New Stationary Methods for Studying the Kinetics of Redox Reactions Occurring at Inert Semiconductor/Redox Electrolyte Electrodes. I. The »L ∩ P« Method

In this first paper, a new method has been theoretically grounded, for studying the kinetics of redox reactions occurring simultaneously at multielectrodes of the type inert semiconductor / redox electrolyte, representing Schottky barriers. The method is based on the simultaneously changing of both the intensity of the illumination (L), and the polarization (P), of the multielectrode; for this reason, the method has been called an »intersection method«, and symbolized by »L ∩ P«. A kinetic model has been developed to account for the effects of these dL and dP variations, in open and closed circuit conditions, and on its basis, the equations of the potentiostatic and galvanostatic »L ∩ P« methods have been obtained. Further, an expression of the specific admittance has resulted, and some particular cases are given, including that of an inert metal/redox electrolyte multielectrode

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

In this second paper an other »intersection« method is theoretically grounded. The method is symbolized »a ∩ P«, 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. Equations for the potentiostatic, respective galvanostatic »a ∩ P« methods have been deduced, and some important kinetic and electroanalytic applications, especially those referring to the inert metallredox 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 expression resulted for the specific admittance is equivalent to that obtained in the first paper by using the theory of the »L ∩ P« method; this demonstrates the correctness of both »L ∩ P«, and »a ∩ P« theories

New Stationary Methods for Studying the Kinetics of Redox Reactions Occurring at Inert Semiconductor/Redox Electrolyte Electrodes. I. The »L ∩ P« Method

In this first paper, a new method has been theoretically grounded, for studying the kinetics of redox reactions occurring simultaneously at multielectrodes of the type inert semiconductor / redox electrolyte, representing Schottky barriers. The method is based on the simultaneously changing of both the intensity of the illumination (L), and the polarization (P), of the multielectrode; for this reason, the method has been called an »intersection method«, and symbolized by »L ∩ P«. A kinetic model has been developed to account for the effects of these dL and dP variations, in open and closed circuit conditions, and on its basis, the equations of the potentiostatic and galvanostatic »L ∩ P« methods have been obtained. Further, an expression of the specific admittance has resulted, and some particular cases are given, including that of an inert metal/redox electrolyte multielectrode