E Chemical Processes and Classical Thermodynamics

These and all previous results of thermodynamic mixture which also fulfil Gibbs-Duhem equations (4.263) show the complete agreement with the classical thermodynamic of mixtures but moreover all these relations are valid much more generally. Namely, they are valid in this material model—linear fluid mixture—in all processes whether equilibrium or not. Linear irreversible thermodynamics [1-4], which studies the same model, postulates this agreement as the principle of local equilibrium. Here in rational thermodynamics, this property is proved in this special model and it cannot be expected to be valid in a more general model. We stress the difference in the cases when (4.184) is not valid—e.g. in a chemically reacting mixture out of equilibrium—the thermodynamic pressures P, Pa need not be the same as the measured pressure (as e.g. X =i Pa) therefore applications of these thermodynamic... 

The processes taking place on the surface of the solid are complicated and great in number. We measure a certain common resultant effect as the powder electrode potential. The full mastery of the subject would have to be based on the elaboration of a chemical and physicochemical model of all processes (i.e., giving the chemical equations of reactions in process, indicating the processes of solution, adsorption, desorption, and secondary reactions, etc.) as well as on the classical thermodynamic description, and possibly by thermodynamics of irreversible processes, and chemical and electrochemical kinetics. 

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