Abstract
The linear Onsager theory of irreversible thermodynamics is extended to include nonlinear phenomenological relations by means of Onsager fluxes. Such fluxes satisfy a full system of reciprocity relations, vanish in thermodynamic equilibrium, and give a non-negative production of entropy. A complete characterization of Onsager fluxes is obtained in terms of non-negative scalar valued functions which vanish in thermodynamic equilibrium. These same functions are also shown to characterize all C 2 fluxes which satisfy the second law of thermodynamics. Each system of Onsager fluxes is shown to derive from a dissipation function which attains its absolute minimum in thermodynamic equilibrium. The reaction rates given by reaction kinetics are shown to be Onsager fluxes and their dissipation functions are explicitly calculated.
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