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Author: Subject: Silver / Copper Nitride
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[*] posted on 19-3-2006 at 11:49


Are you sure about that. I have a book, which states that fulminating silver is a compound of indefinite composition, which can be described as a mix of silver-ammine complexes, with oxygen included as well. The following site gives a net-formula, which also is not correct, formally speaking, but it takes into account the presence of the oxide.

http://www.websters-online-dictionary.org/Fu/Fulminating+sil...

A real accurate formula, giving its structure, cannot be given.

Indeed, fulminating silver may contain some Ag3N, but it definitely is a much more complicated compound.




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[*] posted on 19-3-2006 at 12:23


Actually, I was under the impression that it was mostly Ag3N with Ag2NH and AgNH2 in there as well, the presence of oxygen in there is something I have not heard mentioned before.

I looked some relavent things up in Federoff, and you are right, there can be oxygen in there as well. See the attachments.

I have a feeling the precise composition of fulminating silver would depend on very small procedural modifications and that one batch could be radically different from others in terms of composition and sensitivity.

fulminating silver-federoff2.JPG - 93kB




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[*] posted on 19-3-2006 at 12:24


Another

EDIT: I have my doubts about your websters link, given its formula for silver fulminate(unless theres been some sort of development here which I was unaware of?) and it implies silver fulminate is the same as fulminating silver despite listing different formulas.

[Edited on 19-3-2006 by rogue chemist]

fulminating silver-federoff.JPG - 41kB




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[*] posted on 19-3-2006 at 19:28


I don't know the exact composition, but would suspect that there is more than just nigrogen involved. It does have a faint odor when detonated - not that of ammonia but I doubt silver alone would have an odor.

Anyway, it is an interesting compound. I've had some stored under water for about a month, and it is no longer reactive. I also let some dry (small amounts) originally and today I find this it still detonates.

Supposedly fulminating copper can be formed by adding a copper salt to fulminating silver. This seems suspicious to me given the low soluability of fulminating silver, which does not appear to dissolve at all when I was it after preparation.

Sometime I want to make fulminating gold. But I have not seen gold in tiny quantities on E-Bay in a while, and I'm not willing to pay the price for gold chloride sold by alternative photography suppliers. I have everything needed to make fulminating mercury, but I'm not going to make something that produces tindy droplets or vapor of mercury as the expected result of detonation.
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[*] posted on 20-3-2006 at 14:23


Many 1/4, 1/2, and 1 gram pieces of bullion are sold regularly. Just look in the 'coins' section.



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[*] posted on 21-3-2006 at 14:42


Quote:
Originally posted by rogue chemist
Another

EDIT: I have my doubts about your websters link, given its formula for silver fulminate(unless theres been some sort of development here which I was unaware of?) and it implies silver fulminate is the same as fulminating silver despite listing different formulas.

[Edited on 19-3-2006 by rogue chemist]

The link states things a little bit unclear, by putting the section about silver fulminate under the head of fulminating silver. But two definitely different compounds are mentioned. Silver fulminate is a white, well-defined, white salt. It also is described as a white solid on the link, and it has a formula with C, and without H. Fulminating silver, on the other hand, is described as a black solid.

Whatever the precise composition, it is quite complicated and there are many sources, which tell different things. So, it indeed contains Ag3N, but probably also AgNH2, Ag2O, NH3, and who knows what more.

There are quite a lot of this kind of ill-defined compounds. Another well-known example is "ferric ammonium citrate", which contains Fe(3+), NH3, NH4(+), H2O, citrate ion and a lot of combinations of these.




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[*] posted on 21-3-2006 at 15:38
confused?


A Fulminate must contain CN and the way its produced is about alcohol, nitric acid and grey mercury.. Am I wrong?
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[*] posted on 22-3-2006 at 21:13


"Fulminating", or fulminate is generally an attribute given by early chemists to sensitive explosive materials, and is the root of the happy anion that we know as CNO. Davy refers to NCl3 as a 'fulminating liquid'.



