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The balance 2∙f(O)f(H) provides a general criterion distinguishing between electrolytic redox and non-redox systems of any degree of complexity, in aqueous, non-aqueous and mixed-solvent media. When referred to redox systems, it is an equation linearly independent on charge (ChB) and elemental/core balances f(Yg) for elements/cores Yg 61⁄4 H and O, whereas for non-redox systems, 2∙f(O)f(H) is linearly dependent on these balances. The balance 2∙f(O)f(H) formulated for redox systems is the primary form (pr-GEB) of the generalized electron balance (GEB) as the fundamental equation needed for resolution of these systems. Formulation of GEB for redox systems needs no prior knowledge of oxidation numbers for all elements of the system. Any prior knowledge of oxidation numbers for all elements in components forming a redox system and in the species of the system thus formed is not necessary within the Approach II to GEB. Oxidants and reductants are not indicated. Stoichiometry and equivalent mass are redundant concepts only. The GEB, together with charge balance and concentration balances for elements 61⁄4 H and O, and the complete set of independent equations for equilibrium constants form an algorithm, resolvable with use of an iterative computer program. All attainable physicochemical knowledge can be included in the algorithm. Some variations involved with tests of possible reaction paths for metastable systems can also be made. The effects of incomplete physicochemical knowledge on the system can be also tested. One of the main purposes of this chapter is to provide the GEB formulation needed for resolution of redox systems and familiarize it to a wider community of chemists.

A Distinguishing Feature of the Balance 2∙f(O)−f(H) in Electrolytic Systems: The Reference to Titrimetric Methods of Analysis