Linear sweep voltammetry in flooded porous electrodes at low sweep rates

A theoretical analysis of linear sweep voltammetry (LSV) in flooded-porous electrodes is treated for reversible (Nernstian) and first-order irreversib le reactions. At low sweep rates, the ohmic potential drop within the elect rode is negligible and concentration gradients are predominantly in the axi al direction. The solution to the reversible case is mathematically simple, but the results are presented to understand the influence external mass-tr ansfer resistance has on the voltammogram. For irreversible kinetics, a Gre en's function technique is used to obtain an analytical solution to the dif fusion equation. An analytical solution for the current as a function of th e electrode dimensions, sweep rate and reaction kinetic parameters allows o ne to predict the voltammogram over a wide range of conditions. The analyti cal solution is used to develop correlations that enable the kinetic parame ters (i.e. exchange current density per unit volume and the transfer coeffi cient) to be easily extracted from experimental data. (C) 1998 Elsevier Sci ence S.A. All rights reserved.