O[sub 2] Mass-Transfer Function for Polymer-Filmed Metal Electrodes. Application to the Linear Sweep Voltammetry Method

reduction kinetics on polymer‐filmed electrodes have been investigated theoretically. A general expression is derived for the mass‐transfer function and applied to the linear sweep voltammetry method. The diffusion‐limiting conditions are analyzed, first considering a polymer‐filmed electrode in a quiescent solution, and a case diagram is plotted which makes it possible to predict the operating conditions required for the observation of the limiting voltammograms. The influence of the electrode rotation rate is also investigated for the linear sweep voltammetry method used with rotating disk electrodes. The theoretical derivations are also valid for other electroactive species diffusing both in the solution and in the polymer film. Based on the theoretical derivations, previous results in the electrochemical literature are discussed. © 2000 The Electrochemical Society. All rights reserved.