Thermodynamics of fluid mixtures near to and far from the critical region

A theory for an equation of state for simple fluid mixtures valid both near to and far from critical points is presented. The base equation of state obtained from integral-equation theory using the mean-spherical approximation is used to compute the contribution of short-wavelength fluctuations to the free energy of the fluid mixture. Wilson's phase space cell approximation, as extended by White, is used to compute the contribution of long-wavelength fluctuations. The resulting theory possesses nonclassic critical exponents similar to those observed experimentally. Far from the critical region, where long-wavelength fluctuations are not important, the theory reduces to that corresponding to the base equation of state. The complete theory is used to represent the thermodynamic properties and phase behavior of binary mixtures of methane, carbon dioxide, and n-butane. In the critical region, agreement with experiment is dramatically improved upon, adding to the base equation of state corrections from long-wavelength fluctuations.

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