An Improved Equation for the Liquid Junction Potential at the Interface of Different Solvents

Abstract

The component of the liquid-junction potential due to the diffusion of ions across an interface of electrolyte solutions in different solvents was formulated by taking into account the solvent dependence of the transport numbers, t, and of the chemical potentials of ions in the interphase region as determined from experimental data on their variation in the mixed-solvent compositions. The new equation was applied to NaCl/NaCl and HCl/HCl junctions between water and methanol-water solvents over the entire solvent range. Significant differences between the results obtained with the new equation and the old formulation, which treated the transport numbers as solvent-independent, were observed only for the HCl junctions involving 90-100 wt % aqueous methanol, where t_H exhibits a sharp minimum as a function of the solvent composition.