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Author: Subject: Diethylsulfide from potassium ethylsulfate and sodium sulfide
Myfanwy
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[*] posted on 21-12-2009 at 08:49
Diethylsulfide from potassium ethylsulfate and sodium sulfide


Hey i tried the synthesis of Diethyl sulfide.

I found a patent in the internet with the number US3024263.
There its described, how to make ethylsulfuric acid from ethanol with sodium bisulfate.
Both you can buy everywhere.
C2H5OH + 2NaHSO4 -> C2H5HSO4 + Na2SO4 + H2O
you must heat the bove for some hours in reflux standing in a water bath. when its not bubbling anymore at 100°C you have very pure ethyl sulfuric acid.
then cool down to 30°C, the sodium sulfate will produce with a water a hydrate. The Ethyl hydrogensulfate will decompose in contact with water!

the ethyl sulfuric acid is neutralized with potassium carbonate and is dissolved in water.
Dont take to much water, or the Diethylsulfide will not settle on the bottom.
2C2H5HSO4 + K2CO3 -> 2C2H5KSO4 + H2O + CO2

Then you make a sulfide. I made aluminium sulfide, because its producing with water very pure hydrogen sulfide.
2Al + 3S -> Al2S3
Hydrolyse the aluminium sulfide
Al2S3 + 6H2O -> 3H2S + 2Al(OH)3
the hydrogen sulfide is let into a concentrated solution of sodium hydroxide.

H2S + 2NaOH -> Na2S + 2H2O
put the solution with the sodium sulfide to the potassium ethylsulfate solution.
Now a liquid will form at the bottom. This stuff has an stinky garlic like odor.
2C2H5KSO4 + Na2S -> Na2SO4 + K2SO4 + C4H10S

So you can produce diethyl sulfide. I dont know, if it will hydrolyse with water.
diethylsulfide and chlorine will give mustard gas, but dont do that.
What you can do with DMS?
Interesting odor :D:D
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ScienceSquirrel
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[*] posted on 21-12-2009 at 09:28


Quote: Originally posted by Myfanwy  
So you can produce diethyl sulfide. I dont know, if it will hydrolyse with water.
diethylsulfide and chlorine will give mustard gas, but dont do that.


Diethyl sulfide will not hydrolyse on contact with water in a million years.
There are plenty of ways of making mustard gas but as far as I know reacting diethyl sulfide with chlorine is not one of them.
The best method on a lab scale is thiodiglycol and thionyl chloride.
Making it is easy, handling the stuff safely is hard!
Here is a nice little recipe from the boys and girls at Porton Down :)

http://www3.interscience.wiley.com/journal/112732327/abstrac...

[Edited on 21-12-2009 by ScienceSquirrel]
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Myfanwy
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[*] posted on 21-12-2009 at 10:15


well the french chemist alfred riche made Mustard Gas 1854 from chlorine and diethylsulfide. Im sure this will work, but wont test it :P

i would take concentrated hydrochloric acid as chlorinating agent instead of thionyl chloride^^. thionyl chloride is harder to make.

EDIT :Sorry this link dont work..

[Edited on 21-12-2009 by Myfanwy]
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Peroxid
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[*] posted on 21-12-2009 at 10:31


The link that you post, don't work for me! It says:
"Session Cookie Error
An error has occured because we were unable to send a cookie to your web browser. "

I checked my browser settings but my browser can accept cookies, so i don't understand what is the problem!
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[*] posted on 21-12-2009 at 10:41


I doubt the direct reaction of chlorine with diethyl sulfide would produce much more than a mess that might contain traces of mustard gas, the article does date from 1854.
Direct chlorination is only really useful as a preparative reaction when the mixture produced can be easily separated on an industrial scale eg methane with chlorine or alternatively some structural feature favours one isomer eg toluene to benzyl chloride.
Thiodiglycol is harder to obtain than thionyl chloride. The reaction involves only mixing the two reagents and distilling the product, all the other products are gasses that can be fed into a scrubbing tower in the gas cupboard.
Mixing hydrochloric acid with with thiodiglycol will leave you with a mixture of water and mustard to separate!
You would have to be barking to try this outside a university lab with all the proper authorisations and a letter from the dean in triplicate stating that your work was bona fide so obtaining the chemicals would not be a problem.
Home made mustard gas?
Death or serious injury on the cards, get caught with it and almost indefinite jail I would say :(
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entropy51
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[*] posted on 21-12-2009 at 10:56


Quote:
well the french chemist alfred riche made Mustard Gas 1854 from chlorine and diethylsulfide
Got a reference for that? My references don't say that.
Quote:
You would have to be barking to try this outside a university lab with all the proper authorisations and a letter from the dean in triplicate stating that your work was bona fide so obtaining the chemicals would not be a problem.
Even the dean and governor of the state authorized it, it would still violate the Chemical Weapons Convention.

