Abstract
The formalism realised according to the Generalised Approach to Electrolytic Systems (GATES) is presented and applied to typical redox systems known from the laboratory practice. In any redox system, the Generalized Electron Balance (GEB), perceived as the law of the matter conservation, is derivable from linear combination 2·f(O) – f(H) of elemental balances: f(O) for oxygen and f(H) for hydrogen. It is an equation linearly independent from other (charge and concentration) balances referred to an electrolytic redox system (aqueous media) of any degree of complexity, and named as the primary form of GEB and then denoted as pr-GEB. A compact equation for GEB is obtained from linear combination of 2·f(O) – f(H) with other (charge and concentration) balances. For a non-redox electrolytic system, of any degree of complexity, the balance 2·f(O) – f(H) is not an independent equation. In the derivation of GEB, all known components (species) of the system tested, taken in their real (i.e., hydrated) form, are involved in the balances, and none simplifying assumptions are needed. The redox systems are simulated with use of an iterative computer program.
Highlights
Redox systems are considered as the most important and the most complex electrolytic systems
Of correct mathematical formulation of redox systems of any degree of complexity was possible only after formulation of the Generalized Electron Balance (GEB) that is fully compatible with charge and concentration balances
The generalised approach to electrolytic systems (GATES) involving GEB concept is based on firm, mathematical foundations, not on an extremely ‘fragile’ chemical notation principle, that is only a faint imitation of a true, algebraic notation
Summary
Redox systems are considered as the most important and the most complex electrolytic systems. The great advantage of the Approach II, called as the “long” version of GEB, is that none prior knowledge on oxidation degrees of all elements in complex species of definite composition and charge is needed Both approaches are valid for aqueous and mixed-solvent media, with amphiprotic co-solvents involved. The present article provides typical examples of formulation of the balances according to both Approaches (I, II) for dynamic redox systems, realized within GATES in titrimetric methods of analysis [5] [6] For this purpose, we consider V0 mL of FeSO4 (C0) + H2SO4 (C01) solution as titrand (D) titrated with V mL of KMnO4 (C). All concentrations are expressed in mol/L, and all volumes in mL
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