Semi-ideal Solution Theory. 2. Extension to Conductivity of Mixed Electrolyte Solutions

Abstract

Conductivities were measured for the ternary systems NaCl-LaCl(3)-H(2)O and KCl-CdCl(2)-H(2)O and their binary subsystems NaCl-H(2)O, KCl-H(2)O, CdCl(2)-H(2)O, and LaCl(3)-H(2)O at 298.15 K. The semi-ideal solution theory for thermodynamic properties of aqueous solutions of electrolyte mixtures was used together with the Eyring absolute rate theory to study conductivity of mixed electrolyte solutions. A novel simple equation for prediction of the conductivity of mixed electrolyte solutions in terms of the data of their binary solutions was established. The measured conductivities and those reported in literature were used to test the newly established equation and the generalized Young's rule for conductivity of mixed electrolyte solutions. The comparison results show that the deviation of a ternary solution from the new conductivity equation is closely related to its isopiestic behavior and that the deviations are often within experimental uncertainty if the examined system obeys the linear isopiestic relation. While larger deviations are found in the system with large ion pairing effect, the predictions can be considerably improved by using the parameters calculated from its isopiestic results. These results imply that the previous formulation of the thermodynamic properties of aqueous solutions of electrolyte mixtures has a counterpart for transport properties.