GATES/GEB as the Best Thermodynamic Approach to Electrolytic Redox Systems - a Review

Anna M. Michałowska-Kaczmarczyk,Mohammad Tavakkoli,Tadeusz Michałowski

doi:10.14302/issn.2377-2549.jndc-20-3583

Abstract

The Generalized Approach To Electrolytic Systems (GATES) provides the best possible thermodynamic formulation of redox and non-redox, equilibrium and metastable, mono-, two- and three-phase systems, with all attainable/pre-selected physicochemical knowledge involved, without any simplifying assumptions made for calculation purposes, where different species may occur in batch or dynamic systems, of any degree of complexity. The Generalized Electron Balance (GEB) is the key concept completing the set of algebraic balances referred to redox systems, described according to GATES/GEB ⊂ GATES principles. The GEB, considered as the law of Nature, is fully compatible with charge and concentration balances, and relations for the corresponding equilibrium constants. Within GATES, the electrolytic systems are resolvable with use of MATLAB, or other iterative computer programs, if all necessary physicochemical knowledge is attainable.

Highlights

The paper refers to fundamental/general regularities obligatory for electrolytic systems
It is stated that f12 is (1o) linearly independent on f0,f3, ...,fK for a redox system, or (2o) linearly dependent on f0,f3,...,fK when related to a non-redox system, and the independency/dependency property of f12 (3o) provides a rigorous criterion distinguishing between redox and non-redox systems [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18]
As the independent balance for a redox system, (4o) f12 is considered as the primary form of Generalized Electron Balance (GEB). f12 = pr-GEB, according to Approach II to GEB. (5o) f12 is fully compatible with f0,f3,...,fK, and (6o) f12 completes the set of K equations f0,f12,f3,...,fK, necessary for thermodynamic solution of a redox system according to Generalized Approach to Redox Systems (GATES) [1,19]; (7o) The set of K–1 balances f0,f3,...,fK is necessary for the solution of a non-redox system; (8o) all relevant, available physicochemical knowledge can be applied for this formulation

Summary

Introduction

The paper refers to fundamental/general regularities obligatory for electrolytic systems. (5o) f12 is fully compatible with f0,f3,...,fK, and (6o) f12 completes the set of K equations f0,f12,f3,...,fK, necessary for thermodynamic solution of a redox system according to Generalized Approach to Redox Systems (GATES) [1,19]; (7o) The set of K–1 balances f0,f3,...,fK is necessary for the solution of a non-redox system; (8o) all relevant, available physicochemical knowledge can be applied for this formulation. Within GATES, f12 (14o) indicates the unique, distinctive role of the two elements: Y1 = H and Y2 = O in mathematical description of electrolytic (redox and non-redox) systems of any degree of complexity, limited only by the quantitative, physicochemical knowledge related to the system in question, and GATES/GEB provides the best thermodynamic approach to electrolytic (static and dynamic) redox systems, of any degree of complexity. One can follow measurable quantities (potential E, pH) in dynamic and static processes and gain the information about many details not measurable in real experiments; it refers to dynamic speciation

Linear Dependency or Independency of Equations

Components and Species

Elemental and Core Balances

Static and Dynamic Systems

The D Subsystem

The T Subsystem

Calculation Procedure and Graphical Presentation of the Results Obtained

Final Comments

Instead of Epilogue