Formatik
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Chemical poisoning from dimethyl sulfide attempt
I recently had some very unpleasant experiences after attempting to synthesize a compound.
Some symptoms I've experienced: mostly severe throatache (the worst I've ever had), cough, runny and stuffy nose, blood and pus in the throat,
constant painful clearing of the throat, increased salivation, fatigue, tiredness, headaches, painful sneeze. I feel like shit. All of these problems
began to increase gradually several hours after exposure to sulfur toxin. I don't know what all exactly, H2S was one.
I was attempting to make dimethyl sulfide from sodium methylsulfate mush which sat for around 2 weeks. I made this from H2SO4, methanol, NaHCO3 and
some H2O. I added small amount of Na2S to this, I would constantly check by smell to see if any H2S could form from mixing these (it didn't and
shouldn't even after adding more Na2S and then warming, since the methylsulfate was made basic with excess NaHCO3). I could not establish the distinct
H2S odor anytime. The addition of solid Na2S in large amount to the sodium methylsulfate turned green though and gave off no H2S. Maybe it's possible
some aq. NaHCO3 decomposed in warm solution and liberated H2S from some Na2S through CO2? In fact, H2S was likely one the players involved: passing
steam over Na2S mixed with NaHCO3 was a patented process to making H2S (US951243).
Myfanwy's video for diethyl sulfide mistakenly holds the opinion that NaHCO3 is alright to use to basify ethylsulfate, and that this won't liberate
H2S. He actually only seemed to have tried Na2CO3. He never tried NaHCO3, like the video implies. But I don't care, I'm not watching any of those
videos again.
I started distilling this mixture mentioned above outside near the garage by gentle warming on a hotplate. Even though I always wear a gas mask or
chemical respirator plus work outside when handeling lethal compounds like Cl2, NO2, hydrochloric acid vapors, etc., I had read dimethyl sulfide is of
low toxicity (LC50 in rats is also in the 40,000ppm range) and so wore no respirator (very big mistake).
After some distillation, because of the extremely strong smell which was also coming inside the house (mixture of rotten cabbages, shit and sewer) at
the urging of a family member I discontinued the experiment and ended up with maybe only 3cc of colorless, clear, extremely volatile, absolutley
horrible smelling liquid with an extremely high vapor pressure around room temperature. The experiment made such an offensive smell, it spread over a
very wide area and so quickly. The smell was a bit different than dimethyl sulfide, which I had smelled before from combusting and aged DMSO, which
smells more like rotten cabbage. But for the most part, it seems to be dimethyl sulfide. The liquid ejects itself like diethyl ether when taken up
into a plastic dropper.
So I was washing the materials with aq. NaClO, and this would get rid of the odor from glass, but not plastic or rubber.
The problems in my health started several short few hours after having done this reaction. Journal citation on symptoms of someone who was poisoned
with H2S: "Sulfur compounds are severely irritating to the respiratory tract, leading to rhinorrhea, sneezing, sore throat, wheezing, shortness of
breath, chest tightness, hemoptysis, and a feeling of suffocation." (DOI: 10.4103/0256-4947.59379). Which is some of what I experienced as mentioned
above. H2S is also one of those gases that causes pulmonary edema. So I'm quite fortunate.
The H2SO4 was the only thing not technical or reagent grade. I think part of the problem is from the acid, which was a cheap drain cleaner, dark brown
in color, and it had an odor to it (I suspect also maybe part of this odor stems impurity that helped create an agent that destroyed my breathing
passages, I also doubt dimethyl sulfide can accomplish the damage). I'm not sure if other toxins did not form. The other possibility is that NaClO aq.
forms some toxic compounds when added to methylsulfate and Na2S mixture or dimethyl sulfide. Toxic methanethiol shouldn't have formed, since NaHS was
not used (Klason, Ber. 20, 3412-13 said no methanethiol forms, though he also neutralized H2S using KOH as it was mixed with sodium methylsulfate to
half-saturation).
I've been treating and getting treatment for this for several hours (inhaling oxygen from the tank, drinking tea, lots of water, inhaling steam and
herb/thyme water steam, ate oranges, ibuprofen, pseudoephedrine, resting, etc.), but it still hurted like hell. Some energy shakes (raw eggs, milk and
honey) taken for energy. Some homemade soup eaten. Then ketorolac and vitamin B12 injections in the maximus. Glutathione (10%) inhaled orally through
an oxygen tank mask for 1hr and 20 minutes. After these last three, finally after 18 hours of treating, some marked improvement.
My lesson learned from all of this is to wear the respirator even when I think the target molecule is thought to be relatively harmless, and do more
research, work in smaller amounts. Out of all of the poisons I've been exposed to before, this one really did me in. It's been 4 days and I've been
resting or trying to mainly and treating it, and I'm feeling much better. But now my nervous system feels a bit off. I felt I owe it to you guys to
help prevent a similar misfortune, or someone to be more careful. I'm going to be taking it easy for a while.
[Edited on 12-1-2011 by Formatik]
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Baphomet
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Cool post. Sorry to hear you nearly buried yourself.
Maybe what you have is actually dimethyl sulphate poisoning?
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1037601/?page=1
I doubt it's H2S as the main symptom of that is, um... death. 
