Liquid membrane potential in nonisothermal systems.

Electrical membrane potential equations for liquid ion exchange membranes, characterized by the presence of uncharged associated species and by exclusion of co-ions (no electrolyte uptake) have been derived. The irreversible thermodynamic theories already developed for solid membranes with fixed charged site density have been extended to include the different physicochemical aspects of the liquid membranes. To this purpose the dissipation function has been written with reference to the fluxes of all the species present in the membrane. It has been found that the mobile charged site, the counterions, and the uncharged associated species contribute to the electrical membrane potential through their phenomenological coefficients. The electrical membrane potential equations have been integrated in isothermal and nonisothermal conditions for monoionic and biionic systems. The theoretical predictions have been experimentally tested by studying the electrical potential of liquid membranes formed with solutions of tetraheptylammonium salts in omicron-dichlorobenzene.