Nonequilibrium Thermodynamics of Non-Ideal Chemical Reaction Networks

Abstract

All current formulations of nonequilibrium thermodynamics of open chemical reaction networks rely on the assumption of non-interacting species. We develop a general theory which accounts for interactions between chemical species within a mean-field approach using activity coefficients. Thermodynamic consistency requires that rate equations do not obey to standard mass-action kinetics, but account for the interactions with concentration dependent kinetic constants. Many features of the ideal formulations are recovered. Crucially, the thermodynamic potential and the forces driving non-ideal chemical systems out of equilibrium are identified. Our theory is general and holds for any mean-field expression of the interactions leading to lower bounded free energies.

References in corpus (5)

• Ensemble and Trajectory Thermodynamics: A Brief Introduction
• Stochastic thermodynamics of chemical reaction networks
• Irreversible thermodynamics of open chemical networks I: Emergent cycles and broken conservation laws
• Thermodynamics of Non-Elementary Chemical Reaction Networks
• Length and sequence relaxation of copolymers under recombination reactions

Cited by in corpus (4)

• Nonequilibrium thermodynamics of light-induced reactions
• Trade-offs between number fluctuations and response in nonequilibrium chemical reaction networks
• Linear response in large deviations theory: A method to compute non-equilibrium distributions
• Deficiency, Kinetic Invertibility, and Catalysis in Stochastic Chemical Reaction Networks