Mass-spectrometric Measurement of Activities in Both Solid and Liquid Solutions of the KCl–NaCl System

Abstract
The activities of the KCl–NaCl system were mass-spectrometrically determined by the ion-current-ratio method in the temperature range From 793 to 1083 K. As a result, the activities of KCl or NaCl in the solid solution showed greatly positive deviations from Raoult’s law while the liquid solution at 1083 K gave slightly negative values. The heats of mixing in the solid solution were calculated from the temperature dependence of the modified ion-current ratios, [(INa2Cl+/XNaCl2)/(IK2Cl2/XKCl2)]. The excess entropy of mixing in the solid solution was attributed to the change in the vibrational spectrum, and the vibrational contribution to the heat of mixing was evaluated.

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