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garage chemist
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The reaction occurs at 90- 100°C IIRC and this is strange because of the boiling point of ethanol.
Maybe it is better to carry out the reaction in aqueous solution, you can see that the reaction is complete when the blob at the bottom has
disappeared.
"Die Chemie der Kampfstoffe" is an e- book, it has been scanned by PAC from the E&W.
Here is the link:
http://www.websamba.com/P~A~C/Die%20Chemie%20Der%20Kampfstof...
I haven't seen the book "The War gasses" so I don't know if the "Die Chemie der Kampfstoffe" is just the german
translation of it.
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DDTea
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Ah, this is actually "The War Gases" in German. Same author and such.
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
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JohnWW
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Unless some valuable byproduct can be recovered for other uses, disposal of chemical warfare agents, and similar toxic surplus or condemned chemicals,
by reaction with other chemicals (which may themselves be costly) is usually uneconomic compared to simply burning in a special incinerator, with the
emissions being scrubbed out with water-spray scrubbers in the flue. Another possibility is deep burial in a remote area designated as a hazardous
wastes dumping area. The toxicity of the substances also militates against trying to chemically deactivate them.
Explosives are usually too dangerous to try to treat chemically e.g. with a reducing agent, and unlike war gases they cannot be safely incinerated. As
in Iraq, they can be disposed of safely only by controlled detonation in a pit (then filled in) in a remote area, or by deep burial in a remote area.
After WW2 a lot of explosives were dumped at sea in deep areas, especially the deepest trenches, in the North Atlantic ocean. Unfortunately, some were
dumped in shallower places in fishing areas, and as the result are occasionally dredged up by trawlers. The rusting steel shell and bomb casings make
them dangerous to handle.
John W.
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garage chemist
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Now I've made some bromopicrin.
(NaBrO + TNP)
It smells very sweet and is much less painfull to breathe than chloropicrin.
It caused almost no tearing and no coughing.
The smell is not too similar to chloropicrin, it is easy to distinguish those two by the smell.
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Reverend Necroticus Rex
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Has anyone tried making iodopicrin, or maybe the fluorine analogue, fluoropicrin should be much more toxic due to the F- ion
The sun is shining on a brand new day
Blackened corpses burn where they were slain
Self-flagellation prompts him to confess, Bless me father, for I made this mess.
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fvcked
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Who wants to test smell flouropicrin
Oh bubble trumps!
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garage chemist
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I wonder how to synthesize fluoropicrin?
I mean, hypofluorites don't exist because fluorine reacts violently with water to form HF and O2.
Maybe by reaction of sodium fluoride with chloropicrin? (Finkelstein swap)
I don't know about fluoropicrin but it could be either extremely toxic or not toxic at all.
Some organic fluorine compounds are very toxic (simple alkyl fluorides, Perfluoroisobutylene, Sarin) while others are non- toxic (freon, the
fluranes).
I think iodopicrin would be rather harmless, most likely not too different from iodoform.
I was actually surprised at how harmless bromopicrin was. I could directly sniff the reaction mix and only got some mild eye irritation. It also
smelled rather pleasant.
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BromicAcid
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CF3NO2 appears to be found under the name trifluoronitromethane rather then fluoropicrin for which I got zero results. It seems rather difficult to
synthesize as all the results that I found cited a rather recent source for a direct synthesis of this chemical:
| Quote: | | Lu, N; Thrasher, J. S. “The Direct Synthesis of Trifluoronitromethane, CF3NO2,” J. Fluorine Chem. 2002, 117, 181-184. |
Although there is possibly an indirect method to achieve it that was used previously. It does appear to be quite the rarity though.
Edit: I've heard that hypofluorites can be made by running fluorine gas over a surface that has been prevously wetted with an aqueous alkali.
[Edited on 9/7/2004 by BromicAcid]
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Reverend Necroticus Rex
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Could you perhaps post a direct link to the article you mentioned Bromic, I don't know how to access journals like that from when a name/title is
cited
The sun is shining on a brand new day
Blackened corpses burn where they were slain
Self-flagellation prompts him to confess, Bless me father, for I made this mess.
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BromicAcid
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Sorry but I don't have the article, all I found were citations to it
Edit: Searched around and found an abstract of it.
