AUTOMATIC DERIVATION OF THE GOVERNING EQUATIONS THAT DESCRIBE A TRANSIENT ELECTROCHEMICAL EXPERIMENT, GIVEN A REACTION-MECHANISM OF ARBITRARY COMPLEXITY .1. PROBLEM PARAMETERS AND INITIAL CONDITIONS

We describe a systematic procedure for determining a self-consistent s et of thermodynamic and kinetic parameters and initial conditions that are needed for the simulation of transient electrochemical experiment s, given a reaction mechanism of arbitrary complexity. This is an exte nsion of the algorithm recently suggested by Luo et al. (J. Electroana l. Chem., 368 (1994) 109) to the larger class of reaction networks inv olving elementary or non-elementary electrochemical, heterogeneous non -electrochemical and homogeneous reactions of unrestricted molecularit ies, subject to the power rate law with reaction orders that can be di fferent from stoichiometric coefficients. Equilibrium, non-equilibrium reversible and irreversible reactions between bulk species (distribut ed in the electrolyte) and interfacial species (located at electrodes) are allowed, as well as the presence of species with invariant concen trations. Tests enabling verification of the correctness of the symbol ically written reaction mechanisms are described. The procedure is par t of an algorithm for automatic, computer-aided translation of electro chemical reaction mechanisms into corresponding texts of mathematical governing equations.