Electrocatalytic dechlorination of a PCB congener at a palladized granular-graphite-packed electrode: Reaction equilibrium and mechanism

Abstract

Our previous study on the electrocatalytic dechlorination of 2-chlorobiphenyl at a Pd-loaded granular graphite-packed electrode demonstrated that the process did not follow the first-order kinetics. The rate constant varied with the applied potential at the beginning, but later became irrelevant to the potential. The electrocatalytic kinetic was investigated in this study, in which several experiments were conducted to dechlorinate 2-chlorobiphenyl using a Pd-loaded granular graphite-packed electrode at different potentials and in methanol–water solutions. Analysis of the experimental results reveals that the electrocatalytic process had reached equilibrium in these experiments. The apparent equilibrium constants, as well as the rate constants for the overall forward and backward reactions, were related to the applied potential. These relationships follow the Tafel equation, but the apparent charge transfer coefficients are very small values. The potential dependence of the overall rate constants suggests a reaction mechanism in which the electrocatalytic reaction is the rate-determining step. The influence of methanol on (together with the potential dependence of) the overall rate constants and the apparent equilibrium constant suggests a Langmuir–Hinshelwood mechanism.