Linear sweep voltammetry in flooded porous electrodes at low sweep rates

Abstract A theoretical analysis of linear sweep voltammetry (LSV) in flooded-porous electrodes is treated for reversible (Nernstian) and first-order irreversible reactions. At low sweep rates, the ohmic potential drop within the electrode is negligible and concentration gradients are predominantly in the axial direction. The solution to the reversible case is mathematically simple, but the results are presented to understand the influence external mass-transfer resistance has on the voltammogram. For irreversible kinetics, a Green’s function technique is used to obtain an analytical solution to the diffusion equation. An analytical solution for the current as a function of the electrode dimensions, sweep rate and reaction kinetic parameters allows one to predict the voltammogram over a wide range of conditions. The analytical solution is used to develop correlations that enable the kinetic parameters (i.e. exchange current density per unit volume and the transfer coefficient) to be easily extracted from experimental data.