Theoretical analysis of microscopic ohmic drop effects on steady-state and transient voltammetry at the disk microelectrode: a quasi-conformal mapping modeling and simulation.
The effect of uncompensated solution resistance on steady-state and transient voltammograms at the disk microelectrode was for the first time treated theoretically and numerically at the microscopic level using specific quasi-conformal mapping for the case of absence of electric migration. It has been shown that microscopic distributions of electric potential and current density at a disk microelectrode affect the voltammetric waves at different degrees across the electrode surface due to the variation of elementary resistances and elementary current fluxes over the electrode surface which leads to nonlinear effects that have not been discussed in existing theoretical treatments of ohmic drop at microelectrodes. The analysis of steady state voltammetry in strongly resistive media under Nernstian conditions has allowed justification by appropriate analytical derivations of the widely used potential-shift correction of steady state voltammograms by plotting i vs ( E - iR e).
Amatore
Christian
C
Departement de Chimie, Ecole Normale Superieure, UMR CNRS-ENS-UPMC 8640 PASTEUR, 24 Rue Lhomond, 75231 Paris Cedex 05, France. christian.amatore@ens.fr
Oleinick
Alexander
A
Svir
Irina
I