Channel electrode voltammetry: Thin-layer effects and the shape of quasi-reversible current-voltage curves

A computational approach to the calculation of irreversible and quasi-reversible current voltage curves at channel electrodes is presented. The method has generality since, in particular, no assumptions are made as to the electrode geometry or electrolyte flow rates so that both Lévěque and, with novelty, thin-layer conditions may be explored. An approximate analytical theory for the shape of current-voltage curves which predicts the flow rate dependence of the half-wave potential is presented for the latter case and found to be in good agreement with rigorous computational theory