Abstract

Transport properties of fluid mixtures exhibit anomalous behavior near the vapor-liquid critical line. These anomalies are a result of long-range fluctuations in the system in the vicinity of a critical point. We use mode-coupling theory to describe the critical enhancements of the thermal conductivity, the viscosity, the mutual diffusivity, and the thermal-diffusion coefficients of binary mixtures. The resulting expressions not only are valid in the asymptotic critical region but also describe the crossover to regular behavior far away from a critical point. The crossover functions depend on the thermodynamic properties of the mixtures, background values of all transport coefficients, and two concentration-dependent cutoff wave numbers. We compare the proposed crossover model with experimental thermal-conductivity data for mixtures of carbon dioxide and ethane in the critical region and find good agreement between theory and experiment.

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