Fulminate & COLOR (a chemistry query)
Johnny
C,N,O, Hg = Hg + 2CO + N Why is it that there are color differences
in common Hg-Fulminate? The only variable seems to be the condition
and purity of the Hg. Content of free mercury aside, there has
appeared no common explanation that the color ranges from a buff
yellow to a gray/brown. If free Hg exists in the final product I could
understand the gray/brown coloration but there is commonly reported a
buff-light-yellow, (white as high purity)*, etc, etc..... When the
process takes place does external temp play a part? Old literature
consistently makes references to variances in coloration. Does a
lighter product indicate a higher purity? Is this the goal of a
lab-level production system? And finally, is this a controllable
phenomenon or is this simply a random condition brought about by
external elements like the temp of the air or barometric pressure?
* Does this mean that the lighter the product, the purer?
Psalms:55:21: The words of his mouth were smoother
than butter, but war was in his heart: his words
were softer than oil, yet were they drawn swords.
+...*...+
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LOUIS
-Cristal size: it is wel known that when cristals are reduced to dust
they are apprently clearer/paler.
-Interference of the light and cristal size and surface gives different
shades of colour.
-Artificial light and natural (sun)light gives red or blue shift in
coloration.
-The purity of HNO3, Ethanol, Hg define the level of impurities and thus
the proportion of posible side reactions that will give trace amounts of
byproducts that will eventually serve as cristal germs (while fulminate
cristals are forming) and if those byproducts are coloured, induce
variable color change.
-The initial temperature and maximum temperature reached defines the
reactions that may occure or not.
The reaction of Hg fulminate is quite complex and exothermic and if the
heat is strong enough, side reactions occurs (endothermic or exothermic)
and the amount of byproducts define cristal size and color.
-Time of reaction also provides deeper or lighter colors.
-Insulation of the system or system size define the thermic profile of
reaction and thus plays on the points hereup.
A good cooling and/or agitation, time of cooling play on the the same
level.
-The amount of reactants (exces ethanol, HNO3, Hg, Hg(NO3)2) may provide
an infinity of combinations of thermic profile, side reaction,
byproducts.
-...XYZ unknown factor (catalyst, inhibitor, pressure, moisture,...)
All those parameters that are sometimes crosslinked by self influence
define somehow the system and the field of results is given by a
multicombinatory equation system with a very high number of dimensions.
This is true for all known reaction involving several ingredients.
So results are almost the same but never exactly the same except if you
use the same amounts, the same starting products, at the same
temperature, at the same time, during the same time with the same thermic
profile, the same agitation speed in the same vessel size/geometry, same
operator... then you will have two very close results.Reproductible
experiment.
Note that Hg oxydes might form while processing since HNO3 reduces and
ethanol oxydises (Hg oxydises too but meanwhile may come back using
reducing properties of ethanol, ethanal, acetic acid, ...
Hg oxydes are quite colourised (yellow/red).Colloidal Hg is black-brown
to grey.
Ph Z
Johnny
poses the question: did industry EVER make consistent fulminate
products? I would imagine that MANY tragic accidents were related to
using said compound in fuse caps. Inconsistency may have caused
countless "duds". I am saving your statements on crystal
differentiations and growth as that covers a lot of ground with other
questions in org chem.
LOUIS
and their reasons; then they found solution to get purer Hg fulminate;
they finally got it replaced by other Pb- and Hg-free primaries of the
organic kind.
Most intrighuishing thing, on the organic level, are:
-that from ethanol you have to loose one carbon to get the fulminate but
that methanol or CH2=O or HCO2H are poison to the reaction (inhibitor
effect or too reactive reducers).
Ox = oxydiser = HO-NO2, NOx, Hg(NO3)2
To give you an idea of the complexity of the reaction here is a possible
way.
CH3-CH2-OH -Ox-> heat + CH3-CH=O <==> CH2=CH-OH
CH3-CH=O -Ox-> heat + CH3-CO2H
Hg + 2HNO3 --> Hg(NO3)2 + NOx + H2O + heat
CH2=CH-OH -Ox-> HO-CH2-CO2H + CH3-CO2H + O=CH-CH=O + HO2C-CH=O +
HO2C-CO2H + H2O + CO2 + heat
-that it is known fact that Hg nitromethanate turns into Hg fulminate
upon time and if heaten.
