What is it about?
The concept of equivalent systems from the thermodynamic point of view was originally introduced by Th. De Donder and I. Prigogine. However, the De Donder-Prigogine definition of thermodynamic invariance based only on the invariance of the entropy production is not sufficient to guarantee the equivalence character between two sets of thermodynamic forces and conjugate thermodynamic fluxes. In addition, it is known that there exists a large class of flux-force transformations such that, even though they leave unaltered the expression of the entropy production, they may lead to certain paradoxes. Main objective of this series of works is to determine the non-linear closure equations (i.e. the flux- force relations), valid for thermodynamic systems outside the Onsager region, which do not contain inconsistencies. To this aim, a thermodynamic theory for irreversible processes [referred to as the Thermodynamical Field Theory (TFT)] has been developed. The TFT rests upon the concept of equivalence between thermodynamic systems. More precisely, the equivalent character of two alternative descriptions of a thermodynamic system is ensured if, and only if, the two sets of thermodynamic forces are linked with each other by the so-called Thermodynamic Coordinate Transformations (TCT). In this work, we describe the Lie group associated to the TCT. The TCT guarantee the validity of the so-called Thermodynamic Covariance Principle (TCP): “The nonlinear closure equations, i.e., the flux-force relations, everywhere and in particular outside the Onsager region, must be covariant under TCT”. In other terms, the fundamental laws of thermodynamics should be manifestly covariant under transformations between the admissible thermodynamic forces, i.e., under TCT. The TCP ensures the validity of the fundamental theorems for systems far from equilibrium. We shall see that the requirement of the validity of the TCP will impose strict restrictions allowing determining, for example, the expression of the collisional operator for magnetically confined plasmas.
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Why is it important?
Thermodynamic Covariance Principle (TCP) : All thermodynamic equations involving the thermodynamic forces and conjugate flows (e.g., the closure equations) must be covariant under Thermodynamic Covariant Transformations (TCT).
Perspectives
According to the TCP, "the fundamental laws of thermodynamics should be manifestly covariant under transformations between the admissible thermodynamic forces, i.e., under TCT". The TCP ensures the validity of the fundamental theorems for systems far from equilibrium. We shall see that the requirement of the validity of the TCP will impose strict restrictions allowing determining, for example, the expression of the collisional operator for magnetically confined plasmas.
Prof. Giorgio Sonnino
Université Libre de Bruxelles (ULB)
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This page is a summary of: Current Perspectives on Chemical Sciences Vol. 2, October 2020, Sciencedomain International,
DOI: 10.9734/bpi/cpcs/v2.
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