Nonlinear Closure Relations Theory for Transport Processes in Non-Equilibrium Systems

TL;DR

This paper advances the Thermodynamic Field Theory by removing previous restrictions, introducing a new geometric formalism, and deriving nonlinear transport equations applicable to non-equilibrium systems like plasmas and chemical reactions.

Contribution

It presents a reformulated TFT with a new entropy-covariant formalism and nonlinear closure equations, extending the theory's applicability to complex non-equilibrium systems.

Findings

Validated the universal criterion of evolution geometrically.

Derived nonlinear corrections to Onsager's transport coefficients.

Revealed the thermodynamic space's non-Riemannian geometry, approaching Riemannian at high entropy production.

Abstract

A decade ago, a macroscopic theory for closure relations has been proposed for systems out of Onsager's region. This theory is referred to as the "Thermodynamic Field Theory" (TFT). The aim of the work was to determine the nonlinear flux-force relations that respect the thermodynamic theorems for systems far from equilibrium. We propose a new formulation of the TFT where one of the basic restrictions, namely the closed-form solution for the skew-symmetric piece of the transport coefficients, has been removed. In addition, the general covariance principle is replaced by the De Donder-Prigogine thermodynamic covariance principle (TCP). The introduction of TCP requires the application of an appropriate mathematical formalism, which is referred to as the "entropy-covariant formalism". By geometrical arguments, we prove the validity of the Glansdorff-Prigogine Universal Criterion of Evolution. A new set of closure equations determining the nonlinear corrections to the linear ("Onsager") transport coefficients is also derived. The geometry of the thermodynamic space is non-Riemannian. However, it tends to be Riemannian for high values of the entropy production. In this limit, we recover the transport equations found by the old theory. Applications of our approach to transport in magnetically confined plasmas, materials submitted to temperature and electric potential gradients or to unimolecular triangular chemical reactions can be found at references cited herein. Transport processes in tokamak plasmas are of particular interest. In this case, even in absence of turbulence, the state of the plasma remains close to (but, it is not in) a state of local equilibrium. This prevents the transport relations from being linear.