[Edited on 11-1-2011 by Baphomet]
\"Who ARE you? You\'re like the drummer from REO Speedwagon - nobody knows who you are\" from \'Employee of the Month\'
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smuv
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Sobering Experiences! It seems many chemists on this forum have fallen victim to H2S Exposure. I think this is something that should not be taken
lightly by those intending to work with H2S or its salts.
I am glad to hear that you are feeling better, and hope you make a speedy recovery.
Warmly,
Smuv
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Formatik
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I hadn't thought about that. I'm not familiar with the hydrolysis conditions for the alkyl sulfates, or if DMSO4 indeed formed. I hope it did not
form. Dimethyl sulfate is supernasty, also a DNA damaging monster.
Btw. that article has interesting points using oxygen and steam inhalations for respiratory distress. Even though it's a stinky sulfur compound as
well, glutathione delivered in a nebulizer also can help reduce inflammation in the lungs and throat. I was getting this help and advisement under a
doctor; no way I'm going to try to play doctor. It's good have a parent working in the health industry. In pulmonary edema, one may need the emergency room quick.
At first when warming the mixture above, it smelled basically entirely like dimethyl sulfide, but then after some time and as temperature increased,
the odor became more severe and different. This may have been the H2S, covered in the odor of dimethyl sulfide, but could not be discerned out of the
gases. I didn't measure the temperature with a thermometer, but by hand, I would say it was between 30 to 75 C. As the temperature increased, I think
decomposition of NaHCO3 occurred. Then CO2 acted on the sulfide.
Right now, my throat is still sore and I've got a bit of a headache. But there has been massive improvements, nose is almost entierly clear. And I'm
to the point where I can sleep again.
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woelen
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Good to read that you are recovering again and also good that you posted this message. H2S (or any other sulfide) indeed is dangerous stuff. Two years
ago another member over here also posted about his severe health issues after experimenting with H2S (IIRC this was Klute).
BTW, didn't you have all kinds of curious or even nasty questions about what you were doing with these chemicals? I suppose a doctor will not have
patients very often who (almost) poisoned themself with anything more exotic than lampoil, chlorine bleach or some detergent.
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entropy51
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Quote: Originally posted by woelen  | | I suppose a doctor will not have patients very often who (almost) poisoned themself with anything more exotic than lampoil, chlorine bleach or some
detergent. |
Actually we do. When I worked in a big city ER we saw all kinds of intoxications and poisonings.
Most of the H2S intoxications occurred in men working on sewers. We had an attempted suicide by drinking conc HCl, ingestions of butyl nitrite, and
about once a year a cyanide ingestion (both suicidal and homicidal). Kids will drink anything, including insecticides. Lots of poisonings from
swimming pool chemical and janitorial chemical misadventures. Can't say that we ever saw a poisoning due to amateur chemistry however.
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Panache
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I don't suppose there was an point in the ambulance officers bringing you the cyanide corpses, one would have to be completely inept to fuck up that
suicide attempt.
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smuv
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| Quote: | | I don't suppose there was an point in the ambulance officers bringing you the cyanide corpses, one would have to be completely inept to fuck up that
suicide attempt. |
I believe it, I have known people to try to commit suicide in the most stupid possible ways. One fellow was particularly smart, but tried to kill
himself by drinking a completely non-toxic detergent. Whether he thought he would ACTUALLY be able to kill himself in this way, I did not
ask...but...many times a suicide is more of a cry for help than a whole hearted attempt to end one's own life. Also, related, suicide is usually an
illogical act, don't expect people to logically or rigorously plan it.
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Formatik
National Hazard
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| Quote: Originally posted by woelen | Good to read that you are recovering again and also good that you posted this message. H2S (or any other sulfide) indeed is dangerous stuff. Two years
ago another member over here also posted about his severe health issues after experimenting with H2S (IIRC this was Klute).
BTW, didn\'t you have all kinds of curious or even nasty questions about what you were doing with these chemicals? |
No, most treatments were just done at home.
I did read of Klute\'s experience. Deja vu, maybe? We are used to the stink, but when somebody else warns us we may need to listen. After trying to
make this, I could tell something was wrong it felt like something foul (and no, I don\'t just mean the odor itself) made itself into my lungs.
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peach
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You mentioning detergent reminded that just yesterday I'd quite at random noticed a site flash up in my googling for a split second that said
something along the lines of - number of poisonings by detergent rising.
I then did some more googling just now to see if I could find it again, but instead found something more curious.
A series of sites detailing how there is a trend in Japan (now moving to the US) to produce hydrogen sulphide from drain cleaner and bath sulphur, to
commit suicide. Apparently, some sites in Japan give PDF print out instructions for reference on what to buy, how to use it and include a warning sign
for your to courteously stick up on the way out, warning others about the presence of the gas.
This was handy to me, as I've been looking for various ideas on how to produce the gas easily at home (other than the standard iron sulphide method
alone), as it would be a good way of ensuring one of my electroluminescent paint components was clean.
[Edited on 13-1-2011 by peach]
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smuv
National Hazard
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Yeah, you would be amazed the stuff devoted to suicide you come across on the internet. I remember I was doing research for a bioethics paper (right
to die) and I came across a forum, that was devoted to helping people commit suicide. I mean, any method you could possibly think of to do it...there
was a thread about it.
[Edited on 1-13-2011 by smuv]
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