Conservation Laws and Work Fluctuation Relations in Chemical Reaction Networks

TL;DR

This paper develops a thermodynamic framework for open chemical reaction networks, linking their topological properties and conservation laws to entropy production, work contributions, and fluctuation theorems, with implications for equilibrium and nonequilibrium states.

Contribution

It introduces a nonequilibrium thermodynamic description for CRNs that incorporates conservation laws and topological features, extending fluctuation theorems and Landauer's principle.

Findings

Entropy production decomposed into potential change and two work contributions.

Work contributions satisfy Jarzynski and Crooks fluctuation theorems.

Minimal work to create a nonequilibrium state equals relative entropy to equilibrium.

Abstract

We formulate a nonequilibrium thermodynamic description for open chemical reaction networks (CRN) described by a chemical master equation. The topological properties of the CRN and its conservation laws are shown to play a crucial role. They are used to decompose the entropy production into a potential change and two work contributions, the first due to time dependent changes in the externally controlled chemostats concentrations and the second due to flows maintained across the system by nonconservative forces. These two works jointly satisfy a Jarzynski and Crooks fluctuation theorem. In absence of work, the potential is minimized by the dynamics as the system relaxes to equilibrium and its equilibrium value coincides with the maximum entropy principle. A generalized Landauer's principle also holds: the minimal work needed to create a nonequilibrium state is the relative entropy of that state to its equilibrium value reached in absence of any work.