[Edited on 9/7/2004 by BromicAcid]
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DDTea
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Trifluoronitromethane seems like it would be an extremely aggressive compound. Wouldn't the three Fluorines would create a hyperactive
electrophilic Nitro group?
I'm going to make a conclusion here, based on the assumption that Bromopicrin is NOT as aggressive as Chloropicrin (you may want to check that
again--perhaps you just didn't have a high enough concentration in the post-reaction mixture to cause significant irritation?). The greater the
electronegativity of the CX3, the more electrophilic and aggressive the NO2 is and thus the NO2 causes the irritation. This would explain why
Chloropicrin is significantly more aggressive than Bromopicrin. And continuing this, Trifluoronitromethane ("Fluoropicrin" would be even worse!
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
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DDTea
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Continuing what I said above... I find that Nitro-Halogen compounds and Cyanide-Halogen are fairly comparable. As such, to consider the effect of a
more electronegative Halogen on the aggressiveness of the compound as a whole.
My hypothesis is that the more electronegative the Halogens in Trihalonitromethanes, the more electrophilic and aggressive is the Nitro group. So,
let's take into account the Cyanogen Halides and their irritating properties, according to "The War Gases."
Cyanogen Chloride: "Concentrations of 2.5 mgm per cu. m. of air produce abundant lachrymation in a few minutes. The maximum
concentration which a normal man can support without damage for 1 minute is 50 mgm per cu. m. of air."
Cyanogen Bromide: "Concentrations of 6 mgm. per cu. m cause strong irritation of the conjunctiva and of the mucous membranes of
the respiratory system... the maximum concentration which a normal man can support for a period of 1 minute is 85 mgm per cu m., according to Flury,
and 40-45 mgm. per cu. m. according to Ferrarolo"
Again, the same trend, at least judging by these two compounds. The more electronegative halogen seems to cause greater irritation. So I'm
going to make the assumption that it works the same way with compounds like Chloropicrin.
Strange though; Cyanogen Fluoride and Cyanogen Iodide are both included in The War Gases, but no details to their aggressive properties are given.
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
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Reverend Necroticus Rex
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My guess would be, cyanogen fluoride=HIGHLY toxic, more so due to the toxicity of the F- ion.
Cyanogen iodide would be perhaps less so than the bromide, but still unpleasant stuff to be around
Such a shame astatine doesnt have a longer half life....
The sun is shining on a brand new day
Blackened corpses burn where they were slain
Self-flagellation prompts him to confess, Bless me father, for I made this mess.
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JohnWW
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Because of the greater stability of the C-F bond compared to that of other C-halogen bonds, it would be more resistant to metabolic processes. While
FCN would be more volatile than cyanogen chloride or bromide, it may be less poisonous because of this greater bond stability.
Here is a section from the U.S. Army manual FM8-9, at the web-page
http://www.fas.org/nuke/guide/usa/doctrine/dod/fm8-9/3ch5.ht... :
"SECTION III - CYANOGEN HALIDES
515. Introduction.
Cyanogen chloride and cyanogen bromide after absorption react in such a way that hydrogen cyanide is eventually released. Their effects on the body
are essentially similar to those of hydrogen cyanide, but, in addition, they also have local irritant effects.
516. Physical and Chemical Properties
a. Cyanogen chloride is a colorless, highly volatile liquid. Although only slightly soluble in water, it dissolves readily in organic solvents. Its
vapour, heavier than air, is very irritating to the eyes and mucus membranes. Cyanogen chlorides pungent, biting odour is marked by its irritating
lachrymatory properties. Normally cyanogen chloride is non persistent. (See Table 5-I.)
b. Cyanogen halides are rather poorly absorbed onto charcoal, especially if the charcoal is damp. The cyanide group, not being ionised, does not react
well with the metal salts found in respirator charcoals.
517. Detection.
Automatic detectors are available which detect attack concentrations of vapour. Draegertm tubes are also available, as are water testing kits.
518. Decontamination.
See hydrogen cyanide. [oxidants e.g. permanganate]
519. Mechanism of Action.
Cyanogen chloride acts in two ways. It systemic effects are similar to those of hydrogen cyanide but it also has local irritant effects on the eyes,
upper respiratory tract and lungs.
520. Pathology.
Cyanogen chloride injures the respiratory tract, resulting in severe inflammatory changes in the bronchioles and congestion and oedema in the lungs.
