Pages:
1
2
3 |
KABOOOM(pyrojustforfun)
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
I've read in some books that excess nitric must be used.
I think if there's excess alcohol, the nitrous acid (from oxidation of ethanol with nitric acid to acetaldehyde) will react with the excess
alcohol forming ethyl nitrite instead of reacting with acetaldehyde (to form isonitrosoacetaldehyde/glymonoxime)
mechanism of formation of fulminic acid mentioned in chemistry of powder and explosives is differente from the one in chemistry of explosives
COPAE: HC(=NOH)COOH is nitrated by nitrogen dioxide which is present to form nitroisonitrosoacetic acid (O<sub>2</sub>NC(=NOH)COOH). this
losses carbon dioxide to form formonoitrolic acid (HC(NO<sub>2</sub> =NOH) wich decomposes further into nitrous acid and fulminic acid.
COE: HC(=NOH)COOH <s> ></s> HON=C + HCOOH
I assume the reaction mechanism mentioned in COPAE is more appropriate. what do ya guys think?
|
|
Theoretic
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 776
Registered: 17-6-2003
Location: London, the Land of Sun, Summer and Snow
Member Is Offline
Mood: eating the souls of dust mites
|
|
I think nitration of Anything with NO2 isn't straightfroward, becaus it's a radical and leads to at least two different products, so it
seems unlikely. The splitting of the molecule straight to fulminic acid seems very ready, the fulminic acid molecule is there almost complete. The
COPAE route seems unlikelier still, as decarboxylation doesn't proceed spontaneously.
BTW, where did the product that seems to come from formaldehyde and not acetaldehyde come from? I don't see how formaldehyde could form at all.
The combination of a carboxylic acid is also possible, and that's what is likely to hapopen as I will explain later on. The formaldehyde
derivative seems unlikely unless the acetic acid that is the product of the reaction of the acetaldehyde derivative reacts with nitrous acid.
It also seems a waste to let HNO3 do the oxidation, maybe some H2O2 is permitted by the gods of chemistry, thus using nitrous acid for the
product-forming reactions (directly, not derived from nitric acid), and H2O2 as the oxidizing agent? ![:o](./images/smilies/shocked.gif) ![:o](./images/smilies/shocked.gif)
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
<blockquote>quote:<hr>It also seems a waste to let HNO3 do the oxidation<hr></blockquote>NaNO<sub>2</sub> and
H<sub>2</sub>O<sub>2</sub> is more expensive than nitric. HNO<sub>3</sub> oxidizes the alcohol to acetaldehyde and
turns into nitrous acid which is needed to react with the acetaldehyde. due to unstabliy of HNO<sub>2</sub> which is increased by higher T
some NO<sub>x</sub> also forms and escapes from reaction vessel so we need excess nitrous acid. when using EtOH there'll be quite
excess nitrous acid.
1. HNO<sub>3</sub> + CH<sub>3</sub>CH<sub>2</sub>OH <s> ></s>
HNO<sub>2</sub> + CH<sub>3</sub>CHO
2. HNO<sub>2</sub> + CH<sub>3</sub>CHO <s> ></s> HC(=NOH)CHO +
H<sub>2</sub>O
3. HC(=NOH)CHO + <font color=blue>H<sub>2</sub>O</font> + <font color=red>HNO<sub>3</sub></font>
<s> ></s> HC(=NOH)COOH + HNO<sub>2</sub> + <font
color=blue>H<sub>2</sub>O</font>
4. HC(=NOH)COOH + <font color=blue>H<sub>2</sub>O</font> + <font color=blue>HNO<sub>2</sub></font>
<s> ></s> HON=C + HCOOH + <font color=blue>H<sub>2</sub>O</font> + <font
color=blue>HNO<sub>2</sub></font>
5. <font color=blue>HON=C</font> + <font color=blue>HCOOH</font> + <font
color=blue>H<sub>2</sub>O</font> + HNO<sub>2</sub> <s> ></s> <font
color=blue>HON=C</font> + <font color=blue>HCOOH</font> + <font color=blue>H<sub>2</sub>O</font> +
0.5H<sub>2</sub>O + 0.25NO + 0.25NO<sub>2</sub>
6. HON=C + <font color=blue>HCOOH</font> + <font color=blue>1.5H<sub>2</sub>O</font> + <font
color=blue>0.25NO</font> + <font color=blue>0.25NO<sub>2</sub></font> + <font
color=red>0.5Hg(NO<sub>3</sub> <sub>2</sub></font>
<s> ></s> 0.5Hg(ON=C)<sub>2</sub> + HNO<sub>3</sub> + <font
color=blue>HCOOH</font> + <font color=blue>1.5H<sub>2</sub>O</font> + <font color=blue>0.25NO</font> +
<font color=blue>0.25NO<sub>2</sub></font>
