Physicochemical and Analytical Implications of GATES/GEB Principles

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.

Some Regularities Inherent in the Balance 2∙f(O) – f(H) Formulated for an Electrolytic System with Symproportionation Reactions Involved

The general properties of the balance f12 = 2∙f(O) – f(H), as the linear combination of elemental balances: f1 = f(H) for H and f2 = f(O) for O, formulated for electrolytic systems, are presented. These properties/regularities are inherently related to linear combination (LC) of f12 with charge (f0) and other elemental/core balances fk = f(Yk) (Yk ≠ H, O), expressed by, where the multipliers dk are involved with oxidation numbers (ONs) of the elements in the system in question. The linear dependence or independence of f12 from f0,f3,…, fK, expressed by LC, provides the general criterion distinguishing between non-redox and redox systems. The f12 is the primary form of Generalized electron balance (GEB), completing the set of K independent balances f0,f12,f3,…,fK needed for the solution of a redox system according to GATES/GEB principles. For the solution of a non-redox system, the set of K–1 independent equations f0,f3,…,fK is required. In this formulation, the terms: ONs, oxidant, reductant, and equivalent mass are derivative/redundant concepts. These properties/regularities of f12 are illustrated here by a redox system where symproportionation reactions occur.

Substituent effect on the thermophysical properties and thermal dissociation behaviour of 9-substituted anthracene derivatives

The chemical structure and location of substituents on anthracene derivatives influence the electron balance of the aromatic system, thus determining the wavelengths at which light is absorbed, which results in...

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

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.

Reductive TCA cycle enzymes and reductive amino acid synthesis pathways contribute to electron balance in aRhodospirillum rubrumCalvin cycle mutant

Purple nonsulfur bacteria (PNSB) use light for energy and organic substrates for carbon and electrons when growing photoheterotrophically. This lifestyle generates more reduced electron carriers than are required for biosynthesis, even during consumption of some of the most oxidized organic substrates like malate and fumarate. Excess reduced electron carriers must be oxidized for photoheterotrophic growth to occur. Diverse PNSB commonly rely on the CO2-fixing Calvin cycle to oxidize excess reduced electron carriers. Some PNSB also produce H2or reduce terminal electron acceptors as alternatives to the Calvin cycle.Rhodospirillum rubrumCalvin cycle mutants defy this trend by growing phototrophically on malate or fumarate without H2production or access to terminal electron acceptors. We used13C-tracer experiments to examine how aRs. rubrumCalvin cycle mutant maintains electron balance under such conditions. We detected the reversal of some TCA cycle enzymes, which carried reductive flux from malate or fumarate to α-ketoglutarate. This pathway and the reductive synthesis of amino acids derived from α-ketoglutarate are likely important for electron balance, as supplementing the growth medium with α-ketoglutarate-derived amino acids preventedRs. rubrumCalvin cycle mutant growth unless a terminal electron acceptor was provided. Flux estimates also suggested that the Calvin cycle mutant preferentially synthesized isoleucine using the reductive threonine-dependent pathway instead of the less-reductive citramalate-dependent pathway. Collectively, our results suggest that alternative biosynthetic pathways can contribute to electron balance within the constraints of a relatively constant biomass composition.