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Author: Subject: disulfur dichloride
International Hazard

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[*] posted on 20-5-2015 at 16:08

Quote: Originally posted by CuReUS  
And yes I plan to gas this with Cl2 in an oil bath above the boiling point of SCl2 but below S2Cl2...say 120C. The SCl2 vapors that continuously form will combine with SO2 & excess chlorine over a hot activated charcoal bed in making SOCl2. Which will then be purified and used in the making of alkyl chlorides.

I think you didn't read my post,S2Cl2 can make alkyl halides from alcohols,you don't need to convert it to thionyl chloride

Here is a link to page 191 of "Small-Scale Synthesis of Laboratory Reagents with Reaction Modeling" by Leonid Lerner that discusses purifications issues with respect to SOCl2.


Comments per another source on safe paths to SOCl2:

"The oxidation of SCl2 by atmospheric oxygen has been investigated using activated charcoal as the catalyst. The reaction has been discussed in terms of two reactions. Firstly, the irreversible oxidation of SCl2 to SO2Cl2 :

SCl2 + O2 --> SO2Cl2

and secondly, the reversible reaction between the SCl2 and the SO2Cl2 to form SOCl2 :

SCl2 + SO2Cl2 <--> SOCl2

This oxidation has been investigated at the temperatures 193°C, 138°C and 320°C, and the equilibrium constant of the reversible equilibrium reaction has been determined for each temperature. From the temperature dependence of this equilibrium constant it is found that the reaction is exothermic to the extent of 18 kcal.
(Yield of SOCl2 at 193°C : ~73%) "


While not cited in the original work which dates back to 1947, I would suspect, in actuality, some radical based chemistry via uv radiation creating active species of oxygen, chlorine and sulfur noless (atomic oxgen, singlet oxygen, S2O, SO, S2Cl, for example, see recent paper "Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur ... " available at pages 81 to 85 in particular) in the referenced action of "atmospheric oxygen" on SCl2 forming SO2Cl2.

Some comments by Atomistry ( ), on SO2Cl2 preparation to quote:

"Chlorine and sulphur dioxide will only unite under some accelerating influence. It was by the interaction of these gases in sunlight that sulphuryl chloride was first obtained by Regnault in 1838.

Bone charcoal or activated wood charcoal is a convenient accelerator, combination occurring instantly. If the vessel in which the reaction is carried out is cooled to 30° C., the sulphuryl chloride is condensed and may be drained away as rapidly as it is formed. The terpene hydrocarbons, especially pinene and limonene, also certain ethers, phenols and esters, are effective catalysts, as also is camphor.

The formation of sulphuryl chloride is favoured by low temperature and its decomposition by high temperature:

SO2 + Cl2 ⇔ SO2Cl2.

Both these reactions are .catalysed by the foregoing catalysts. For the efficient preparation of the chloride, the dry reacting gases are brougght together at ordinary temperatures in the presence of a catalyst such as "Norit," a highly activated powdered carbon. The mixture is then cooled to -10° C. to ensure complete combination, filtered from the catalyst and carefully distilled, the heat being applied to the liquid for as short a time as possible. "

[Edited on 21-5-2015 by AJKOER]
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[*] posted on 14-9-2015 at 15:29

I can't seem to find the result of the reaction
Na2S + S2Cl2 -> ?
Does anybody know good books about sulfur compounds, especially sulfur halides? (gmelin's?)
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