so:
<font color=green>2HNO<sub>3</sub></font> + CH<sub>3</sub>CH<sub>2</sub>OH +
0.5Hg(NO<sub>3</sub> <sub>2</sub>
<s> ></s> 0.5Hg(ON=C)<sub>2</sub> + <font
color=green>HNO<sub>3</sub></font> + HCOOH + 1.5H<sub>2</sub>O + 0.25NO + 0.25NO<sub>2</sub>
summarized reaction for intermediates mentioned in COE:
<b>4HNO<sub>3</sub> + 4CH<sub>3</sub>CH<sub>2</sub>OH + 2Hg(NO<sub>3</sub> <sub>2</sub> <s> </s><u><sup>excess
HNO3</sup></u><s> ></s> 2Hg(ON=C)<sub>2</sub> + 4HCOOH + 6H<sub>2</sub>O + NO +
NO<sub>2</sub></b>
summarized reaction for intermediates mentioned in COPAE:
<b>8HNO<sub>3</sub> + 4CH<sub>3</sub>CH<sub>2</sub>OH + 2Hg(NO<sub>3</sub> <sub>2</sub> <s> </s><u><sup>excess
HNO3</sup></u><s> ></s> 2Hg(ON=C)<sub>2</sub> + 4CO<sub>2</sub> +
12H<sub>2</sub>O + 3NO + 3NO<sub>2</sub></b>
if COE is right boilibg a solution of Hg(NO<sub>3</sub> <sub>2</sub> glymonoxime and H<sub>2</sub>O<sub>2</sub> should yield MF.
(anyway happy regularing )
|
|
Theoretic
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 776
Registered: 17-6-2003
Location: London, the Land of Sun, Summer and Snow
Member Is Offline
Mood: eating the souls of dust mites
|
|
It looks like COPAE's reaction only differs in that formic acid is oxidized with more nitric acid, forming CO2 and NOx, which is undesirable. So
it turns out that two different reaction routes lead to essentially identical outcomes. The formic acid oxidation happens more readily than the
oxidation of alcohol, so in a way, COPAE wins!
"(anyway happy regularing "
Thanks! ![:D](./images/smilies/biggrin.gif)
BTW, can nitrous acid react directly with alcohol? If so, then:
C2H5OH + 2HNO2 => 2HONC + 3H2O is possible!
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
"can nitrous acid react directly with alcohol?"
yup but it makes ethyl nitrite
both ethyl nitrite and ethyl nitrate can form in a MF batch
|
|
Theoretic
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 776
Registered: 17-6-2003
Location: London, the Land of Sun, Summer and Snow
Member Is Offline
Mood: eating the souls of dust mites
|
|
What I mean is that nitrous acid bonds to the intermediates in the process by eliminating an oxygen from itself and two hydrogen atoms from the
organic molecule, could it bond to ethanol (and generally alcohols) directly? Apparently it bonds to the methyl group of acetic acid, could that hapen
to ethanol? If so, then after the elimination of fulminic acid from the reaction product of ethanol and HNO2, methanol is left, which could react
similarly. Thus fulminic acid would be produced full yield based on alcohol (and somewhat on nitrous acid too, since seedy oxidations by HNO3 with
undesirable NOx are avoided)!
Or is the carboxylic group of acetic acid required to promote the reaction?Also, would higher temperatures inhibit ethyl nitrite formation?
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
"Apparently it bonds to the methyl group of acetic acid"
as showed it bonds to the methyl group of acetALDEHYDE but if acetic acid works ... I read somewhere that methylene group in neighborhood with a
carbonyl group reacts with nitrous acid to form the isonitroso compound, thus EtOH can't react the way you explained.
"It looks like COPAE's reaction only differs in that formic acid is oxidized with more nitric acid"
Overall, sounds like that. but remember COPAE doesn't mention any formic acid to form, it passes through disparate intermediates
|
|
Theoretic
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 776
Registered: 17-6-2003
Location: London, the Land of Sun, Summer and Snow
Member Is Offline
Mood: eating the souls of dust mites
|
|
"I read somewhere that methylene group in neighborhood with a carbonyl group reacts with nitrous acid to form the isonitroso compound"
Which means acetic acid or acetone and nitrous acid will produce HONC full yield, no oxidations and all!
[Edited on 12-1-2004 by Theoretic]
|
|
ME
Harmless
Posts: 1
Registered: 30-1-2004
Location: on earth
Member Is Offline
Mood: No Mood
|
|
acid
I'm no chemist , so i dont know if this will work.
