Electrode Kinetic Studies on Electro‐Organic Syntheses Involving Carbonium Ions: I . Anodic Oxidation of Acetate Ions to Methyl Acetate

Abstract

Anodic electrosynthesis of methyl acetate on graphite electrodes in aqueous acetate solutions is known to proceed via intermediate formation of carbonium ions. Kinetic‐mechanistic aspects of this reaction have not been examined previously and an attempt has been made in the present investigation to elucidate these aspects by carrying out electrode kinetic studies. Potentiostatic Tafel plots, potentiodynamic profiles, anodic charging curves, open‐circuit potential decay measurements, capacity‐potential relationships, apparent heats of activation, and reaction order derivatives are reported for this system. On the basis of an analysis of these data, it has been suggested that initial discharge step is the rate‐determining step (r.d.s.) in the over‐all reaction. Possible explanation for the occurrence of a carbonium ion pathway, in preference to a radical one as observed for the Kolbe reaction, in the present case is also put forward.