A General Property Differentiating Between Redox and Non-Redox Electrolytic Systems and Its Consequences

The general property of electrolytic systems with aqueous solutions is presented. For this purpose, the linear combination 2∙f(O) – f(H) of elemental balances: f(H) for hydrogen (H) and f(O) for oxygen (O) is put in context with other elemental or core balances f(Ym) (Ym ≠ H, O), and charge balance (ChB) related to the system in question. It is stated that 2∙f(O) – f(H) is (a) linearly independent on f(Ym) and ChB for a redox system, or (b) is linearly dependent on ChB and f(Ym) when related to a non-redox system. The general manner of formation of the intended/desired linear combination is indicated. The balance 2∙f(O) – f(H) is the primary form of the generalized electron balance (GEB), completing the set of equations needed for quantitative description of electrolytic redox systems, pr-GEB = 2∙f(O) – f(H), according to principles of the generalized approach to electrolytic systems (GATES). The GEB is perceived as a Law of Nature, as the hidden connection of physicochemical laws. This manner of GEB formulation needs none prior information on oxidation numbers for elements in components forming a (static or dynamic) system, and in the species of the system thus formed. Within GATES/GEB, the roles of oxidants and reductants are not indicated a priori at the stage of formulation of the related balances in redox systems. These properties can be generalized on non-redox and redox systems of any degree of complexity, also in mixed-solvent media, with amphiprotic co-solvent(s) involved.