Hg(-O-N(=O)=CH2)2 --> Hg(-O-N=C)2 + 2H2O
-that nitroacetic acid decarboxylate spontaneously to provide
nitromethane/nitromethanic acid
O2N-CH2-CO2H ==> CH3-NO2 + CO2 (g)
CH3-NO2 + base --> CH2=N(=O)-OH
Base might be an hydroxyde, or an oxyde
Conclusion:
All this must thus go through something like Hg(O2C-CH2-NO2)2 -->
Hg(O-N=C)2 + 2 H2O + 2CO2
A good idea would be to test if HNO3/NOx + Hg/Hg(NO3)2 and CH3-NO2
provides fulminate too
Ph Z
Johnny
produces fulminate (Y/N?)
Is one I may attempt in the near future....it appears to pose a
question that I have little experience with. - On the other hand I
have known that methanol killed the fulminating process but never
understood how H2O influenced same. - As I am sure you know some ethyl
alcohols that had been used in the distent past were quite impure;
most containing water to a degree. I would like to understand the
influence oxygen (additional) has on the process and it appears to
coincide with the above experiment as well.
donald j haarmann
"Johnny" <you_no_m...@home.com> wrote in message news:09iu409o4gns8clk1...@4ax.com...
> Given that the process for Hg Fulminate looks like ;
> C,N,O, Hg = Hg + 2CO + N Why is it that there are color differences
> in common Hg-Fulminate?
[snip]
----------
Good old Urbanski [1984] notes that "The problem of differences in colour of mercuric fulminate
(grey and white xlts) does not seem to be fully solved." He references several papers that claim the
differences are do to organic impurities e.g., resinous polymers of fulmeric acid. And notes that "Crystallization
of the substance from a solvent always yields a white product." He then quotes Bagal -
"Technical mercuric fulminate contains mercuric oxalate, mercurous oxides, inclusion of reaction
liquor, mercuric chloride..... metallic mercury."
--
donald j haarmann - colophon
lamedeer
used it to make tordedos to throw at girls. No wonder I couldn't get a date
in junior high school.
Anyhow, The flash from the torpedos was always red. Not any of the colors
you described.
"Johnny" <you_no_m...@home.com> wrote in message
news:09iu409o4gns8clk1...@4ax.com...
donald j haarmann
"lamedeer" <lamedeer@swissinfoDOTorg> wrote in message news:NbmdnZ_qj6X...@adelphia.com...
> A friend and I used to make mercury fulminate from thermometer mercury. We
> used it to make tordedos to throw at girls. No wonder I couldn't get a date
> in junior high school.
>
> Anyhow, The flash from the torpedos was always red. Not any of the colors
> you described.
>
---------
I would be so bold as to suggest — you misread the question/answer. The colour
is that of the fulminate its self, not the colour of its detonation products/flame.
Time for this .......................................................................................... again!
John Read
Explosives
Pelican Books London 1942
Chapter XI
Explosives That Excite Others [in part]
FOR THE FORCES
Leave this book at a Post Office when you have read it,
so that the men and women in the Services may enjoy it too.
Detonation and the Damsel
A chapter of this kind, bristling with frisky compounds, may well end with a
striking story, and this narrative is literally striking as well as-being true.
Once upon a time, now many years ago, a worthy Professor of Chemistry was
lecturing in an Australian university. His subject was mercury fulminate. It was a
very hot and humid day in November; his lecture theatre was filled to capacity
with a hundred and seventy frisky young Australians, and it had a galvanised
iron roof upon which the sun shone from a cloudless sky. Through the windows
came incespritly the vibratory shrilling of-the cicadas, or "bush canaries", mingled
with the odour of sunbeaten eucalyptus leaves.
Now in this audience the young ladies sat in the front seats, immediately facing
the lecture bench, and upon this torrid day of early summer one of them in
particular was feeling the heat and humidity. As the lecturer wended
remorselessly onwards, after the manner of professors immersed in their
subjects, the distressed damsel became increasingly aware of the
oppressiveness of her environment. At last the Professor warmed to his climax a
long-anticipated experiment on the detonation of mercury fulminate.
"You will observe on the anvil," came the familiar and, untiring voice, "a
specimen - a very small specimen-of this most powerful explosive, mercury
fulminate. I am now about to strike it with a hammer. I invite you all, ladies and
gentlemen, to pay attention to the result, and to recall in so doing what I have
told you about the activating effects of the detonation wave which I regret I
cannot demonstrate to you as well."
The hammer fell.