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[*] posted on 23-3-2006 at 03:16


The fulminate ion is CNO-. Don't confuse this with cyanate, NCO-.

Fulminating does not mean the same thing as fulminate. Silver fulminate is AgCNO, fulminating silver is the mess we're discussing. Just wanted to clear that up.

[Edited on 23-3-2006 by neutrino]




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[*] posted on 18-4-2006 at 13:39
Fulminating Gold


I purchased 1g of gold bullion on E-Bay. I tested the purity by attempting to dissolve in 70% HNO3. As expected, no reaction. I added HCl (5 to 1 by volume). The gold dissolved over the course of a couple hours. Here is a picture of the resulting orange solution, which contains the 1g of dissoved Au. I split this into 5 parts for experiments.
<img src ="http://www.sciencemadness.org/scipics/DSC00671.jpg"></img>

I added concentrated NH4OH and obtained an orange precipitate. I treated part of this precipitate with NaOH (analogy to Ag3N preparation), and left the rest untreated. After allowing to sit for several hours and then washing the precipitate several times, here is how it looked:
<img src ="http://www.sciencemadness.org/scipics/IMG_0322.jpg"></img>

I picked up about 10mg of the precipitate using a pipette. I placed this on the sink to dry.

I also tried using only NH4OH and no NaOH (NaOH might not be required because, unlike with silver solution, the fulminating gold precipitates on adding NH4OH).

Once dry, I found the resulting explosive to be more powerful than, but considerably less sensitive than fulminating silver. When I touched it with the flame of a barbecue lighter, there was a loud pop. However, only the part of the precipitate that was touched by the flame detonated. The rest remained. I was able to get several pops by touching different parts of the precipitate with the flame. Often the flame was blown out. In addition, little pieces of the precipitate scattered nearby so that running the flame of the lighter around on the nearby surface resulted in more pops.

There was not much difference between the precipitate prepared by the two methods, either in look or activity, although I think the batch prepared using only NH4OH seemed to be a bit more uniform and powerful than the batch prepared also using NaOH.

Fulminating silver is much more sensitive. It is impossible to detonate just part of it. However, the pop is nearly as loud with just a portion of the fulminating gold detonating as when the whole 10mg or so of fulminating silver detonates. With fulminating silver, I don't see any smoke. Careful examination shows nearby small particles of something (presumably silver). With the fulminating gold, I got a faint black smoke which appears to have trouble rising very far. Presumably the particles are gold.

I'm sure the fulminating gold would all detonate at once if packed. Fulminating gold seems to be a lot safer than fulminating silver and I think would make a good novelty explosive if it were not for its high cost.

I plan on trying to form gold acetylide at some point. A search for gold acetylide on Google did find matches. It appears to be used for some types of organic chemistry, but no mention is made of whether it is explosive or not.
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[*] posted on 18-4-2006 at 14:41


Hodges, here's a short description of Gold Acetylide taken from PATR2700 vol.1. Hope this helps.

Au2C2.JPG - 71kB
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[*] posted on 19-4-2006 at 17:45


Thanks Phel.

I assume "Very sol in w" means "Very soluable in water". If so, this is going to be hard to separate, unlike silver acetylide.
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[*] posted on 19-4-2006 at 19:27


Does that mean, like calcium acetylide, it could be used to prepare acetylides, but not by being the primary source of acetylide(2-) but rather because it's soluble instead of reacting with H2O?

For that matter, why doesn't it just bubble off leaving gold [hydr]oxide and acetylene? I thought acetylide hydrolized because it's an uber weak acid. Does it coordinate?

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[*] posted on 7-7-2006 at 08:55


Has anyone tried this process for Zinc; using perhaps ZnO?



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[*] posted on 22-3-2008 at 19:53


@CPC:

Zinc would not work, because zinc nitride decomposes in water.

@everyone:

I recently found out that Longs Drugs sells speaker wire, with one side made of silver wire and the other side made of copper wire. I bought some and was wondering how to make silver oxide from silver. Should I put it in a flame, put some peroxide on it, do electrolysis, or is there some other process?




