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. 2007 Jan 3;2(1):e144.
doi: 10.1371/journal.pone.0000144.

Relationship between thermodynamic driving force and one-way fluxes in reversible processes

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Relationship between thermodynamic driving force and one-way fluxes in reversible processes

Daniel A Beard et al. PLoS One. .

Abstract

Chemical reaction systems operating in nonequilibrium open-system states arise in a great number of contexts, including the study of living organisms, in which chemical reactions, in general, are far from equilibrium. Here we introduce a theorem that relates forward and reverse fluxes and free energy for any chemical process operating in a steady state. This relationship, which is a generalization of equilibrium conditions to the case of a chemical process occurring in a nonequilibrium steady state in dilute solution, provides a novel equivalent definition for chemical reaction free energy. In addition, it is shown that previously unrelated theories introduced by Ussing and Hodgkin and Huxley for transport of ions across membranes, Hill for catalytic cycle fluxes, and Crooks for entropy production in microscopically reversible systems, are united in a common framework based on this relationship.

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Conflict of interest statement

Competing Interests: The authors have declared that no competing interests exist.

Figures

Figure 1
Figure 1. Example enzyme mechanisms for the reaction AB.
The left panel illustrates the Michaelis-Menten scheme of Equation (8), in which enzyme binds to substrate A, forming a complex C. The product B reversibly dissociates from the complex C, forming unbound enzyme E. The right panel illustrates a more complex mechanism involving three enzyme states E1, E2, and E3. Enzyme kinetic theory assumes that the state transitions follow mass-action kinetics, as described by Equation (8) for the left panel and Equation (23) for the right panel.

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