The Professor had been too modest in his closing words. The experiment
succeeded beyond his expectations. For when the hammer fell, the fulminate
detonated with a loud report, and simultaneously the aforesaid damsel, seated in
close proximity to the centre of disturbance, swooned away, after the manner of
agitated young ladies.
The Professor, jerked out of his wonted self-possession by this unwanted
response to the detonation wave, unwisely called for volunteers to carry the fair
victim of detonative aggression out of the crowded room.
The Australians are a gallant race. The response was all that could have been
expected, even in this Queen City of the South; for the eager class volunteered
en masse, headed by the brawny captain of the University Rugby Football XV,
the gigantic and lion-hearted Jumbo Woods. Having successfully removed the
fainting lady, the class "called it a day".
On the following morning the Professor met his class again. There was a full
attendance, including the heroine of the detonation wave. To the surprise of the
class, the anvil still reposed on the lecture bench, and the Professor opened his
lecture, by taking up the hammer.
"It occurs to me, ladies and gentlemen," he began, "that owing to an
unfortunate incident at the close of our last lecture you may not have grasped
the full significance of the detonation of mercury fulminate. I am therefore about
to repeat the experiment. But before I do so, I now afford anyone suffering from
weak nerves an opportunity of leaving the room."
The Professor paused, with the uplifted hammer in his hand, and gazed
pointedly at the innocent cause of yesterday's interrupted lecture. She, however,
was feeling quite at her ease: a "southerly buster" had come up the coast in the
afternoon, and the room was fresh and cool. So the damsel sat on demurely,
pencil poised above note-book, and did not budge.
But to his misfortune, the Professor's words, unlike his glance, were not
specific; and while he waited expectantly, with his eyes fixed upon the static
lassie, a dynamic figure arose in the back row, descended the sloping gangway
with thunderous tread, and stalked solemnly out through the open doorway in full
view of the spellbound Professor and his momentarily dumbfounded class. And,
lo, the departing figure was the figure of that mighty man of valour and hero of a
hundred stricken fields-the lion-hearted Jumbo Woods.
--
donald j haarmann — eminence grise
lamedeer
"donald j haarmann" <donald-...@worldnet.att.net> wrote in message
news:UJu4c.6963$Pa7.1...@bgtnsc05-news.ops.worldnet.att.net...
>
> "lamedeer" <lamedeer@swissinfoDOTorg> wrote in message
news:NbmdnZ_qj6X...@adelphia.com...
> > A friend and I used to make mercury fulminate from thermometer mercury.
We
> > used it to make tordedos to throw at girls. No wonder I couldn't get a
date
> > in junior high school.
> >
> > Anyhow, The flash from the torpedos was always red. Not any of the
colors
> > you described.
> >
>
>
> ---------
colour
> is that of the fulminate its self, not the colour of its detonation
products/flame.
>
>
> Time for this
............................................................................
> donald j haarmann - eminence grise
>
>
>
>
LOUIS
69% HNO3 will have a cooling/tempering effect because of the heat
capacity of water; It works perfectly with concentrated 94% pure ethanol
(from suggar homemade fermentation distillation) and with HNO3 69%
besides that I imagine the reaction doesn't occure in more dilluted
systems. I have tried with comercial ethanol for burning lamps (blue
stuff - 90% denaturated ethanol + ???) and HNO3 69%; once it worked
nicely (long time ago), the next time with another ethanol bottle it
didn't...maybe that the denaturant had changed and the amount of ethanol
too.Now the same brand ethanol bottles indicates 80% ethanol .
When I say that it didn't worked there was actually an energetic reaction
leading to a solid precipiate but it wasn't cristalline, nor explosive,
nor flamable...it left a yellow -orange residue after heating and finally
volatilises Hg vapor when over heated, no cracks or sparks; it was thus
another salt of mercury that formed.
In contradiction all the successful reaction lead to cristalline
fulminate from white to grey...wich displayed strong flame sensitivity,
and explosive properties...sparks and cracks and no residue at all from
heating.
All reaction where similar and vigorous...evolution of suffocating white
smokes and near ebullition batch, very hot.
I don't understand what you mean by oxygen effect...there is no O2
involved here except the one present as nitrate or NOx.
At such a reaction temperature O2 will never enter the system despite
some H2O content to be of any use as reactant...Henry's law of solubility
of gases in water or other solvent is ruled by concentration of soluble
molecules (cations and anions are taken as independant molecules) and by
the temperature.