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[*] posted on 23-3-2008 at 00:02


Electrolysis would be best unless you have nitric acid.

Silver anode in a nitrate solution with good stirring should do it, doing it in a base solution may coat the anode too quick, passivating it. A nitrate solution will at least be easier to filter the oxide out of.

However I think it would be preferable to cease the discussion of the precursors for silver nitride in this thread, and put it in a new thread.




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[*] posted on 19-4-2008 at 13:59


Quote:
Originally posted by hodges
I have read that silver nitride (Ag3N) is about as easy to make as nitrogen tri-iodide and just as sensitive.


But one difference between NI3 ammoniate* and Ag3N, it can explode even under water by contact with hard objects, when dry it explodes from the slightest agitation. In air the compounds sensitivity decreases as it decomposes, and thus after about 10 days its sensitivity is said to have completley worn off. From very concentrated solutions it can explode spontaneously.

*[Note from Gmelin J, pg. 8, NI3.NH3 does explode under water or when wet if it exists in coarse aggregates. I had seen demonstrations of it when wet and figured it didn't react this way, but not necessarily].

You can reduce the explosibility of Ag3N as mentioned in Gmelin [B1] Ag, p. 143 if gelatin is added to the solution to be reacted, this is said to work as a saftey colloid. The risk of explosion is increased if during the preparation the mixture is (1) heated, (2) use of concentrated solutions, (3) unevenness in the walls of the vessels containing it.

Its explosive tendency is minimized when during its preparation NH4+ salts are added which are of oxygen containing inorganic or organic acids in aqueous solution, before the reaction with Ag2O is carried out. For this purpose such NH4+ compounds are NO3-, CO3(-2), SO4(-2), CH3CO2-, citrate and oxalate. To completley protect from the explosion of the system, 0.6 NH4+ equivalent salt per equivalent of Ag2O should be solubilized. This action is thought to be due to a inhibiting action of those compounds having a buffering effect (lowering of the pH).

Quote:
What about copper nitride - is it easily made and is it explosive?


Yes, it is explosive according to Gmelin Cu [B] p. 60, but they say Cu3N is less schock-sensitive than other nitrides citing E.C.Franklin (J.Am.Soc. 34 [1912] 1501/7, 1503). According to one observer there was no decomposition by shock, pressure or friction. It is a green or black powder, or olive-green powder that from the pressure of a polishing stone leaves behind shiny, dark, brass-yellow streaks. Another observer noted green-black for its color. At 300 deg.C. in air it decomposes to Cu and N2 under the formation of light, to other gases (CO2, NH3) first at higher temperatures. Heating in an open tube CuO or a mixture of Cu and Cu2O results. It explodes easily when heated in air.

It's quite difficult to prepare as opposed to Ag3N mixture, e.g. (1) by heating CuO or anhydrous CuSO4 with Mg3N2 which yields a yellow-green copper nitride along with Cu as a thermal decomposition product. (2) heating a mixture of fine copper powder with CaC2 in air forms some copper nitride. (3) reaction of a solution of Cu(NO3)2 in liquid NH3 with KNH2 yields an olive-green compound (likely CuNH2, copper (I) amide, also explosive), which when heated under a vacuum at 160 deg.C. releases NH3 and via Cu2NH converts to Cu3N, in total: 3 Cu(NO3)2 + 6 KNH2 = Cu3N + 6 KNO3 + 4 NH3 + 1/2 N2, etc. Its preparation by heat enough is already impractical without the necessary equipment. Water decomposes it with a strong evolution of heat, so it's not possible to prepare in aqueous solution. But the compound is said to be stable at normal temperatures in air and in a vacuum. It reacts also vigorously with acids, notably energetically with concd. H2SO4 or HNO3.

[Edited on 19-4-2008 by Schockwave]

[Edited on 19-4-2008 by Schockwave]

[Edited on 19-4-2008 by Schockwave]
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[*] posted on 18-5-2008 at 12:00


"Fulminating copper": just found this. They dissolve pure Cu in dilute HNO3 (might need some heat) and then pour in "liquid Ammonia" (likley just aqueous NH3) to get a precipitate, they dry it (with heat!) and say rubbing it causes a loud explosion. 2 grains (129.6 mg) of it over a fire for a bit is said to produce a loud explosion.
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[*] posted on 18-5-2008 at 13:43


Ins't this simply TACN?

