A channel electrode array, with electrodes ranging in size from the millimeter to the submicrometer scale, is used for the amperometric interrogation of mechanistically complex electrode processes. In this way, the transport-limited current, measured as a function of both electrode size and electrolyte flow rate (convection), is shown to provide a highly sensitive probe of mechanism and kinetics. The application of "two-dimensional voltammetry" to diverse electrode processes, including E, ECE, ECEE, EC', and DISP2 reactions, is reported.

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The theory of``two-dimensional voltammetry'' using arrays of gold channel microband electrodes ranging in size from the millimeter to the micrometer scale is extended to permit the deduction of electrochemical rate constants through the analysis of hydrodynamic voltammograms as a function of both electrode size and electrolyte¯ow rate (convection). The technique is applied to the reduction of p-chloranil and the oxidation of 2,3,7,8-tetramethoxythianthrene both in acetonitrile solution and electrochemical rate constants are reported.