exciting!


Well, er, geee thanks, Bert! :o

But it's strictly pussy for me . . . sorry . . . :D

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