Ultrasonic Effects on Electroorganic Processes. Part 10. Product‐Selectivity in Mixed Kolbe Electrolysis of Carboxylic Acids

Abstract

Abstract Product‐selectivity was examined in mixed Kolbe electrolysis of carboxylic acids on a platinum anode in aqueous methanolic solutions under ultrasonic irradiation. It was found that an ultrasonic effect on the selectivity is caused not only by promotion of mass transport across the electrode interface but also by adsorption control of intermediated radical species by ultrasonic acoustic and cavitation effects. Namely, formation of the one‐electron oxidation products is favourable at low current densities compared with two‐electron oxidation products under irradiation, while the two‐electron oxidation is promoted at high current density. This is the ultrasonic effect characteristic of the Kolbe electrolysis. The mechanism of the ultrasonic effect is discussed with a hypothesis.