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XIV.—The Electrolysis of Mixtures of Acetates and Trichloracetates

Published online by Cambridge University Press:  15 September 2014

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Summary

When potassium acetate and trichloracetate are electrolysed together, mixed compounds are formed, but only to a very slight extent. A small quantity of trichlormethyl acetate is to be found among the reaction products. The presence of either salt affects the reactions of the other by diminishing the yields of the normal products and by promoting the production of substances like trichlormethyl alcohol and ethylene which result from the oxidation of single molecules of each acid. A short explanation of this phenomenon has been given. No methyl alcohol appears among the final products, but formaldehyde is found in considerable quantities. This oxidation is connected with the production of an oxidising agent such as chlorine at the anode. Hexachlorethane and methyl chloride are also produced during the electrolysis of this mixture.

The author desires to take this opportunity of thanking Professor Sir James Walker, F.R.S., upon whose suggestion this work was begun, for his helpful advice and criticism during its execution.

Type
Proceedings
Copyright
Copyright © Royal Society of Edinburgh 1925

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References

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page 145 note ‡ The volume of gas left after the various absorptions was too small for analysis, but, as it contained ethane, methyl chloride, and nitrogen, the actual amount of ethane was probably less than one-half the value given.

page 146 note * Op. cit., p. 308.

page 147 note * The inclusion of ethylene in this group is justified on the following grounds. When fatty acids, other than acetic and formic acids, are electrolysed, unsaturated compounds which are obviously derived from single molecules of the acid are formed and appear in the final products. This is illustrated by the production of large amounts of ethylene during the electrolysis of potassium propionate. CH3. CH2 COOH + O = CH2: CH2 + CO2 + H2O. No compounds of the type CH3CH: CH.CH3 have been isolated. In the case of pottassium acetate the expected unsaturated compound is methylene (CH2), which is, in all probability, first formed, but as it is incapable of a separate existence it appears in the end products as the polymerised compound, ethylene.

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