INDIRECT ELECTROCHEMICAL PROCESSES AT A ROTATING-DISK ELECTRODE - OLEFIN BROMOHYDRINATION

Steady-state transport to a rotating disk electrode coupled with a second-order homogeneous reaction of arbitrary stoichiometry is analyzed to obtain limiting current enhancement factors as functions of the second-order rate constant. Analytic solutions are obtained for infinitely fast reaction, and numerical solutions are obtained for finite rates by orthogonal collocation. Anodic bromohydrination of olefins is a hypocatalytic process in which half of the bromide in the electrolytically produced bromine is released by the homogeneous reaction. Enhanced bromide limiting currents are observed in the presence of allyl alcohol and of propylene and compared with the model to estimate the homogeneous rate constants.