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 set of thermodynamic and kinetic parameters and initial conditions that are needed for the simulation of transient electrochemical experiments, given a reaction mechanism of arbitrary complexity. This is an extension of the algorithm recently suggested by Luo et al. (J. Electroanal. Chem., 368 (1994) 109) to the larger class of reaction networks involving elementary or non-elementary electrochemical, heterogeneous non-electrochemical and homogeneous reactions of unrestricted molecularities, subject to the power rate law with reaction orders that can be different from stoichiometric coefficients. Equilibrium, non-equilibrium reversible and irreversible reactions between bulk species (distributed in the electrolyte) and interfacial species (located at electrodes) are allowed, as well as the presence of species with invariant concentrations. Tests enabling verification of the correctness of the symbolically written reaction mechanisms are described. The procedure is part of an algorithm for automatic, computer-aided translation of electrochemical reaction mechanisms into corresponding texts of mathematical governing equations.