APO
National Hazard
Posts: 627
Registered: 28-12-2012
Location: China Lake
Member Is Offline
Mood: Refluxing
|
|
Simple potassium fulminate synthesis
can I add potassium metal to fuming nitric acid and then add ethanol to make potassium fulminate?
|
|
|
DraconicAcid
International Hazard
Posts: 4298
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
Quote: Originally posted by APO  | | can I add potassium metal to fuming nitric acid and then add ethanol to make potassium fulminate? |
I have added potassium metal to fuming nitric acid before. You get a lovely purple flame for about three seconds before the entire apparatus
evaporates.
To answer your question, probably not.
|
|
|
Adas
National Hazard
Posts: 711
Registered: 21-9-2011
Location: Slovakia
Member Is Offline
Mood: Sensitive to shock and friction
|
|
| Quote: Originally posted by DraconicAcid | I have added potassium metal to fuming nitric acid before. You get a lovely purple flame for about three seconds before the entire apparatus
evaporates.
To answer your question, probably not. |
EPIC WIN 
Rest In Pieces!
|
|
|
Ral123
National Hazard
Posts: 735
Registered: 31-12-2011
Member Is Offline
Mood: No Mood
|
|
I have a video of magnesium in WFNA. It's literally my hottest experiment But
you'd be right to suggest adding EtNO3 just in case
|
|
|
APO
National Hazard
Posts: 627
Registered: 28-12-2012
Location: China Lake
Member Is Offline
Mood: Refluxing
|
|
Adding potassium hydroxide to the nitric acid and then ethanol?
|
|
|
Motherload
Hazard to Others
Posts: 245
Registered: 12-8-2012
Location: Sewer
Member Is Offline
Mood: Shitty
|
|
The only fulminates that can be made .... to the best of my knowledge .... via the Metal + HNO3 + EtOH are Mercury and Silver.
All other fulminates have to be derived from these.
By Adding KOH to HNO3 and EtOH .... you'll just end up with a really hot alcoholic solution of KNO3 with a lot of KNO3 ppt.
Highly reactive metals DO NOT like H2O let alone WFNA.
DO NOT try this at home !
[Edited on 15-2-2013 by Motherload]
"Chance favours the prepared mind"
"Fuck It !! We'll do it live !!"
|
|
|
The_Davster
A pnictogen
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
| Quote: Originally posted by Motherload | The only fulminates that can be made .... to the best of my knowledge .... via the Metal + HNO3 + EtOH are Mercury and Silver.
All other fulminates have to be derived from these.
|
yep.
make silver or hg fulminate and react it with k amalgam to get k-fulminate.
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by Motherload | The only fulminates that can be made .... to the best of my knowledge .... via the Metal + HNO3 + EtOH are Mercury and Silver.
All other fulminates have to be derived from these. |
As long as the resulting metal fulminate is insoluble and precipitates out before it can be further oxidized. The reaction also cannot contain any
copper, since this poisons the reaction (it is thought that the fulminate proceeds through the transient formation of hydroxylamine, and that the
copper catalyzes the decomposition of this intermediate before it can condense into fulminate).
I believe the fulminate group is considered a "pseudohalogen", as such it should form insoluble precipitates with any transition metal that also
precipitates out with chloride ( Pb, Ag, Hg ).
Copper fulminate does exist, not surprising since Cu(I) chloride is insoluble, but cannot be made directly.
I have read sources suggesting the possibility of dehydrating nitromethane into fulminic acid. Production of actual fulminates directly from
nitromethane may be possible.
One source states that the dehydration of nitroethane, using phenyl isocyanate and triethylamine, yields acetonitrile oxide, CH3CNO
Thermal dehydrochlorination of a hydroximoyl chlorides yields nitrile oxides.
RCCl=NOH (heat, minus HCl) --> RCNO
(phosgene oxime Cl2C=NOH might be a suitable reactant in the above reaction, it can be produced by hypochlorite chlorination of nitromethane to
chloropicrin, followed by reduction with Sn/HCl, but I am unsure whether the reaction would work if the R is a hydrogen atom)
[Edited on 16-3-2013 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
AJKOER
Radically Dubious
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
More on Fulminic Acid, CNOH per Atomistry.com (http://carbon.atomistry.com/fulminic_acid.html ) to quote:
"Fulminic Acid, CNOH, formed the subject of the first investigation of isomerism by Liebig and Wohler, since its salts were found to possess an
identical qualitative and quantitative composition with those of cyanic acid. The mercuric salt of this acid is prepared by adding alcohol to a
solution of mercury in excess of nitric acid; and the acid itself, which is exceedingly unstable, is obtained in ethereal solution when its mercuric
salt, suspended in ether, is decomposed with dry hydrogen chloride. Fulminic acid is also formed and its silver salt obtained when
aminomethylnitrosolic acid decomposes in presence of nitric acid and silver nitrate:
ONC(NH2):N-OH → H2O + N2 + C:N-OH.
Methenylamino-oxime, when treated with nitric acid and silver nitrate, also yields silver fulminate:
CH(NH2):N-OH → NH3 + C:N-OH.
It has been shown by Nef and Scholl that the acid is carbyloxime, C=N-OH; Palazzo, however, regards it as tautomeric and a pseudo-acid:
HC≡N=O → C=N-OH.
