Mathematical Formalism of Nonequilibrium Thermodynamics for Nonlinear Chemical Reaction Systems with General Rate Law

TL;DR

This paper develops a mathematical framework for nonequilibrium thermodynamics in nonlinear chemical reaction systems, extending classical thermodynamics to stochastic models with general rate laws and establishing new principles like a generalized free energy and fluctuation theorem.

Contribution

It introduces a novel macroscopic chemical free energy function and balance equation derived from mesoscopic Markovian kinetics, generalizing classical thermodynamics to nonequilibrium nonlinear systems.

Findings

Established a generalized macroscopic free energy function.

Proved a fluctuation dissipation theorem for stochastic reaction kinetics.

Demonstrated how macroscopic laws emerge from mesoscopic stochastic models.

Abstract

This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with $N$ species, $M$ reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemistry kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy function and its associated balance equation with nonnegative source and sink are the major discoveries. The proof is based on the large deviation principle of this type of Markov processes. A general fluctuation dissipation theorem for stochastic reaction kinetics is also proved. The mathematical theory illustrates how a novel macroscopic dynamic law can emerges from the mesoscopic kinetics in a multi-scale system.