Extended Irreversible Thermodynamics (PDF)

Classical irreversible thermodynamics, as developed by Onsager, Prigogine and many other authors, is based on the local-equilibrium hypothesis. Out of equilibrium, any system is assumed to depend locally on the same set of variables as when it is in eqUilibrium. This leads to a formal thermody­ namic structure identical to that of eqUilibrium: intensive parameters such as temperature, pressure and chemical potentials are well-defined quantities keeping their usual meaning, thermodynamic potentials are derived as Leg­ endre transformations and all equilibrium thermodynamic relations retain their validity. The theory based on this hypothesis has turned out to be very useful and has achieved a number of successes in many practical situations. of interest in going However, the recent decade has witnessed a surge beyond the classical formulation. There are several reasons for this. One of them is the development of experimental methods able to deal with the response of systems to high-frequency and short-wavelength perturbations, such as ultrasound propagation and light and neutron scattering. The ob­ served results have led to generalizations of the classical hydrodynamical theories, by including memory functions or generalized transport coefficients depending on the frequency and the wavevector. This field has generated impressive progress in non-equilibrium statistical mechanics, but for the moment it has not brought about a parallel development in non-equilibrium thermodynamics. An extension of thermodynamics compatible with gener­ alized hydrodynamics therefore appears to be a natural subject of research.