KNO3 + H2SO4 = HNO3 + K2SO4
Why not:
MF + HCL = F,acid + MgCl
....Just an idea.
sadfdljkf
|
|
Marvin
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 995
Registered: 13-10-2002
Member Is Offline
Mood: No Mood
|
|
Unfortunatly fulminic acid is chemically unstable and tends to decompose if you try to make it. Trying to form the acid from a salt and HCl causes it
to hydrolyse IIRC.
|
|
Nick F
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
It's the same with nitrotetrazoles that I'm playing with at the moment - the salts are quite stable, with mercuric nitrotetrazole being
proposed as a replacement for lead azide, but the free acid has been known to detonate spontaneously.
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
HCl reacts with fulminic acid forming (mono)chloroformoxime I don't at what conditions though
(Nick F: I'm very interested in you're tetrazol advantures.. I remember the story from the older threads... what about making a thread
dedicated to tetrazols generally? or have you already done it on E&W?)
|
|
Nick F
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
I've been posting a little bit about it in the "my favourite primary explosive" thread over at the E&W Forum. There's some
that I still need to write up (purification of the sodium salt, formation of the silver salt, my attempts at recrystalising the silver salt to give
high bulk density...), but I won't be able to do any more experimenting until June. I'm still trying to find out more about
5,5'-azoditetrazole, other than "formed by oxidising aminotetrazole with permanganate in alcohol." The Uni library will help, I hope...
I might write a thread about it all in June, when I get more experimenting done...
|
|
The_Davster
A pnictogen
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
Well, I attempted to make copper fulminate with seemingly bad results.
Silver fulminate was dissolved in concentrated ammonia and a piece of copper wire was placed into the solution. After 24h of sitting a blue solution
resulted with the remaining copper wire and a fine layer of silver powder on the bottom. I tested the silver powder on the bottom to see if contained
fulminate by lighting it...it did not explode or crackle. The silver powder was filtered out. To the blue solution was added 56% AcOH till the pH
tested neutral. It became a slightly lighter shade of blue. There was a small ammount of blue precipitate on the bottom, but very little. It has
not been tested for explosive properties yet. To this suposed solution of copper fulminate a few tests were preformed. First some dilute NaOH was
added in the hopes to get a Cu(OH)2 precipitate and a solution of sodium fulminate. Strangly, the solution became purple, and nothing precipitated.
Next some silver nitrate was added(to a fresh sample of the 'copper fulminate' in the hopes to get some silver fulminate which would confirm
that I did indeed have copper fulminate solution. Immediatly upon adding the AgNO3 a white ppt resulted. It was not explosive. Unlike silver
fulminate it also seemed to decompose to silver oxide after around a min indoors under atificial lighting.
So in short...I have no idea what the blue solution is.
Thoughts?
[Edited on 13-7-2005 by rogue chemist]
|
|
Lambda
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 566
Registered: 15-4-2005
Location: Netherlands
Member Is Offline
Mood: Euforic Online
|
|
Copper (I & II) fulminate via Mercury fulminate
Rogue chemist, have you checked out the "Handbook of Preperative Inorganic Chemistry volume 1-3" by Brauer. I seem to recall that there is a
methode of Copper (I & II) fulminate synthesis via Mercury fulminate.
Your purple solution may just be (Cu(NH3)4)++ ,a Copper (II) tetramine complex.
[Edited on 14-7-2005 by Lambda]
|
|
The_Davster
A pnictogen
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
But there has to be an anion in there as well, unfortunatly not fulminate as the tests indicated, but I am curious as to what it might be when I
started with pure dry silver fulminate.
I'll have to check out the referance you mentioned.
[Edited on 14-7-2005 by rogue chemist]
|
|
Marvin
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 995
Registered: 13-10-2002
Member Is Offline
Mood: No Mood
|
|
Sounds to me like you mostly have a mixture of copper and ammonium acetate in solution, possibly containing hydrolysis products of the fulminate.
Acetic acid won't cause the precipitation of copper fulminate, as this is highly soluable in water. Silver and mercury versions arn't.
If you want to try this again just leave water, silver fulminate and copper powder in contact. Driving off the water without decomposing the
fulminate might be a little bit more tricky.
The silver test does suggest some contamination of the fulminate used.
|
|
The_Davster
A pnictogen
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
Quote: | Originally posted by Marvin
If you want to try this again just leave water, silver fulminate and copper powder in contact. |
Tried that, just some copper wire with silver fulminate under water, swirled occasionally for a few hours. Well a reaction did take place, there is
silver particles around and the silver fulminate in the bottom has turned a brown green. It explodes nicely,but not noticibly different than silver
fulminate. Strangly however the solution is still colorless, so perhaps copper fulminate is not as soluble as thought? Or something went wrong.
