非平衡热力学 .pptVIP

And Eckart did not stop with single fluids. He applied his scheme to mixtures of fluids as well. In that case he started with the Gibbs equation for a mixture, see Chap. 5 and identified thermodynamic fluxes and forces as shown in Table 8.2. Obviously diffusion and chemical reactions are taken into account Phenomenological relations in the case of mixtures are more rich than for a single fluid; they read * Phenomenological relations in the case of mixtures are more rich than for a single fluid; they read… The entropy inequality is satisfied, if the matrices and are positive semi - definite, and the viscosity ?? must be non-negative. Clearly both Fourier’s and Fick’s laws are now made considerable more general than either Fourier or Fick had them. They allow for cross effects such that a temperature gradient may create diffusion and a concentration gradient may create heat conduction. Moreover, the concentration gradient of one effects may occur between the reaction rates and the dynamic pressure, although I believe that they have never been observed. * Eckart never received much credit for his work, because shortly after his publications Josef Meixner (1908–1994) published a very similar theory,28 and so did Ilya Prigogine (1917– ).29 In contrast to Eckart the latter authors stayed in the field and monopolized the subject, as it were. On somewhat uncertain grounds they added Onsager reciprocity relations for transport coefficients, see below. As a result it is not uncommon to hear Eckart’s theory described as Onsager’s theory. TIP became also known as the thermodynamics of the Dutch school, because many Dutch thermodynamicists contributed to it. The major monograph on the subject was written by de Groot and Mazur.30 The book gives a fairly clear account of TIP; it puts some emphasis upon the so-called Curie principle by which thermodynamic forces and fluxes cannot be related linearly unless they have the same tensorial rank. * Before we leave Eckart, we must mentio