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Guide Binary Gaseous, Liquid, Near-Critical, and Supercritical Fluid Systems of Nonelectrolytes

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In this paper, we discuss the methods to obtain values of A Kr from various types of experimental information on the thermodynamic properties of binary systems, and use these methods to evaluate the Krichevskii parameter for more than 30 aqueous nonelectrolytes. The possibility of calculating the values of the Krichevskii parameter for solutes at infinite dilution in water from the van der Waals and Peng-Robinson equations of state was also checked.

It is shown that the classical cubic equations of state may be used to predict the values of A Kr for small nonpolar solutes in water, but grossly overestimate A Kr for larger compounds. As an alternative, we propose an empirical correlation between the Krichevskii parameter and the Gibbs energy of hydration at Predictions, related to the sign of the Krichevskii parameter for a number of aqueous inorganic and organic nonelectrolytes, are made, which can be verified experimentally. Estimation of the Krichevskii parameter for aqueous nonelectrolytes.

N2 - The Krichevskii parameter determines the sign and magnitude of the near-critical divergence of the partial molar thermodynamic properties of infinitely dilute solutions. Estimation of the values of the Krichevskii parameter, AKr, would be helpful in improving the quality of predictions of the infinite dilution partial molar properties of aqueous nonelectrolytes at near-critical and supercritical conditions.

In this paper, we discuss the methods to obtain values of AKr from various types of experimental information on the thermodynamic properties of binary systems, and use these methods to evaluate the Krichevskii parameter for more than 30 aqueous nonelectrolytes. It is shown that the classical cubic equations of state may be used to predict the values of AKr for small nonpolar solutes in water, but grossly overestimate AKr for larger compounds.

AB - The Krichevskii parameter determines the sign and magnitude of the near-critical divergence of the partial molar thermodynamic properties of infinitely dilute solutions. Abstract The Krichevskii parameter determines the sign and magnitude of the near-critical divergence of the partial molar thermodynamic properties of infinitely dilute solutions. Fingerprint nonelectrolytes. Gibbs free energy. Equations of state. Thermodynamic properties. Triolo, M. Blum, and. Florianon , Simple electrolytes in the mean spherical approximation.

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Bibliographic Information

Martin, J. Canales , Simple statistical mechanics of electrolytes with a concentration dependent dielectric constant. Part 1. The pressure equation , Journal of Solution Chemistry , vol.

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Gas solubility and Henry's law near the solvent's critical point

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