Theory for Surface Structure of Electrolyte Solutions.

A theory is developed for the salt concentration profile and ion-ion correlations near surfaces of electrolyte solutions. We use the random phase approximation to study the primitive surface model employed by Onsager and Samaras, and others. In this model the chief technical complication is the correct treatment of image forces. We invent an exact rearrangement of the mathematical formulation of the problem which makes especially transparent the special case solutions (infinite dielectric constant mismatch) previously found. This reformulation guides an analytical solution for arbitrary dielectric constant mismatch between the two phases, subject to other assumptions adopted by previous workers. Similarly general results are derived for mixtures of ionic and dipolar solutes. These general results form the basis for extending our theoretical studies in several new directions. First, higher concentration corrections are investigated. It is shown that over an experimentally significant range of low concentrations for aqueous solutions the initial concentration correction to the Onsager-Samaras absorption has a negative definite sign. The theory, including concentration corrections, is compared to available computer simulation data, and close agreement is found for aqueous solutions below a few tenths molar. Second, the theory is developed to treat asymmetric electrolytes, and applied to ionic surfactants spread on water-hydrocarbon interfaces. Again, the theory accurately describes available experimental data. Third, the theory is broadened to acknowledge the solubility of the salt in both phases. It is found that this generalization changes the qualitative nature of the low concentration limiting law for the excess surface tension: the limiting behavior is changed from the (rho)ln(rho) dependence predicted by Onsager and Samaras to a more generally correct (rho)(' 1/2) dependence. Experimental data which might test this (rho)(' 1/2) behavior are not presently available. It is suggested that experimental studies of the limiting law behavior as a liquid-vapor critical point is approached, where substantial salt concentration in both phases is expected, would clearly establish the general limiting law.