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Myfanwy
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[*] posted on 21-12-2009 at 10:59


well anyway i will never make mustard gas, its a really reactive and toxic compound. But its interesting to talk about that. But destilling mustard gas is not really smart. it decomposes at his boiling point.

But what you can do with DMS?

Im wondering how to make the nitrogen mustards? did anyone know?

EDIT :
entropy i found it on the german wikipedia.

[Edited on 21-12-2009 by Myfanwy]

EDIT number 2:
http://www.chemheritage.org/pubs/ch-v24n2-articles/feature_b...





[Edited on 21-12-2009 by Myfanwy]
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entropy51
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[*] posted on 21-12-2009 at 11:09


Quote:
destilling mustard gas is not really smart. it decomposes at his boiling point
The usual stuff is called HD. D = Distilled. (Note correct spelling of distilled.)

Quote:
entropy i found it on the german wikipedia.
Wiki is not really considered a reference in chemistry circles, even amateur ones. Because, as you've just found out, it is often wrong. Better to get your chemistry from books.

Well, Chemical Heritage is better than Wiki, but all my refererences say Riche used the same method as Despretz. Riche also didn't note the stuff he made burned him up, as did other chemists who prepared authentic mustard, so there's some doubt he made mustard. But I've never seen Riche's paper. Sartori's War Gases also doesn't mention a diethyl sulfide route, which I would expect if it were a viable method.

[Edited on 21-12-2009 by entropy51]

[Edited on 21-12-2009 by entropy51]
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Myfanwy
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[*] posted on 21-12-2009 at 11:23


The usual stuff is called HD. D = Distilled. (Note correct spelling of distilled.)

oh sorry my bad. and jes my english isn`t perfect =D
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[*] posted on 21-12-2009 at 12:20


Mustard is normally distilled under reduced pressure.
Fractional distillation of a sample extracted from a German shell was the standard method of analysis during World War I to determine the proportion of mustard and to see if they had added any other nasties.
It should be noted that this distillation was done on the open bench using a manometer and a standard water driven aspirator!
Equipment was cleaned by dumping it in to a bath of chlorinated lime and water.
Mustard is pretty horrible stuff but it is not the killer of legend, now Lewisite that is the gear.
There are exceptions to the CWC, research is allowed if it is conducted on a small scale and there is a clear aim to achieve medical benefits and not make a weapon, certainly that is the UK position.
A friend of mine did his PhD on novel routes to and metal complexes of phosgene. He had licenses coming out of his ears to do it but it was allowed.
Nitrogen mustards are trivial to synthesise.
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[*] posted on 21-12-2009 at 16:35


When you made your (CH3CH2)2S, how did you deal with, or suppress, its intense garlicky smell? Did you wear a gas mask? Did the neighbors complain? The vapor of the stuff would also be highly toxic by inhalation, in the same way as H2S.
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entropy51
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[*] posted on 21-12-2009 at 16:59


Quote:
The vapor of the stuff would also be highly toxic by inhalation, in the same way as H2S
Well, it probably does have good warning properties, AKA stench.
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Myfanwy
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[*] posted on 22-12-2009 at 02:57


Jes Diethylsulfide is stinky, but never as toxic as Hydrogen sulfide.

nope i didnt wear a gasmask. But i made the experiment
outside. The Hydrogen sulfide generation i made outside, too.

I dont have the toxicology datas about that stuff. But it may be harmful and skin irritant. I think its comparable with Diethyl ether in his properties. Both are highly flammable.
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Peroxid
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[*] posted on 22-12-2009 at 05:53


Diethylsulfide: LD50 (oral-rat): 2030.00 mg/kg so it is less toxic than H2S
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Myfanwy
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[*] posted on 22-12-2009 at 07:02


thx Peroxid, 2300mg/kg is really much Oo this stuff is nearly harmless.

this time i tried the experiment again, but something got wrong...
First i made 5,4g H2S and let the Gas into a concentrated solution of NaOH. Colour changed to yellow, and 12g Na2S fall out, when the baker get cold.

then i put 33g H2SO4 (a little bit more to convert all of the ethanol to EtHSO4, because DES is fully miscible with EtOH) and 15g EtOH together. Colour changed to yellow. I let stay the mixture for 10minutes and heat up to 120°C for 5minutes or so. Then i neutralized the hot acid with 22g K2CO3. After 5 minutes no carbon dioxide was generated more and i put 70-80g Water to the PES. Than i gave 100ml of the Na2S(12g) to the PES-solution.
it foam up. i was wondering why and than it smelled really bad like rotten eggs. Dont take too much H2SO4 for the synthesis of the EtHSO4!!! my whole basement and stairway smelled like rotten eggs. in my basement is a huge concentration of H2S. Because of the Gas i started swetting strongly, ang got dizzy.

