4-Stroke
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Sulfur Chlorides With Alternative Chlorine Sources
While sulfur chlorides are usually prepared by passing chlorine into molten sulfur, there are other ways to do it. At least one method that works for
sure is directly distilling a mixture of TCCA and sulfur. While this method does not require the HCl to generate chlorine, it gives far smaller
yields, so the total cost stays about the same. I have also seen older threads about heating a mixture of sulfur and CuCl2, but the results
are inconclusive.
So, my question is, what else can be used to make sulfur chlorides? Someone has mentioned that a mixture of sulfur and salt could work, but that seems
unlikely. Could a chloride with a lower melting point (e.g. ammonium chloride) be used? Would performing the reaction under significant pressure
change things (because sulfur's boiling point will be increased and so higher temperatures could be achieved)?
Thanks.
Ukrainium
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Texium
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Thread Moved 24-11-2024 at 10:56 |
4-Stroke
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Would it be feasible to produce sulfur chlorides by combining ammonium chloride, sulfur, and MnO2 in a vessel that is heated to about
400°C? This is just below the boiling point of sulfur. The ammonium chloride would decompose into HCl and ammonia. The ammonia would hopefully bubble
out unchanged, while the HCl would react with the MnO2 to produce chlorine that would in turn react with sulfur to produce sulfur
chlorides?
If possible, this pathway to sulfur chlorides would be significantly better than any of the current ones, but is it viable?
Thanks.
Ukrainium
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bnull
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The three substances in the same place at the same time? Not likely. What will probably happen is the oxidation of sulfur by manganese dioxide. Lots
of sulfur dioxide, some manganese sulfide with traces of sulfite and sulfate (who knows) and no free chlorine.
I have two suggestions. (1) try heating carefully a mixture of manganese dioxide and sulfur. You should be safe enough using less than 1 gram of the
mixture and doing it outside. I don't know what variety of manganese dioxide you have; if it is the one from batteries, then it should be carefully
washed to remove the last traces of alkaline hydroxide and dried. I also have no idea of what proportions you intend to use, hence I can't recommend
one; I suppose MnO2 will be in excess.
(2) Consult Ullmann's Encyclopedia of Industrial Chemistry, Brauer's Handbook of Preparative Inorganic Chemistry (in the Library), Blanchard's Synthetic Inorganic Chemistry (there's a copy in the Library), and the Kirk-Othmer Encyclopedia of Chemical Technology
volumes that deal with manganese dioxide and sulfur chlorides. It is a huge wealth of material. But, hey, you intend to create a new process; it will
be a lot of work anyway, and the more you know, the better. It helps avoiding mishaps.
Edit: One more thing. When HCl reacts with MnO2, what happens to hydrogen? When you find the answer, you'll see the situation growing in
complexity.
[Edited on 24-11-2024 by bnull]
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clearly_not_atara
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I considered KICl4 and KMnCl4 for this, but both salts are frustrating to prepare.
Combining TCCA with a metal halide might work. CaCl2 seems ideal. But some reactions with TCCA have been known to explode. I don't know the energetics
very well.
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teodor
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I would prefer "any reaction with something alternative to sulfur chlorides" to "sulfur chlorides with alternative chlorine sources". Because the
thing stinks and the bottles and boxes will stink forever (not sure is it the peroperty of the pure chloride or one of its byproducts but it is likely
you want to add something to the mix more than Cl2 and S). Working with just chlorine will not make your lab stinky after finishing your experiment.
Even H2S could be vented out, so it's better.
And, by the way, there are many ways starting with virtually any compounds containing S/O/Cl to get a stinky mix of sulfur chlorides as a byproduct,
so the concern for me is usually to avoid their formation in any sulfur experiments if Cl is also present.
And I am sure there are even more ways to avoid sulfur chlorides usage in virtually any reaction than how to make them. Unless you follow some data
from wikipedia which doesn't care usually about routes beyond what is economical for industrial production.
[Edited on 27-11-2024 by teodor]
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