TACN indeed is an explosive compound and it is made from a copper(II) solution with ammonia and nitrate. It is a nice deep blue compound, which pops when heated.

http://woelen.homescience.net/science/chem/compounds/tacn.ht...

<!-- bfesser_edit_tag -->[<a href="u2u.php?action=send&username=bfesser">bfesser</a>: fixed external link(s)]

[Edited on 7.1.14 by bfesser]




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[*] posted on 18-5-2008 at 14:00


I cannot see it as being anything other than the TACN. Keeping in mind the age of that book(1822 (if anyone can get me a pdf of this book, I will be indebted)) and from that age they knew of the fulminating Hg, Ag, Au made by a similar process, but however their characterization at the time may have been insufficient(they did have some awesome characterization methods, but noone may have cared enough to characterize it) so as it came from an identical synthetic route, they called it a fulminating compound.

EDIT: Also note their synthesis of 'fulminating mercury' actually gives mercury fulminate, so their terminology is simply wrong in this book.

EDIT2: Oh my...in many of their syntheses of fulminating/ fulminates they measure a complete washing of a precipitate by the wash water becoming tasteless...including for mercury fulminate:o

[Edited on 18-5-2008 by The_Davster]




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[*] posted on 18-5-2008 at 14:09


TACN is probably it. I didn't think about that. Nitric acid at varying strengths reacts differently with metals producing NOx, N2, hydroxylamine, hyponitrous acid, H2, or NH3 , so I was thinking maybe they had formed some other compound.
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[*] posted on 18-5-2008 at 14:16


Quote:
Originally posted by The_Davster
I cannot see it as being anything other than the TACN. Keeping in mind the age of that book(1822 (if anyone can get me a pdf of this book, I will be indebted)) and from that age they knew of the fulminating Hg, Ag, Au made by a similar process, but however their characterization at the time may have been insufficient(they did have some awesome characterization methods, but noone may have cared enough to characterize it) so as it came from an identical synthetic route, they called it a fulminating compound.

EDIT: Also note their synthesis of 'fulminating mercury' actually gives mercury fulminate, so their terminology is simply wrong in this book.

EDIT2: Oh my...in many of their syntheses of fulminating/ fulminates they measure a complete washing of a precipitate by the wash water becoming tasteless...including for mercury fulminate:o

[Edited on 18-5-2008 by The_Davster]


Copper fulminate preparations are found in various places: Powerlabs indicates that a procedure for making Silver, Mercury and Copper fulmate appears here:
http://www.powerlabs.org/chemlabs/fulminate.htm

Also, as for it being TACN, it seems that the preparation involves heating the precursors to 200C. I'm not sure of the decomposition temperature of TACN, however it is likely less than 200C. (The book also mentions using "liquid ammonia," which doesn’t seem to be likely given the 200C evaporation until "wet"--it is likely Ammonium Hydroxide.)




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[*] posted on 18-5-2008 at 14:26


While Barros's powerlabs does imply that copper fulminate can be made in the same manner as Ag and Hg versions, this is wrong. Copper fulminate cannot be formed in the same way. In addition he does not provide a source or experiment to back up his claim. Copper fulminate can only be formed from other fulminates; metathesis from sodium fulminate or redox from the silver or Hg salt.

Also, I believe they are using the Fahrenheit scale, so 200F is less than 100C




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[*] posted on 21-5-2008 at 14:19


Quote:
Originally posted by The_Davster
While Barros's powerlabs does imply that copper fulminate can be made in the same manner as Ag and Hg versions, this is wrong. Copper fulminate cannot be formed in the same way. In addition he does not provide a source or experiment to back up his claim. Copper fulminate can only be formed from other fulminates; metathesis from sodium fulminate or redox from the silver or Hg salt.