Cgas = K/(T*Cxyz)
Thus here since we have high concentrations of H(+), Hg(2+), NO3(-),
Ethanol, Water, ...and approx 80°C O2 solubility will be very poor.
Ph Z
Coalbunny
in granite...
>A friend and I used to make mercury fulminate from thermometer mercury. We
>used it to make tordedos to throw at girls. No wonder I couldn't get a date
>in junior high school.
>
>Anyhow, The flash from the torpedos was always red. Not any of the colors
>you described.
>
The mere thought of you tossing an explosive device at anyone is stupid. And
you got away with it? No one got hurt? I have to ask, where you exceptionally
lucky or are you lying?
Just wondering,
Carl
lamedeer
magnitude.
"Coalbunny" <h2t3m4l5...@7yahoo.com> wrote in message
news:4053a64...@news.vcn.com...
Johnny
question was poor: I WAS referring to the H2O issue in the fulminating
process in regards to oxygen. As such, does water in ethanol affect
the process? You imply that there may be a cooling effect and or a
slowing of the process. - If I am understanding you correctly...
You have pointed out so MANY variables that I am at wonder as to how
early 20th century factories maintained consistency.
Thanks
On Sat, 13 Mar 2004 23:32:47 +0100, LOUIS <Loui...@SKYNET.be> wrote:
>I don't understand what you mean by oxygen effect...there is no O2
>involved here except the one present as nitrate or NOx.
>At such a reaction temperature O2 will never enter the system despite
>some H2O content to be of any use as reactant...Henry's law of solubility
>of gases in water or other solvent is ruled by concentration of soluble
>molecules (cations and anions are taken as independant molecules) and by
>the temperature.
>Cgas = K/(T*Cxyz)
>Thus here since we have high concentrations of H(+), Hg(2+), NO3(-),
>Ethanol, Water, ...and approx 80°C O2 solubility will be very poor.
>
>Ph Z
>
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Johnny
<donald-...@worldnet.att.net> wrote:
>Good old Urbanski [1984] notes that "The problem of differences in colour of mercuric fulminate
>(grey and white xlts) does not seem to be fully solved." He references several papers that claim the
>differences are do to organic impurities e.g., resinous polymers of fulmeric acid. And notes that "Crystallization
>of the substance from a solvent always yields a white product." He then quotes Bagal -
>"Technical mercuric fulminate contains mercuric oxalate, mercurous oxides, inclusion of reaction
>liquor, mercuric chloride..... metallic mercury."
A contradiction: no? Or is this the John Kerry methodology of chemical
variance explanation? ;-) On one hand he said all pure Hg-Fulminate
is one color but on another he claims that a mystery still exists... I
wonder how in the 1980's Urbanski would still not have solidified an
answer. Was that the pubishing date....was his work re-written or did
he, at that time, still do research?
Johnny
ahhhh youth.......so strange a sonnet.
donald j haarmann
> On Sat, 13 Mar 2004 00:50:00 GMT, "donald j haarmann"
> <donald-...@worldnet.att.net> wrote:
>
>
> >Good old Urbanski [1984] notes that "The problem of differences in colour of mercuric fulminate
> >(grey and white xlts) does not seem to be fully solved." He references several papers that claim the
> >differences are do to organic impurities e.g., resinous polymers of fulmeric acid. And notes that "Crystallization
> >of the substance from a solvent always yields a white product." He then quotes Bagal -
> >"Technical mercuric fulminate contains mercuric oxalate, mercurous oxides, inclusion of reaction
> >liquor, mercuric chloride..... metallic mercury."
>
>
> A contradiction: no?
-----------
NO. There is technical grade i.e., manufactured and pure hg fulminate cleaned up by re-crystallization.
Just everyday chemical housecleaning.
--
donald j haarmann - independently dubious
LOUIS
--> all kinetics are slowered
--> since water has a cooling effect some reactions doesn't occure because
activation energy isn't reached noticeably by a given % of the molecular
population (slow speed and exotherm tempered so no higher exotherm can
occure).
If the system is too dilluted, nothing happens...the margin of critical water
contain should lay over 35% water in global.
Note that when you use the standard method: 69% HNO3 and 96% Ethanol, you
get between 20-10% water.
x ml HNO3/V total *31% water in HNO3 + y ml Ethanol/ V total * 4% water in
ethanol = % water in global
And V total (ml)= x + y + z (mercury)
but since z << y and x ; then V = x +y
We get x /(x+y)*31/100 + y/(x+y)*4/100 = GW%
(0,31 x + 0,04 y) /(x+y) = GW% thus
The more you have ethanol, the closest you are to 4% (y high) and the higher
the x, the closer you are to 31%.
