Importance of Correct Prediction of Initial Concentrations in Voltammetric Scans: Contrasting Roles of Thermodynamics, Kinetics, and Natural Convection

In order to successfully model an electrochemical reaction mechanism one must ensure that all the equations, including initial conditions, satisfy the pertinent thermodynamic and kinetic relationships. Failure to do so may lead to invalid results even if they are mathematically correct. This fact has been previously emphasized (Luo, W.; Feldberg, S. W.; Rudolph, M. J. Electroanal. Chem. 1994, 368, 109-113; Rudolph, M. Digital Simulation in Electrochemistry. In Physical Electrochemistry; Rubenstein, I., Ed.; Marcel Dekker: New York, 1995; Chapter 3) and existing computer software for electrochemical simulations, such as DigiSim (Rudolph, M.; Reddy, D. P.; Feldberg, S. W. Anal. Chem. 1994, 66, 589A; http://www.basinc.com/products/eadigisima offer the option of enforcing the so-called pre-equilibration which evaluates thermodynamic concentrations of all species prior to beginning a voltammetric scan. Although this approach allows setting consistent thermodynamic values it may result in a nonrealistic initial concentrations set because it corresponds to the whole solution status at infinite time for infinite kinetic constants. However, the perturbation created by the working electrode poised at its rest potential is necessarily limited by the size of the electrode, reaction kinetics, and duration of the rest period. Furthermore, natural convection limits even more the importance of the perturbation. This is analyzed theoretically through comparison of simulation results by DigiSim and KISSA-1D software for certain common electrochemical mechanisms in order to illustrate the importance of correct prediction of initial concentrations.