Is the Le Chatelier-Braun Principle Valid in General in Linear Nonequilibrium Thermodynamics?

Abstract

In this paper it is shown that the validity of the Le Chatelier-Braun principle (CHBP) in linear nonequilibrium thermodynamics (LNT) is connected with the symmetry properties of the kinetic coefficients in Onsager's relations of reciprocity. If the CHBP is understood as the stability criterion of the stationary state, it is concluded that it remains valid independently of the symmetry or antisymmetry of the cross-kinetic coefficients. Another approach involves the fact that CHBP gives an account of the system's response to a real external effect due to which the system passes from the initial nonequilibrium stationary state into another nonequilibrium stationary state. We show here for a system with n forces and fluxes that the CHBP does not apply in general in the case of antisymmetric cross-kinetic coefficients. We also prove that in this case the minimum entropy production law does not apply.

Symmetry Properties of Reciprocity Relations and Conditions for Minimum Entropy Production Law (In)validity

“…As an example of the application of the obtained results we gave an analysis of the thermo-electro-magnetic phenomenon [23]. Our analysis gives the result that in this case the condition for the MEP law validity, that is, (25), is not fulfilled, thus MEP law is not valid.…”

“…The present authors analysed a system with coupled thermo-electro-magnetic effects (for more see, e.g., [23]) where the symmetric and antisymmetric cross coefficients are present. The studied system is described by four thermodynamic forces and four fluxes.…”