Even if you have water, and that oxygen get on the place, oxygen will not
react in the process. Except maybe is you have a large batch with an excess
100% HNO3, a lot of mercury and some dry ethanol...then maybe a fire (or
explosion) could take place and be entertained by oxygen although it doesn't
need oxygen to get a fire out of an overheated runnawaying batch where HNO3
decompose to NOx and Hg(NO3)2 turns into HgO and Hg + O2 if hot enough.
Ph Z
LOUIS
reaction...interdependant and linked to: the initial and maximal temperature reached , to the time of reaction and to
the time of cooling,....The system is so complex that you get a matrix of possibilities with colours depending on the
"tiny" % of impurities....recrystallisation yields always the same product white product because it diminishes the
impurities level.
The mystery only comes from what reactions does really take place and what is the multiparameters effect on those but
since the aim is only to get pure reliable fulminate why bother study 10-100 kinetics and furtive spieces at the same
time...none of real industrial interest since the reaction goes to the end with as major >90% product the fulminate.
Ph Z
Coalbunny
in granite...
>The ansewr to your question is that you are definitly a jerk of the first
>magnitude.
>
Yep! I may be a jerk, but at least I'm not throwing explosive devices at others
while NOT entertained in acts of war. Remember what you said you did when
someone does that to OUR KIDS. You may see it a bit differently.
Don T
> On Wed, 17 Mar 2004 06:48:52 -0800, "lamedeer" <lamedeer@swissinfoDOTorg>
carved
> in granite...
>
> >The ansewr to your question is that you are definitly a jerk of the first
> >magnitude.
> >
> Yep! I may be a jerk, but at least I'm not throwing explosive devices at
others
> while NOT entertained in acts of war. Remember what you said you did when
> someone does that to OUR KIDS. You may see it a bit differently.
> Carl
>
Considering the poster is using swissinfo, and considering the possibility
that there are very few "Native-Americans" living in Switzerland, the poster
picked a very interesting e-dress. Very descriptive also I might add. Lame
ass attempt to impress people who work with explosives to start with and
then when rebuked he sends out a 7th grade retort. Lame. Fitting.
No charge for the analysis.
I will add that the flame color of Hg fulminate is more violet than red
though, so perhaps lamedeer is also color-blind.
--
Don Thompson
"The only stupid questions are those that should have been asked, but
weren't, or those that have been asked and answered over and over, but the
answers not listened to." Peter Rowe
Johnny
Louis and Don, I really apprieciate your time that you have taken in
this post...I frankly have copied the text as it delves into areas of
fulminate properties that I have, here-to-fore, not had answers to.
----Thanks again
On Wed, 17 Mar 2004 20:23:31 +0100, LOUIS <Loui...@SKYNET.be> wrote:
>Not at all a contradiction...since all parameters taken in account, it seems logical that due to various side to side
>reaction...interdependant and linked to: the initial and maximal temperature reached , to the time of reaction and to
>the time of cooling,....The system is so complex that you get a matrix of possibilities with colours depending on the
>"tiny" % of impurities....recrystallisation yields always the same product white product because it diminishes the
>impurities level.
>The mystery only comes from what reactions does really take place and what is the multiparameters effect on those but
>since the aim is only to get pure reliable fulminate why bother study 10-100 kinetics and furtive spieces at the same
>time...none of real industrial interest since the reaction goes to the end with as major >90% product the fulminate.
>
>Ph Z
>
-----= Posted via Newsfeeds.Com, Uncensored Usenet News =-----
lamedeer
July celebrations before fire works were banned. You would do well to talk
to some of your older relatives about such things. You could very well learn
quite a bit about that and other things.
The flash from Hg fulminate is never violet. Perhaps you are trolling for
some attention?
"Don T" <flas...@ix.netcom.comghost> wrote in message
news:pl26c.45203$aT1....@newsread1.news.pas.earthlink.net...
Don T
the nuts.
--
Don Thompson
"The only stupid questions are those that should have been asked, but
weren't, or those that have been asked and answered over and over, but the
answers not listened to." Peter Rowe
"lamedeer" <lamedeer@swissinfoDOTorg> wrote in message
news:QKCdnVWsHfi...@adelphia.com...