Irreversible thermodynamics of multicomponent fluids and its statistical mechanics basis

The irreversible thermodynamics of a multicomponent fluid is reviewed. This includes a discussion of the role of individual component fluxes. It is argued that their differences vanish on the same time scale as that which establishes local thermodynamic equilibrium and thus do not play an independent role in fluid dynamics, but only arise in response to gradients in conserved thermodynamic variables. The contributions to the energy flux are examined and it is argued that there should be explicit contributions associated with the various component fluxes, which are not mentioned in standard kinetic theory presentations. Three different thermodynamic perspectives are discussed as to their form, with the respective equations for the entropy flux and production described and contrasted. The Onsager reciprocal relations are considered to be a consequence of the single-valuedness of the entropy production with the chemical potential gradients as the driving forces for diffusion. These are specialized to ideal gas mixtures using the component density gradients associated with Fick's laws and to using the mole fraction gradients that are standardly used in gas kinetic theory. The ideal gas Onsager relations are identical to those deduced from the Boltzmann equation. Irving and Kirkwood's statistical mechanics treatment of the evolution equations of a one-component fluid [J. Chem. Phys. 18, 817 (1950)] is generalized to multicomponent fluids and agrees with the thermodynamic perspective that treats the energy transfers as reversible.