Irreversible thermodynamic formulation transport equation

The fundamental question in transport theory is Can one describe processes in nonequilibrium systems with the help of (local) thermodynamic functions of state (thermodynamic variables) This question can only be checked experimentally. On an atomic level, statistical mechanics is the appropriate theory. Since the entropy, 5, is the characteristic function for the formulation of equilibria (in a closed system), the deviation, SS, from the equilibrium value, S0, is the function which we need to use for the description of non-equilibria. Since we are interested in processes (i.e., changes in a system over time), the entropy production rate a = SS is the relevant function in irreversible thermodynamics. Irreversible processes involve linear reactions (rates 55) as well as nonlinear ones. We will be mainly concerned with processes that occur near equilibrium and so we can linearize the kinetic equations. The early development of this theory was mainly due to the Norwegian Lars Onsager. Let us regard the entropy S(a,/3,. ..) as a function of the (extensive) state variables a,/ ,. .. .which are either constant (fi,.. .) or can be controlled and measured (a). In terms of the entropy production rate, we have (9a/0f=a)... 

Another attempt to correlate transport and self-diffusivities has been based on a generalization of the Stefan-Maxwell formulation of irreversible thermodynamics [111-113]. By introducing various sets of parameters describing the facility of exchange between two molecules of the same and of different species, the resulting equations are more complex than eqs 27 and 28 They may be shown, however, to include these relations as special cases... 

Formally, it will be even necessary to make corrections already in the starting flux equations. The detailed formulation of linear irreversible thermodynamics also includes coupling terms (cross terms) obeying the Onsager reciprocity relation. They take into account that the flux of a defect k may also depend on the gradient of the electrochemical potential of other defects. This concept has been worked out, in particular, for the case of the ambipolar transport of ions and electrons.230... 

In the formulation of the microscopic balance equations, the molecular nature of matter is ignored and the medium is viewed as a continuum. Specifically, the assumption is made that the mathematical points over which the balance field-equations hold are big enough to be characterized by property values that have been averaged over a large number of molecules, so that from point to point there are no discontinuities. Furthermore, local equilibrium is assumed. That is, although transport processes may be fast and irreversible (dissipative), from the thermodynamics point of view, the assumption is made that, locally, the molecules establish equilibrium very quickly. 

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