Nonequilibrium Thermodynamics of Non-Ideal Chemical Reaction Networks

TL;DR

This paper develops a general nonequilibrium thermodynamics framework for open chemical reaction networks that includes interactions between species, extending beyond the ideal non-interacting assumption and identifying key thermodynamic quantities.

Contribution

It introduces a mean-field approach with activity coefficients, modifying rate equations to include concentration-dependent kinetics for non-ideal systems.

Findings

Reproduces features of ideal formulations

Identifies thermodynamic potential and driving forces in non-ideal systems

Provides a general theory applicable to various interaction models

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.