It is named fulminic acid on account of its explosive properties, and its mercuric salt is much employed for the manufacture of detonators and
explosive caps. In accordance with its explosive character, this acid is endothermic, the mercuric salt liberating 116,000 calories per gram molecule
on its decomposition into mercury, nitrogen, and carbon monoxide. By the action of concentrated hydrochloric acid on mercuric fulminate the oxime of
chloroformaldehyde, , results, whilst dilute acid produces hydroxylamine and formic acid. The spontaneous polymerisation of fulminic acid yields
metafulminuric acid (isocyanuric acid), which is probably..."
-----------------------------------------
Also from Bretherick’s Handbook of Reactive Chemical Hazards, Sixth Edition, Volume 1, on Fulminic acid (Hydrogen cyanide N-oxide), page 147, to
quote:
"2. Wentrup, C. et al., Angew. Chem. (Intern. Ed.), 1979, 18, 467
It is fairly stable as an ethereal solution, but the isolated acid is explosively
unstable, and sensitive to heat, shock or friction [1]. In a new method of preparation
of the acid or its salts, pyrolysis of 4-oximato-3-substituted-isoxazol-5(4H)-ones
or their metal salts must be conducted with extreme care under high vacuum to
prevent explosive decomposition [2]."
Also, same source:
"Copper(II) fulminate
[22620-90-2] C2CuN2O2
Cu(CN->O)2"
Other listed fulminates include:
"0537. Sodium fulminate
[15736-98-8] CNNaO
NaC≡N->O
Smith, 1966, Vol. 2, 99
Even sodium fulminate detonates when touched lightly with a glass rod"
"0539. Thallium fulminate
[20991-79-1] CNOTl
TlC≡N->O
Boddington, T. et al., Trans. Faraday Soc., 1969, 65, 509
Explosive, even more shock- and heat-sensitive than mercury(I) fulminate."
"0589. Cadmium fulminate
[42294-95-6] C2CdN2O2
Cd(C≡N->O)2
It is a moderately endothermic compound (1H°f (s) C163.2 kJ/mol, 0.80 kJ/g)."
"Mercury fulminate, readily formed by interaction of mercury(II) nitrate, nitric
acid and ethanol, is endothermic (1H°f (s) C267.7 kJ/mol, 0.94 kJ/g) and was a
very widely used detonator. It may be initiated when dry by flame, heat, impact,
friction or intense radiation. Contact with sulfuric acid causes explosion [1]. The
effects of impurities on the preparation and decomposition of the salt have been
described [2]."
"Dimethylthallium fulminate
[ ] C3H6NOTl
Me2TlC≡N-> O
Beck, W. et al., J. Organomet. Chem., 1965, 3, 55
Highly explosive, unlike the diphenyl analogue."
"Tripropyllead fulminate
[43135-83-7] C10H21NOPb
Pr3PbC≡N--> O
Houben-Weyl, 1975, Vol. 13.3, 101
An extremely explosive solid."
------------------------------------------
Another good source "FULMINATES: A LITERATURE SURVEY" (http://www.dtic.mil/dtic/tr/fulltext/u2/625397.pdf ) to quote:
"The cadmium, thallous, and cuprous salts of fulminic acid were obtained by reaction of either mercuric or silver fulminate with the amalgam of the
particular metal, in dry methanol and a hydrogen atmosphere, the products being precipitated out with ether (42,43). Cd fulminate is stable when dry
but readily decomposes in water and is sensitive to heat or shock. The Cu(I) salt is insoluble in water and also highly explosive. Thallous fulminate
is sensitive to moisture and light and susceptible to heat and shock but does not explode
violently. Langhans (44) reviewed tho preparation of fulminates (and also noted the effect of moist mercury fulminate upon metals). The fulminates of
sodium, potassium, calcium, strontium, and barium were similarly prepared by reaction of the appropriate amalgam with mercuric fulminate, in
BaO-distilled methanol (42,45). Shaking of the reaction medium was continued until Hg was no longer detected with SnCe 2 . Temperatures from -50 to
-150 C were ured to avoid polymerization. The solutions were filtered into cold, dry ether in an oxygen-free atmosphere. The alkaline earth fulminates
separated with 1 mole of methanol, which could not be driven off without decomposition of the salts. Both the alkali and the alkaline earth
fulminates are unstable to CO2 and moisture. Rubidium and cesium fulminates were prepared by Hackspill and Schumacher (46), and crystals, probably in
the hexagonal system, were formed by evaporation from methanol solution (47). The dry alkali fulminates detonate easily by friction or temperature
increase, and the higher the molecular weight the more violent is the detonation. Double salts of the alkali fulminates with mercuric fulminate are
even more sensitive. Complex argentofulminates such as NH4Ag(CNO) 2 and MgAg(CNO) 2 were prepared from silver fulminate and the corresponding iodide
in ether (45). Neither salt is light-sensitive; the latter detonates violently under certain conditions. Well-crystallized complexes containing 2
moles of pyridine were obtained for the fulminates of Zn, Cu(l), Ag, Cd (and Hg) by shaking mercuric fulminate in pyridine with the respective metal
amalgams....."
[Edited on 21-3-2013 by AJKOER]
|
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