Very low concentrations (e.g., 10-20
mg. min. m-3 ) produce eye irritation and lachrymation.
521. Signs and Symptoms.
The signs and symptoms caused by cyanogen chloride are a combination of those produced by hydrogen cyanide and a lung irritant. Initially, cyanogen
chloride stimulates the respiratory centre and then rapidly paralyses it. In high concentrations, however, its local irritant action may be so great
that dyspnoea is produced. Exposure is followed by an immediate intense irritation of the nose, throat and eyes, with coughing, tightness in the chest
and lachrymation. Afterwards the exposed person may become dizzy and increasingly dyspnoeic.
Unconsciousness is followed by failing respiration and death within a few minutes. Convulsions, retching and involuntary defecation may occur. If
these effects are not fatal, the signs and
symptoms of pulmonary oedema may develop. There may be persistent cough with much frothy sputum, rales in the chest, severe dyspnoea and marked
cyanosis.
522. Treatment.
Cyanogen halide poisoning should be treated in the same way as hydrogen cyanide poisoning as regards its cyanide-like effects. [with amyl or sodium
nitrite, vitamin B-12]. Pulmonary irritation should be treated in the same way as
phosgene poisoning.
523. Course and Prognosis.
Recovery from the systemic effects of cyanogen halide poisoning is usually as prompt as in hydrogen cyanide poisoning. However, a higher incidence of
residual damage to the central nervous system is to be expected. Depending on the concentration of cyanogen halide to which the casualty has been
exposed, the pulmonary effects may develop immediately or may be delayed until the systemic effects have subsided. Early prognosis must, therefore, be
guarded."
These war gases (only chloride and bromide mentioned) thus owe their toxic effect to the CN- group as in HCN (which is more volatile), and additional
lachrymatic and vesicant effect to the halogen part, requiring dissociation in metabolism for both effects. Dissociation would be probably too slow in
the case of FCN. The chloride and bromide do not persist because they are slowly hydrolysed by water; FCN would be resistant to hydrolysis. The
greater molecular weight of ICN would make it insufficiently volatile for easy dispersal, the iodine also being less hazardous, although it is even
more easily dissociated. HOCN is also much less volatile because of hydrogen-bonding.
John W.
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sylla
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| Quote: | Originally posted by PHILOU Zrealone
In the industry, they make NM/NaOH/H2O mix and then bubble exces Cl2 in it! |
I tried it and something really strange had happend.
I first mixed nitromethane with some NaOH 1M, it was quite exothermic so I added ice. After a few minutes it went dark brown/orange. Then I've
bubbled excess Cl2 into it and nothing special appeared... so I decided to add the nitromethane/NaOH (does it really form sodium nitronate or maybe
the water break it to another thing ?) directly to the hypochlorite solution (12°) slowly.
At first the solution was cloudy and white but after having added all the solution of nitromethane (or derivate) it became orange and some crystals
began to precipitate.
After a few minutes my solution was covered by those crystals (beige and with density <~ 1). Of course there was no chloropicrin at all (if I do
the same synthesis without NaOH I get lots of chloropicrin)...
So I'm wondering what I actually made :| Does someone here have an idea ?
[Edited on 19-10-2004 by sylla]
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DDTea
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You added the NaOH directly to the Nitromethane? That in itself should have formed Sodium Nitronate, yes... I have no idea what chlorinating such a
mixture would give. It seems more sensible to make a hypochlorite mixture w/ NaOH and HCl, and then add Nitromethane to that. In fact, according to
the patent, NM is added to the Hypochlorite, not the other way around. Doing that simply change really made my yield a lot better when I did this (or
at least made it easier to see/extract).
Another interesting route to Chloropicrin is Nitromethane + Cyanuric Chloride. Adding 1 mole of Cyanuric Chloride per mole of Nitromethane should
form Cyanuric Acid + Chloropicrin. The mixture would then be treated with 3 moles Sodium Bicarbonate and poured into a large volume of cool water.
The Chloropicrin, not being water soluble, could be easily extracted while the sodium cyanurate solution would be disposed of.
I like this method more than the Hypochlorite method since it involves working with smaller volumes of liquid--making extraction a lot easier. It
might lend itself better to making PS from impure (35%) Nitromethane mixtures, too.
Anyone care to try it? 
