Thermodynamic Theory of Diffusion and Thermodiffusion Coefficients in Multicomponent Mixtures

Transport coefficients (like diffusion and thermodiffusion) are the key parameters to be studied in non-equilibrium thermodynamics. For practical applications, it is important to predict them based on the thermodynamic parameters of a mixture under study: pressure, temperature, composition, and thermodynamic functions, like enthalpies or chemical potentials.

The current study develops a thermodynamic framework for such prediction. The theory is based on a system of physically interpretable postulates; in this respect, it is better grounded theoretically than the previously suggested models for diffusion and thermodiffusion coefficients. In fact, it translates onto the thermodynamic language of the previously developed model for the transport properties based on the statistical fluctuation theory.

Many statements of the previously developed model are simplified and amplified, and the derivation is made transparent and ready for further applications. The n (n + 1) / 2n(n+1)/2 independent Onsager coefficients are reduced to 2 n + 12n+1 determining parameters: the emission functions and the penetration lengths.

The transport coefficients are expressed in terms of these parameters. These expressions are much simplified based on the Onsager symmetry property for the phenomenological coefficients. The model is verified by comparison with the known expressions for the diffusion coefficients that were previously considered in the literature.