EDIT: I cannot seem to find my copy of brauer, I know I have it on disc somewhere but I cannot find it, if you were to put it up on rapidshare Lambda
I would be very greatful.
[Edited on 21-7-2005 by rogue chemist]
|
|
Lambda
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 566
Registered: 15-4-2005
Location: Netherlands
Member Is Offline
Mood: Euforic Online
|
|
Handbook of Preparative Inorganic Chemistry Volume 1 & 2 by G. Brauer (2nd edition)
Here you are Rogue chemist, but no Copper fulminate manufacture in "Brauer", except Copper azide and Copper acetylide. The Encyclopedia of
Explosives and Related Items by Fedoroff may have the information you are looking for. This encyclopedia gives excelent refferences to articals that
go more abundantly into the matter.
Handbook of Preparative Inorganic Chemistry Volume 1 & 2 by G. Brauer (2nd edition) available for downloade.
Posted on 21-7-2005 by Lambda in the thread "Books":
https://sciencemadness.org/talk/viewthread.php?tid=2569&...
|
|
The_Davster
A pnictogen
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
Well, I left the mixture I mentioned in my last post for a few days...there are now bright green particles floating around in a very light green
solution with silver dust on the bottom of the beaker. Copper fulminate when wet burns with a bit of a crackle, much less energetic than silver
fulminate, but with a pretty green flame.
Now to figure out how to separate silver from copper fulminate...time for some heavy research.
|
|
Blasty
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 107
Registered: 25-7-2008
Member Is Offline
Mood: No Mood
|
|
There's some interesting information about copper fulminates (notice, plural, since there appear to be several of them) in Thomas Thomson's A
system of chemistry of inorganic bodies, Volume 2 (see attachment)
I wonder if some of these might have potential use in making snap-like impact firecrackers. Particularly interesting for such a purpose would be the
ones which explode with a red flame (fulminate of nickel by double decomposition & white fulminate of zinc) or a green flame (white fulminate of
copper.)
Attachment: Pages on fulminates from A system of chemistry of inorganic bodies, Volume 2 -Thomas Thomson.pdf (538kB) This file has been downloaded 818 times
|
|
The WiZard is In
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 1617
Registered: 3-4-2010
Member Is Offline
Mood: No Mood
|
|
alcohol - nitric acid - N trioxide - Cu nitrate
From the similarity of copper to mercury and silver in its relations
toward nitric acid, as recently discussed by Divers in his paper on "
Hydroxylamine," the authors were led to make several trials to
prepare copper fulminate from alcohol, and either copper nitrate
and nitrogen trioxide ; or copper nitrate and nitric acid ; or copper
nitrate, nitric acid, and nitruus acid, but all without success. The
active catalytic oxidising power of cupric salts, which affects the
act';.Mi of nitric acid upon copper (Acworth und Armstrong), and
so readily causes the destruction of hydroxylamine (or isonitrosyl
hydride), is sufficient to explain the failure. In proof of its being
exerted in this case, they state that when nitrogen trioxide is
passed for some time into an alcoholic solution of copper nitrate,
an abundant precipitation of copper oxalate is produced without
any evident activity of the nitrous anhydride which all along
becomes quietly absorbed by the alcohol.
[OCR by Google.com/books]
Chemical news and journal of industrial science, Volume 52
By Sir William Crookes
1885
http://tinyurl.com/25q7r6p
|
|
hissingnoise
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3940
Registered: 26-12-2002
Member Is Offline
Mood: Pulverulescent!
|
|
N2O3 should be called dinitrogen trioxide - its correct name, to avoid confusing people starting chemistry. . .
|
|
d010060002
Harmless
Posts: 11
Registered: 5-7-2010
Member Is Offline
Mood: No Mood
|
|
I read through the thread, and I know that it's been gone over before, but I just read a method for making copper fulminate from scratch. I don't know
if the source is reliable, but it's on googlebooks.com under The Preparatory Manual of Explosives By Jared Ledgard. Just if you guys wanted to look at
it, it's page 119.
|
|
Blasty
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 107
Registered: 25-7-2008
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by d010060002 ![](images/xpblue/lastpost.gif) | I read through the thread, and I know that it's been gone over before, but I just read a method for making copper fulminate from scratch. I don't know
if the source is reliable, but it's on googlebooks.com under The Preparatory Manual of Explosives By Jared Ledgard. Just if you guys wanted to look at
it, it's page 119.
|
Read the quote posted by The WiZard is In. Such a method does not work with copper. Copper fulminates have to be prepared from other fulminates. For
these methods look at the file I posted in this very thread.
|
|
Pages:
1
2
3 |