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The Generalized Approach To Electrolytic Systems (GATES) (Michalowski, 2001, 2010) provides the possibility of thermodynamic description of equilibrium and metastable, redox and non-redox, mono-, twoand three-phase systems, with the possibility of all attainable/pre-selected physicochemical knowledge to be involved, with none simplifying assumptions done for calculation purposes, where different types of reactions occur in batch or dynamic systems, of any degree of complexity. The Generalized Electron Balance (GEB) concept, devised and formulated by Michalowski (1992), and obligatory for description of redox systems, is fully compatible with charge and concentration balances, and relations for the corresponding equilibrium constants. Up to 1992, the generalized electron balance (GEB) concept was the lacking segment needed to formulate the compatible set of algebraic balances referred to redox systems. The GEB is also applicable for the systems where radical species are formed. Shortly after GEB formulation, the GATES involving redox systems of any degree of complexity, was elaborated. In this chapter, some examples of complex redox systems, where all types of elementary chemical reactions proceed simultaneously and/or sequentially, are presented. In all instances, one can follow measurable quantities (potential E, pH) in dynamic and static processes and gain the information about details not measurable in real experiments; it particularly refers to dynamic speciation. In the calculations made according to iterative computer programs, e.g., MATLAB, all physicochemical knowledge can be involved and different “variations on the subject” are also possible; it particularly refers to metastable and non-equilibrium systems. The Generalized Equivalent Mass (GEM) concept, also devised (1979) by Michalowski (Michalowski et al., 2010), has been suggested, with none relevance to a chemical reaction notation. Within GATES, the chemical reaction notation is only the basis to formulate the expression for the related equilibrium constant.

Application of GATES and MATLAB for Resolution of Equilibrium, Metastable and Non-Equilibrium Electrolytic Systems