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Abstracto

GATES as the Unique Tool for Simulation of Electrolytic Redox and Non-Redox Systems

Anna Maria Michalowska- Kaczmarczyk and Tadeusz Michalowski

The Generalized Approach to Electrolytic Systems (GATES), based on physical (charge conservation), physicochemical (conservation of elements) and chemical (mass action) laws is the best theory applicable for computer simulation of equilibrium, non-equilibrium and metastable, mono- and polyphase electrolytic redox and non-redox systems. The Generalized Electron Balance (GEB) concept, related to electrolytic redox systems, is put in context with the principle of conservation of all elements in electrolytic redox systems, with aqueous, non-aqueous or mixedsolvent media. Two equivalent approaches to GEB are presented, and termed as the Approach I and Approach II to GEB. The GEB, that enters GATES as GATES/GEB, is fully compatible with charge and concentration balances and completes the set of equations necessary for thermodynamic resolution of redox systems. Computer simulation of such systems is based on all attainable physicochemical knowledge involved in the related algorithm, solvable with use of an iterative computer program, and then presented graphically. This paper is referred mainly to dynamic redox systems, realized according to titrimetric mode. The speciation diagrams for dynamic redox systems are perceived as a reasonable alternative to (static) Pourbaix diagrams. The GEB concept, unknown before 1992, is perceived as the law of the matter conservation, as the general law of Nature. From the GATES viewpoint, the stoichiometric reactions are only the basis to formulate the related equilibrium constants. GATES is also the basis for Generalized Equivalence Mass (GEM) concept, formulated with none relevance to the stoichiometry of chemical reaction notation. From the GATES viewpoint, the stoichiometry is a superfluous concept.