Estimation of compressibility and volume of electrostriction layer in water-methanol system and its application to the partial molar volumes of LiCl, KCl, and CsCl in this system.

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A theory of electrostriction based on the spherical symmetry of electric field around ion and the dielectric continuum of solvent has been applied to the mixed solvent of water–methanol. The isothermal compressibility, κT, and the volume decrease, ΔV of primary solvation layer have been calculated for univalent ions. Calculation procedure consists of two steps; 1) calculation of the variation of electric field strength and dielectric constant with the distance from ion, 2) calculation of the compressibility and the volume decrease of electrostriction layer. In step 2), the calculation method proposed by Desnoyers et al. (J. Chem. Phys., 43, 243 (1965)) was used. Parameters necessary for the calculation were estimated in an appropriate manner and the results of calculation are shown as plots of κT and ΔV, vs. the distance from the center of ion. Partial molar volumes of LiCl, KCl, and CsCl in water–methanol system have been measured and the disordered part of partial molar volume has been determined after taking account of the values of κT and ΔV of the primary solvation layer.
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