Stochastic thermodynamics of reactive systems: An extended local equilibrium approach.

Abstract

The recently developed extended local equilibrium approach to stochastic thermodynamics is applied to reactive systems. The properties of the fluctuating entropy and entropy production are analyzed for general linear and for prototypical nonlinear kinetic processes. It is shown that nonlinear kinetics typically induces deviations of the mean entropy production from its value in the deterministic (mean-field) limit. The probability distributions around the mean are derived and shown to qualitatively differ in thermodynamic equilibrium, under nonequilibrium conditions and in the vicinity of criticalities associated to the onset of multistability. In each case large deviation-type properties are shown to hold. The results are compared with those of alternative approaches developed in the literature.