On the Validity of the Assumption of Local Equilibrium in Non-Equilibrium Thermodynamics

TL;DR

This paper critically examines the foundational assumptions of non-equilibrium thermodynamics, questioning the validity of local equilibrium, the definition of entropy-density, and the derivation of entropy production, thus challenging the applicability of thermodynamics to far-from-equilibrium systems.

Contribution

It provides a rigorous critique of the assumptions underlying non-equilibrium thermodynamics, highlighting fundamental issues with local equilibrium and entropy concepts.

Findings

Local equilibrium assumption is ill-founded

Difficulty in defining an entropy-density function

Uncertainty about integrating entropy-density to obtain total entropy

Abstract

The extension of equilibrium thermodynamics to non-equilibrium systems is based on the assumption of "local equilibrium," followed by the assumption that an entropy-density function may be defined, and that this entropy-density would have the same functional dependence on the local densities, (u,v,n), as the total entropy S on the variables (U,V,N). In this article we question the validity of all the assumptions made in the theory of non-equilibrium thermodynamics. We find that the assumption of "local equilibrium" is ill-founded, that it is not clear how to define an entropy-density function, and it is far from clear that such a function, if it exists at all could be integrated to obtain the so-called "entropy production" of the entire system. These findings shed serious doubt on the validity of applying thermodynamic theory to systems far from equilibrium systems.