The second law of thermodynamics as variation on a theme of Carathéodory

Abstract

This paper revisits the second law of thermodynamics via certain modifications of the axiomatic foundation provided by the celebrated 1909 work of Carathéodory. It is shown that his postulate of adiabatic inaccessibility represents one of several constraints on the energy balance that serve to establish the existence of thermostatic entropy as a foliation of state space, with temperature representing a force of constraint. To achieve the thermostatic version of the second law, as embodied in the postulates of Clausius and Gibbs, work principles are proposed to define thermostatic equilibrium and stability in terms of the convexity properties of internal energy, entropy and related thermostatic potentials. Comparisons are made with the classic work of Coleman and Noll on thermostatic equilibrium in simple continua, resulting in a few unresolved differences. Perhaps the most novel aspect of the current work is an extension to irreversible processes by means of a non-equilibrium entropy derived from recoverable work, which generalizes similar ideas in continuum viscoelasticity. This definition of entropy calls for certain revisions of modern theories of continuum thermomechanics by Coleman, Noll and others that are based on a generally inaccessible entropy and undefined temperature.