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
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garage chemist
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If I only had some nitromethane...
Making picric acid is so time donsuming and expensive, and it doesn't always work.
Actually, there is an auction on 2 Liters of NM right now at ebay, but it's very expensive and 2 Liters is WAY too much for me. I don't make
any HE charges so it doesn't have any uses for me other than making chloropicrin.
I most likely won't buy it.
Is cyanuric chloride the same as trichloroisocyanuric acid?
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chemoleo
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Sylla, I also don't quite understand what you did.
First you mixed a solution of 1M NaOH (how much) with how much NM? Then, you bubbled Cl2 directly into it? Or did you make the hypochlorite solution
by bubbling Cl2 into it? Where does the 12 % hypochlorite solution come into this?
Then, what did you do with the crystals? Did you subject them to flame, or whatever?
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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garage chemist
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Finally, I found something about the actual smell of chloropicrin, now the thread title has its justification.
WW2 Gas identification posters
Here is the poster for chloropicrin:
Although I never smelled flypaper...
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sylla
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| Quote: | Originally posted by chemoleo
Sylla, I also don't quite understand what you did.
First you mixed a solution of 1M NaOH (how much) with how much NM? Then, you bubbled Cl2 directly into it? Or did you make the hypochlorite solution
by bubbling Cl2 into it? Where does the 12 % hypochlorite solution come into this?
Then, what did you do with the crystals? Did you subject them to flame, or whatever? |
Actually I did two things :
I first bubled Cl2 intro the sodium nitronate (or watchever it is) solution which yield nothing ; no chloropicrine and no insoluble salt or colour
change.
I then tried to add another solution of sodium nitronate to hypochlorite solution (12° chlorometric, so 5% not 12%) which gave me the strange
crystals.
I didn't tried to filter them ; I'm too scared about chloropicrin toxicity , aren't you ?
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garage chemist
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I had succes with a new route to chloropicrin which is much less time consuming than the TNP or NM route. No bleach is used, since I hate using bleach
because of the large reaction volumes.
Also no fuming nitric acid is needed.
I got the idea from the article "Chloropicrin" from the FTP (thanks to whoever uploaded it).
2 ml of 65% nitric acid were mixed with 3 ml 37% hydrochloric acid, in a 30ml pear shaped flask. A slightly yellow, warm aqua regia was obtained.
0,5ml acetone were added at once and the contents of the flask swirled to ensure mixing. The yellow color of the acid vanished and it became clear and
fizzed a bit. Then I heated it. It quickly became yellow, then brown, and a reaction set in and the mix boiled violently, evolving NO2. I quickly
placed the flask in a cooling bath, which moderated the boiling. I took it out again and slowly heated with a bunsen burner, the mix had a dark red
color and was cloudy. Some more NO2 was evolved, and the reaction was left to continue on its own until it had returned to room temperature.
20 ml of water were added to the mix and a red drop of chloropicrin (approx. 0,1ml) seperated out. It was extracted with a pipette and washed with
water, which turned it clear.
Note that the chloropicrin dissolves in the hot acid, only the dilution of the acid precipitates it completely.
Don't try to make a much larger batch than the described one, because the reaction is violent and can get out of control easily.
An attempt with fuming nitric acid produced no significantly larger yield, but the reaction was even more violent.
[Edited on 23-6-2005 by garage chemist]
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IrC
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Garage Chemist, do you know any other links to "Die Chemie der Kampfstoffe"? The link above is either dead, or I have a really crappy ISP?
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garage chemist
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You can find the english version in the SCM library under the name "The War Gases: Chemistry and analysis" from Mario Sartori (near the
bottom of the list).
Note that the production of chloropicrin from aqua regia isn't covered there.
Also look in the FTP, if "Die Chemie der Kampfstoffe" isn't up there, then I could upload it.
[Edited on 23-6-2005 by garage chemist]
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IrC
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Thanks. I looked around a while in axehandles ftp and looked at the file lists, but did not see it. Since he has such a large amount of stuff in there
(I put a few hundred MB's there myself in the last 2 months) I may have missed it but no matter, I went to the SCM book section and D/L'ed
the english version you mentioned.
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12AX7
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What I'm left wondering is, what does chloropicrin have to do with picric acid or vice-versa? What would be dechloropicrin and why does it have
a different name?
Tim
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