On the apparent molar volumes of nonelectrolytes in water |
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Authors: | Andrzej Anderko John P. Chan Kenneth S. Pitzer |
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Affiliation: | (1) Department of Chemistry and Lawrence Berkeley Laboratory, University of California, 94720 Berkeley, CA;(2) Present address: Simulation Sciences, 601 S. Valencia Ave., 92621 Brea, CA |
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Abstract: | Apparent molar volumes of aqueous solutions of argon and xenon have been calculated using a previously developed comprehensive equation of state for nonelectrolyte systems. The equation consists of a virial expansion truncated after the fourth virial coefficient and a closed-form term approximating higher coefficients. Mixing rules are based on the composition dependence of virial coefficients, which is known from statistical mechanics. The equation accurately represents vapor-liquid and gas-gas equilibria for the Ar+H2O and Xe+H2O systems over wide ranges of pressure and temperature using two binary parameters. With the binary parameters determined from phase equilibrium data, the equation accurately predicts apparent molar volumes V in the near-critical and far-from-critical regions. Apart from reproducing experimental V data, the equation reveals remarkable maxima of V as a function of pressure and temperature in the near-critical region. The implications of this equation with respect to the Ar–H2O potential are discussed via the second virial coefficient. |
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Keywords: | Apparent molar volumes vapor-liquid equilibria aqueous nonelectrolytes equations of state near-critical region |
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