USE OF SENSITIVITY ANALYSIS-METHODS IN THE MODELING OF ELECTROCHEMICAL TRANSIENTS - PART 1 - GAINING MORE INSIGHT INTO THE BEHAVIOR OF KINETIC-MODELS

Sensitivity analysis is a commonly accepted methodology of studying th e effect of parameter variations on the behaviour of mathematical mode ls in various branches of chemical kinetics. However, it has not yet f ound wider application in electrochemical kinetics. In this paper we p erform an introductory investigation of the utility of formal methods of sensitivity analysis for the modelling of electrochemical transient s. We calculate and analyse first-order parametric sensitivity coeffic ients for the cyclic voltammetric transient corresponding to a quasi-r eversible charge-transfer reaction E-qrev, assuming potential-dependen t charge-transfer coefficients, and for the chronopotentiometric trans ient corresponding to a CrevE reaction mechanism, taken as example pro blems. We show that this local sensitivity analysis provides straightf orward quantitative answers to a number of fundamental questions about the dependencies of the transients on model parameters. Therefore, we recommend that sensitivity analysis be used in conjunction with tradi tional digital simulations, resulting in an added insight into the beh aviour of kinetic models. (C) 1998 Elsevier Science S.A.