Non-equilibrium nanothermodynamics

TL;DR

This paper develops a framework for understanding entropy production in nanosystems outside the thermodynamic limit using Hill's nanothermodynamics, linking external influences to irreversible work and confirming Onsager's symmetry under certain conditions.

Contribution

It introduces a formulation of entropy production for nanosystems using Hill's nanothermodynamics and establishes conditions for Onsager's symmetry to hold in such systems.

Findings

Entropy production expressed as flux-force products.

Onsager's symmetry proven for nanosystems under specific conditions.

Explicit relations between macroscopic and nanosystem coefficients.

Abstract

Entropy production for a system not in the thermodynamic limit is formulated using Hill's nanothermodynamics, in which a macroscopic ensemble of such systems is considered. External influence of the environment on the average nanosystem is connected to irreversible work with an explicit formula based on Jarzynsky equality. Entropy production retains its usual form as a sum of products of fluxes and forces and Onsager's symmetry principle is proven to hold for the average nanosystem if it is valid for the macroscopic ensemble, by two methods. The first one provides expressions that relate the coefficients of the two systems. The second gives a general condition for a system under a external force to preserve Onsager's symmetry.