New Stationary Methods for Studying the Kinetics of Redox Reactions Occurring at Inert Semiconductor/Redox Electrolyte Electrodes. II. The »aÇP « Method

In this second paper an other »intersection « method is theoretically grounded. The method is symbolized »aP«, and it is based on the simultaneously changing of both the activity (activities) of one (or more) electrochemical active species (a), and the polarization (P), of the multielectrode: inert semiconductor/redox electrolyte. Equa-tions for the potentiostatic, respective galvanostatic »aP « methods have been deduced, and some important kinetic and electroanaly-tic applications, especially those referring to the inert metal/redox electrolyte unielectrodes are given. These methods permit not only to determine the kinetic parameters, but also to separate the total current density j(U) into the two partial current densities j+(U), j–(U), irrespective of the electrode potential U. Finally, the expres-sion resulted for the specific admittance is equivalent to that ob-tained in the first paper by using the theory of the »LP « method; this demonstrates the correctness of both »LP«, and »aP « theo-ries. Key words: kinetics of redox reactions, multielectrodes, activities, polarization, inert semiconductor/redox electrolyte * Author to whom correspondence should be addressed. CROATICA CHEMICA ACTA CCACAA 73 (2) 471¿484 (2000