New trends in studies on electrolytic redox systems

The paper provides comprehensive, compatible and consistent knowledge on thermodynamics of electrolytic redox systems, and referred to aqueous media. A keystone of the overall knowledge are elemental balances: f(H) for hydrogen (H), and f(O) for oxygen (O). A new approach (Approach II) to a Generalized Electron Balance (GEB) formulation is based on a linear combination pr-GEB = 2.f(O) - f(H) of the balances, considered as the primary form of GEB in redox systems. It is proved that the pr-GEB, as the essence of the Approach II, is equivalent to the Approach I to GEB, based on the principle of common pool of electrons. The fundamental advantage of the Approach II is that none prior knowledge on oxidation degree of elements in complex species of definite elemental composition and charge is needed. The GEB is perceived as the general law of matter conservation, related to electrolytic (aqueous media) redox systems. The Approaches I and II are illustrated with several redox systems. (C) 2013 Elsevier Ltd. All rights reserved.