Electrochemical kinetics at microelectrodes: Part II. Cyclic voltammetry at band electrodes

Abstract

Cyclic voltammetry has been considered at a band electrode, a two dimensional structure with a length much longer than its width and situated in an insulating plane. The relevant diffusion-electrochemical equations have been evaluated by digital simulation. The simulation employs the hopscotch method and uses a conformal map which simplifies the problem of nonuniform current distribution across the band at low scan rates or at small values of the band width. The results of the simulation are found to agree with voltammograms obtained for the oxidation of ferrocene at a band electrode. In addition, the simulation predicts that reasonable estimates of the voltammetric shape and amplitude can be made by considering electrochemical processes at cylinder electrodes, a case for which analytical solutions are available. Examination of the simulated current density for the case of slow charge transfer shows that the current is more uniform across the surface for this case than for the reversible case.