Abstract
The fundamental property of electrolytic systems involved with linear combination f12 = 2∙f(O) – f(H) of elemental balances: f1 = f(H) for Y1 = H, and f2 = f(O) for Y2 = O, is presented. The dependency/independency of the f12 on Charge Balance (f0 = ChB) and other elemental and/or core balances fk = f(Yk) (k = 3,…,K) is the general criterion distinguishing between non-redox and redox systems. The f12 related to a redox system is the primary form of a Generalized Electron Balance (GEB), formulated for redox systems within the Generalized Approach to Electrolytic System (GATES) as GATES/GEB ⊂ GATES. The set of K balances f0,f12,f3,…,fK is necessary/ sufficient/needed to solve an electrolytic redox system, while the K-1 balances f0,f3,…,fK are the set applied to solve an electrolytic non-redox system. The identity (0 = 0) procedure of checking the linear independency/ dependency property of f12 within the set f0,f12,f3,…,fK (i) provides the criterion distinguishing between the redox and non-redox systems and (ii) specifies Oxidation Numbers (ONs) of elements in particular components of the system, and in the species formed in the system. Some chemical concepts, such as oxidant, reductant, oxidation number, equivalent mass, stoichiometry, perceived as derivative within GATES, are indicated. All the information is gained on the basis of the titration Ce(SO4)2 (C) + H2SO4 (C1) + CO2 (C2) ⇨ FeSO4 (C0) + H2SO4 (C01) + CO2 (C02), simulated with use of the iterative computer program MATLAB.
Highlights
Redox systems are the most important and the most complex electrolytic systems, when formulated for thermodynamic purposes
The f12 related to a redox system is the primary form of a Generalized Electron Balance (GEB), formulated for redox systems within the Generalized Approach to Electrolytic System (GATES) as GATES/GEB GATES
The correct thermodynamic approach to the problem within GATES/GEB is based on a solution of a system of algebraic equations, not on a chemical reaction notation, as were done previously/elsewhere
Summary
Redox systems are the most important and the most complex electrolytic systems, when formulated for thermodynamic purposes. Derivation of GEB according to the Approach II is more laborious (timeconsuming), it enables to formulate this balance without prior knowledge of Oxidation Numbers (ONs) for the elements, involved in components forming a system, and in species of the system formed. Different forms of GEB, resulting from linear combinations of charge and elemental balances related to D + T system, will be obtained. According to Approach I to GEB, the common pool of electrons, introduced by Fe and Ce as the electronactive elements (players) [15], is (ZFe-2)·N01 + (ZCe-4)·N05 These electrons are dissipated between different species formed by Fe and Ce in the mixture, namely: (ZFe-2)N9 of Fe-electrons in Fe+2·n9H2O, (ZFe-2)N13 of Fe-electrons in FeOH+1·n13H2O, ...
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