Non-equilibrium thermodynamics. II: Application to inhomogeneous systems

TL;DR

This paper extends non-equilibrium thermodynamics to inhomogeneous systems by considering subsystems and their interactions, deriving entropy formulations, and discussing implications for thermodynamic potentials, internal variables, and irreversible processes.

Contribution

It introduces a Gibbsian framework for inhomogeneous systems composed of quasi-independent subsystems, differing from traditional approaches by incorporating medium parameters and relative motions.

Findings

Entropy additivity requires quasi-independence of subsystems.

Thermodynamic potentials depend on medium parameters even if not locally defined.

Relative motion between subsystems leads to viscous dissipation.

Abstract

We provide an extension of a recent approach to study non-equilibrium thermodynamics [Phys. Rev. E 81, 051130 (2010), to be denoted by I in this work] to inhomogeneous systems by considering the latter to be composed of quasi-independent subsystems. The system {\Sigma} along with the (macroscopically extremely large) medium {\Sigma} forms an isolated system {\Sigma}_0. Starting from the Gibbsian formulation of the entropy for {\Sigma}_0, which is valid even when {\Sigma}_0 is out of equilibrium, we derive the Gibbsian formulation of the entropy of {\Sigma}, which need not be in equilibrium. The additivity of entropy requires quasi-independence of the subsystems, which limits the size of various subsystems. The thermodynamic potentials of subsystems such as the Gibbs free energy are determined by the field parameters (temperature, pressure, etc.) of the medium even if the latter may not exist for the subsystems. This and the requirement of quasi-independence make our approach different from the conventional approach due to de Groot and others. As the energy depends on the frame of reference, the thermodynamic potentials and Gibbs fundamental relation, but not the entropy, depend on the frame of reference. The possibility of relative motion between subsystems described by their net linear and angular momenta gives rise to viscous dissipation. Important consequences of internal equilibrium are discussed. Internal variables as variables that cannot be controlled by the observer for non-equilibrium evolution are also discussed. We finally formulate the non-equilibrium thermodynamics of inhomogeneous systems. We also briefly discuss the case when bodies form an isolated system without any medium to obtain their irreversible contributions and show that this case is no different than when bodies are in an extremely large medium.