Copper fulminate is easily oxidized and doesn't form from a copper and acid attempt. Gmelin (Cu [B] 867) says CuONC is stable in a dry atmosphere but oxidizes easily in moist air, though due to its insolubility it is barely hydrolyzed. The procedure they give for its preparation is done under a H2 atmosphere. It is bright-grey with a green tint and is about as sensitive to heat as Cd and Hg fulminate, but it is less sensitive to impact than those.

It'd be interesting to know which metals besides Ag and Hg do give fulminates. There were some experimentors who tried to get fulminates with other metals in the same manner as Hg and Ag, IIRC metals like manganese, cobalt, copper, zinc, tin, and cadmium but without success.

The website used concentrated acid, it's possible as Liebig did (Ann. Pharm. 95, 284) to obtain Hg(ONC)2 using a subconcentrated acid (56% HNO3): 3 pts Hg dissolved in 36 pts HNO3 (sp. gr. = 1.34 to 1.345) in a wide, large flask so nitrous acid remains in it. Then added this to 17 pts of alcohol which is of 90 to 92 degrees (density) in another vessel, then quickly poured this back into the big flask and swished it around to absorb the nitrous acid. In 5 to 10 minutes gas bubbles form, and then this is further agitated gently and then it turns black with some separation of Hg metal, then a very violent reaction occurs alongside thick white vapors and nitrogen oxides, this can be moderated by adding gradually 17 more pts of the same alcohol. The black goes away and mercury fulminate will start to separate out. The result is also no remaining mercury is said to be in solution.

Howard also used an even lesser concentration, an acid with a d = 1.30 (49%): 1 pt Hg in 7.5 pts HNO3 and mixed with 10 pts alcohol (d = 0.85, 75-77%) and then heated the mixture until it frothed, with the crystals forming on cooling, filtered, washed and dried yielding 1.20 to 1.32 pts Hg(ONC)2.

But one does not need nitric acid for fulminates as it is on that webpage, according to Chemisches Zentralblatt 70 (1884), p. 68, Liebig made AgONC by leading nitrous acid into alcoholic AgNO3. This also does not cause a boiling of the solution. The authors of that article also repeated Liebig’s results with success, but they said there was alongside the fulminate traces of another organic silver salt.

And in place of alcohol with the acid it's possible to use some other organic compounds with at least two carbon atoms, namely lignon, dimethyl- or diethylacetal, acetaldehyde, paraldehyde, metaldehyde, and malonic acid as mentioned in Initialexplosivstoffe by R. Escales, A. Stettbacher, p. 103 and COPAE p. 407.

Quote:
Originally posted by ShadowWarrior4444 Also, as for it being TACN, it seems that the preparation involves heating the precursors to 200C. I'm not sure of the decomposition temperature of TACN, however it is likely less than 200C. (The book also mentions using "liquid ammonia," which doesn’t seem to be likely given the 200C evaporation until "wet"--it is likely Ammonium Hydroxide.)


Close; from Gmelin (Cu [B] 181): TACN melts around 210ºC (decomposing), the melt for a short time develops some gas bubbles and then decomposes explosively at 212ºC.

[Edited on 22-5-2008 by Schockwave]
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[*] posted on 18-5-2011 at 14:52


What about Lead Nitride, Pb3N2, not to be confused with Lead Azide, Pb(N3)2?

Properties?

Lead Oxide also reacts with KOH forming a complex (hydroxoplumbates):

PbO + H2O + KOH = K[Pb(OH)3]

With ammonia, 3 possible reactions:

PbO + 3 NH3 + H2O ==> [Pb(NH3)3](OH)2
or:
3 PbO + 2 NH3 ==> N2 + 3 H2O + 3 Pb
or:
3 PbO + 2 NH3 ==> Pb3N2 + 3 H2O

as compared to Silver Oxide, which forms Diamine Silver Hydroxide:

Ag2O +3 NH4OH = 2 [Ag(NH3)2]OH + H2O

which decomposes on standing to Ag3N,
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