Abstract

The thermodynamic perturbation theory of Stell, Rasaiah and Narang is generalized to the case of multi-component Stockmayer fluids. The effects of polarization by the permanent dipoles is included to first order and the perturbation series is summed approximately to all orders in the dipole moments by means of two Pade approximants. The two-body and triplet terms in the expansion have been evaluated by Monte Carlo integration for a specific choice of the reference Lennard-Jones mixture and the results are used to study systematically the effect of dipolar interactions on excess thermodynamic properties. The utility of a one-fluid theory based on the van der Waals model is investigated and it is shown that the approach is useful for obtaining semi-quantitative information on mixtures of weakly polar fluids. The special case of mixtures of hydrogen chloride and xenon is considered and it is shown that the potential model used is inadequate to account for the large deviations from ideality which are observed...

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