Comparative Examination of Nonequilibrium Thermodynamic Models of Thermodiffusion in Liquids

We analyze existing models for material transport in non-isothermal non-electrolyte liquid mixtures that utilize non-equilibrium thermodynamics. Many different sets of equations for material have been derived that, while based on the same fundamental expression of entropy production, utilize different terms of the temperature- and concentration-induced gradients in the chemical potential to express the material flux. We reason that only by establishing a system of transport equations that satisfies the following three requirements can we obtain a valid thermodynamic model of thermodiffusion based on entropy production and understand the underlying physical mechanism: (1) maintenance of mechanical equilibrium in a closed steady-state system, expressed by a form of the Gibbs-Duhem equation that accounts for all the relevant gradients in concentration, temperature, and pressure and respective thermodynamic forces; (2) thermodiffusion (thermophoresis) is zero in pure unbounded liquids (i.e., in the absence of wall effects); (3) invariance in the derived concentrations of components in a mixture, regardless of which concentration or material flux is considered to be the dependent versus independent variable in an overdetermined system of material transport equations. The analysis shows that thermodiffusion in liquids is based on the entropic mechanism.