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Vapor-liquid equilibria at high pressures: Calculation of critical temperatures, volumes, and pressures of nonpolar mixtures



An analysis of critical data for a larger number of binary mixtures of normal fluids shows that the critical temperature and the critical volume can each be expressed as quadratic functions of the surface fraction. Each of these functions requires one adjustable parameter characteristic of the binary pair; for any family of chemical components, these parameters, upon suitable reduction, follow definite trends. It was shown that the surface fraction gives much better correlation than any other size-weighted variable. For the critical pressure, however, no quadratic function was adequate. To calculate critical pressures, the correlations for critical temperature and critical volume were used in conjunction with a slightly altered version of the Redlich-Kwong equation.

Generalizations to systems containing more than two components follow without additional assumptions. The methods presented in this paper provide good estimates for critical constants of multicomponent mixtures. These are particularly useful for analyzing and correlating vapor-liquid equilibria in the critical region.

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