Abstract
The product distribution of the Kolbe electrolysis, which varies with the kind of carboxylic acid electrolysed, has been considered from the thermochemical standpoint. Approximating the bond dissociation energy of the carboxylic hydrogen, D(RCOOM, to be 115 Kcal/mol, the heat of reaction for various possible elementary processes of the Kolbe reaction has been calculated. It has been concluded that the easiness of the elimination of a carbon dioxide from a carboxylate-free radical has an important effect on the resultant distribution of the products. Olefin and ester may be expected for the case where the rate of decaboxylation is not large enough.
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