Hopefully i got no serious poisoning. Experiments like that everytime under the fumehood or outside!

Unforntunately i got no DES =(. But the mixture got dark greenish, and it smelled like garlic or rotten vegetables.
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entropy51
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[*] posted on 22-12-2009 at 07:54


Quote:
my whole basement and stairway smelled like rotten eggs. in my basement is a huge concentration of H2S. Because of the Gas i started swetting strongly, ang got dizzy
You know neighbors sometimes call the police or fire department when they smell sulfides? They think it's a gas leak.
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Myfanwy
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[*] posted on 22-12-2009 at 08:02


Jes i know :|

I opened all windows and the door, after the Hydrogen sulfide evolution. But you can even smell it in the basement...
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[*] posted on 23-12-2009 at 00:02


Quote: Originally posted by Myfanwy  
H2S + 2NaOH -> Na2S + 2H2O
put the solution with the sodium sulfide to the potassium ethylsulfate solution.


Klason (Ber. 20, 3413) uses sodium ethylsulfate and KOH, and says the aq. KOH isn't more saturated than half with H2S. After work-up, this will yield almost quantitative sulfide also free from ethanethiol.

Quote: Originally posted by Myfanwy  
well the french chemist alfred riche made Mustard Gas 1854 from chlorine and diethylsulfide.


Riche, Ann. 92 [1854], 358 to 360 describes action of Cl2 onto diethyl sulfide and distillation products. Various products are described, no idea if any are mustard. Though the formulas are all wrong, e.g. diethyl sulfide is "C4H5S". The assigned formulas of the various compounds are: C4H3Cl2S, C4H2Cl3S, C4HCl4S, C4Cl4S, C4Cl6. Chemistry has come quite a way since the 1850s. The last one is hexachloroethane. Mustard is C4H8Cl2S. I also can't find any corroboration of any of those being mustard.

Quote: Originally posted by Myfanwy  
But what you can do with DMS?


If you mean DES, then it can be oxidized to form DESO (Saizew, Ann. 144, 154). Diethylsulfone from stronger oxidation.

[Edited on 23-12-2009 by Formatik]
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Myfanwy
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[*] posted on 23-12-2009 at 02:56



Quote:

Klason (Ber. 20, 3413) uses sodium ethylsulfate and KOH, and says the aq. KOH isn't more saturated than half with H2S. After work-up, this will yield almost quantitative sulfide also free from ethanethiol.


Would sodium ethylsulfate and sodium (hydrogen)sulfide would work, too? Would be the same reaction, just with two mols Sodium (hydrogen)sulfate as the products.
Or by mixing solid SES and solid S(H)S and distilling the DES.


Quote:

Though the formulas are all wrong, e.g. diethyl sulfide is "C4H5S".


Oo diethyl sulfide is (C2H5)2S or C4H10S. two ethyl groups bounded with a sulfur atom in the middle!


And whats with Sulfur dichloride, or thionyl chloride as chlorination agent?
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Formatik
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[*] posted on 24-12-2009 at 15:43


I don't see why it should also not work to use salts of the same alkali here.
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Myfanwy
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[*] posted on 25-12-2009 at 00:26


Thanks formatik. I try it out on Saturday/Sunday. This time i`ll take a reflux for the synthesis of EtHSO4.
And i neutralize all of the acid, dont want hydrogen sulfide in my house again =O

And i`ll try to destill the DES by heating a dry mixture of EtNaSO4 and Na2S...
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Myfanwy
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[*] posted on 3-1-2010 at 05:46


I tried it with Sodium Hydrogensulfate and Ethanol one week ago.
The main product of this is ether. Sodium hydrogensulfate is just a catalyst. Just a tiny bit Ethyl sulfuric acid was formed.

After heating the mixture the temperature stays for 20min at 80°C, then it goes very slowly up to 140°C.
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[*] posted on 11-1-2010 at 15:25


Just to avoid any confusion. Half-saturation is corresponding to the desired alkali sulfide, (x)2S, whereas entierly saturating a base like NaOH gets NaHS. That's what you don't want because then you will also have the thiol alongside the sulfide. If you do want the thiol then it would need to be fractionated. Also, if you can't handle H2S, forget about making it and see if you can obtain the alkali sulfide.

Gmelin.png - 29kB

[Edited on 11-1-2010 by Formatik]
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Myfanwy
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[*] posted on 12-1-2010 at 12:42


Yes i got now 18g Diethyl sulfide.

http://www.youtube.com/user/Myfanwy94#p/a/u/0/dXaCIoSm8v0
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[*] posted on 12-1-2010 at 13:54


You really should wear gloves.. I hope you've at least got some googles on :)



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