The Role of the Second Law of Thermodynamics in Continuum Physics: A Muschik and Ehrentraut Theorem Revisited

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In continuum physics, constitutive equations model the material properties of physical systems. In those equations, material symmetry is taken into account by applying suitable representation theorems for symmetric and/or isotropic functions. Such mathematical representations must be in accordance with the second law of thermodynamics, which imposes that, in any thermodynamic process, the entropy production must be nonnegative. This requirement is fulfilled by assigning the constitutive equations in a form that guaranties that second law of thermodynamics is satisfied along arbitrary processes. Such an approach, in practice regards the second law of thermodynamics as a restriction on the constitutive equations, which must guarantee that any solution of the balance laws also satisfy the entropy inequality. This is a useful operative assumption, but not a consequence of general physical laws. Indeed, a different point of view, which regards the second law of thermodynamics as a restriction on the thermodynamic processes, i.e., on the solutions of the system of balance laws, is possible. This is tantamount to assuming that there are solutions of the balance laws that satisfy the entropy inequality, and solutions that do not satisfy it. In order to decide what is the correct approach, Muschik and Ehrentraut in 1996, postulated an amendment to the second law, which makes explicit the evident (but rather hidden) assumption that, in any point of the body, the entropy production is zero if, and only if, this point is a thermodynamic equilibrium. Then they proved that, given the amendment, the second law of thermodynamics is necessarily a restriction on the constitutive equations and not on the thermodynamic processes. In the present paper, we revisit their proof, lighting up some geometric aspects that were hidden in therein. Moreover, we propose an alternative formulation of the second law of thermodynamics, which incorporates the amendment. In this way we make this important result more intuitive and easily accessible to a wider audience.