Entropy Balance Near the Reversible-Thermodynamic Equilibrium

1 Entropy Balance Near the Reversible-Thermodynamic Equilibrium 

To apply the usual formalism of irreversible thermodynamics to the scheme (14), the excess concentrations js = cs — cs and jg = cg — cg over the reversible values (cs, cg) are introduced. Using also c = vcs with v 1 (Sect. 3.2.2), Eq. (14) are transformed to  

within the limits of the perturbation calculus (js/cs 1 and jjcg 1), the equations of system (15b) can be combined with the definitions of the excess concentrations, giving 

The entropy production (150 vanishes in the reversible-thermodynamic equilibrium where all generalized forces and all flows vanish in the system sol/gel  

In this case, the system of Eqs. (14) is complete so that the matrix (15e) represents a symmetrical Onsager matrix the equality L12 = L2l with kg = kg then yields the condition of the reversible-thermodynamic equilibrium in the PDC-column 

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