Phase equilibria and volumetric properties of aqueous CACl2 by an equation of state

Authors

  • Shaoyi Jiang,

    1. Dept. of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, CA 94720
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  • Kenneth S. Pitzer

    Corresponding author
    1. Dept. of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, CA 94720
    • Dept. of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, CA 94720
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Abstract

A comprehensive equation of state was developed to represent the phase equilibria and volumetric properties of aqueous calcium chloride solutions at temperatures above 523 K. The equation consists of a reference part and a perturbation contribution. The reference function is developed from the statistical mechanical theory for mixtures of dipolar and quadrupolar hard spheres, which agrees well with the Monte Carlo simulation results. In this treatment, calcium chloride is described by the completely undissociated model. The empirical perturbation function is a truncated series of virial expansion terms. Thus, mixing rules are guided by those of virial coefficients, which are derived rigorously from statistical mechanics. The equation reproduces experimental saturated vapor pressures and volumetric data within experimental uncertainty for temperatures to 623 K. At higher temperatures, few and less accurate experimental data are available, but values of the saturated vapor pressures of the liquid have been reported and are represented satisfactorily.

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