Abstract

According to second law of thermodynamics, the local entropy production must be nonnegative for arbitrary thermodynamic processes. In 1996, Muschik and Ehrentraut observed that such a constraint can be fulfilled in two different ways: either by postulating a suitable form of the constitutive equations, or by selecting among the solutions of the systems of balance laws those which represent physically realizable thermodynamic processes. Hence, they proposed an amendment to the second law which assumes that reversible process directions in state space exist only in correspondence with equilibrium states. Such an amendment allowed them to prove that the restriction of the constitutive equations is the sole possible consequence of non-negative entropy production. Recently, Cimmelli and Rogolino revisited the classical result by Muschik and Ehrentraut from a geometric perspective and included the amendment in a more general formulation of the second law. Herein, we extend this result to nonregular processes, i.e., to solutions of balance laws which admit jump discontinuities across a given surface. Two applications of these results are presented: the thermodynamics of an interface separating two different phases of a Korteweg fluid, and the derivation of the thermodynamic conditions necessary for shockwave formation. Commonly, for shockwaves the second law is regarded as a restriction on the thermodynamic processes rather than on the constitutive equations, as only perturbations for which the entropy continues to grow across the shock can propagate. We prove that this is indeed a consequence of the general property of the second law of thermodynamics that restricts the constitutive equations for nonregular processes. An analysis of shockwave propagation in different thermodynamic theories is developped as well.

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