Second law and Liu relations: the no-reversible-direction axiom—revisited

A thermodynamic process is governed by balance equations in field-formulated thermodynamics. Especially the balance equation of entropy takes a prominent role: it introduces the Second Law in the form of a dissipation inequality via the non-negative entropy production. Balance equations and dissipation inequality are independent of the considered material which is described by additional constitutive equations which need the introduction of a state space which is spanned by the state space variables. Inserting these constitutive equations into the balance equations results in the balance equations on state space which include the first order time and position derivatives of the state space variables, called “higher derivatives” wich are directional derivatives in a mathematicle sense. Why do not appear the latter in the Liu Relations which pretend to describe material as well as the equations on state space do ? The answer is that the Liu Relations describe materials whose entropy production does not depend on the higher derivatives. Consequently, the Liu Relations are more specific than the balance equations on state space. A toy example concerning heat conduction in compressible fluids is in two different versions added for elucidation.