A comparative study of the coupling of flow with non-Fickean thermodiffusion. I: Extended irreversible thermodynamics
Non-Fickean thermodiffusion in binary fluids within the framework of three recent theories of non-equilibrium thermodynamics, namely extended irreversible thermodynamics (EIT),\break GENERIC (General Equation for the Non-Equilibrium Reversible Irreversible Coupling) theory and thermodynamics with internal variables (IVT) is analysed. In the first part, presented in this paper, the EIT description of viscous fluids is developed. The basic idea underlying the EIT theory is to add to the set of independent physical variables (as the conserved quantities mass, momentum and energy) the fluxes (e.g.\ the diffusion and energy fluxes) of the system. In the paper, first the simple problem of molecular diffusion at uniform temperature in a binary mixture is examined for the cases of the linear and weakly nonlinear thermodynamic regimes. A generalized evolution equation for the diffusion flux (generalized Fick law) is derived, which predicts the propagation of concentration waves. Within the linear regime, the generalized Fick law reduces to the classical, steady Fick law when the relaxation time \(\tau\) of the system tends to zero. It is also shown that the generalized Gibbs equation in the linear regime, in comparison with the classical irreversible thermodynamics, contains an additional contribution proportional to the diffusion flux, which vanishes at \(\tau\rightarrow 0\). The entropy flux keeps its classical expression in the linear regime. After molecular diffusion, heat transport in a one-component viscous fluid is studied separately within the frame of the caloric model. The main result is that heat is not conducted by a Fourier law but by a Cattaneo relation exhibiting the existence of temperature waves. At the end, thermodiffusion in a binary mixture is analysed coupling the results for pure mass diffusion and heat conduction. The obtained evolutionary equation for thermodiffusion generalizes the Soret and Dufour laws towards the unsteady regime.
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