Nonequilibrium Thermodynamics of Chemical Reaction Networks: Wisdom from Stochastic Thermodynamics

TL;DR

This paper develops a rigorous nonequilibrium thermodynamic framework for open chemical reaction networks, linking energy, entropy, and information measures, and analyzing their steady states and relaxation dynamics.

Contribution

It introduces a comprehensive thermodynamic description for open chemical networks driven by chemostats, including energy and entropy balances and a nonequilibrium Gibbs free energy.

Findings

The nonequilibrium Gibbs free energy quantifies minimal work by chemostats.

Entropy production splits into dissipation and transient contributions.

Framework applies to biochemical networks with time-dependent energy and information transduction.

Abstract

We build a rigorous nonequilibrium thermodynamic description for open chemical reaction networks of elementary reactions. Their dynamics is described by deterministic rate equations satisfying mass action law. Our most general framework considers open networks driven by time-dependent chemostats. The energy and entropy balances are established and a nonequilibrium Gibbs free energy is introduced. The difference between this latter and its equilibrium form represents the minimal work done by the chemostats to bring the network in its nonequilibrium state. It is minimized in nondriven detailed-balanced networks (i.e. networks which relax to equilibrium states) and has an interesting information-theoretic interpretation. We further show that the entropy production of complex balanced networks (i.e. networks which relax to special kinds of nonequilibrium steady states) splits into two non-negative contributions. One charaterizing the dissipation of the nonequilibrium steady state and the other the transients due to relaxation and driving. Our theory lays the path to study time-dependent energy and information transduction in biochemical networks.