Molecular Diffusion Coefficients in Ethanol/Water/Carbon Dioxide Mixtures

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Abstract
Supercritical and liquid mixtures of ethanol/H2O/CO2 are increasingly used to extract solutes from solid or semisolid matrixes when nontoxic solvents and fast extraction kinetics are desired. Accordingly, to better understand the mass transport capabilities of these mixtures, the diffusion coefficients of benzene, anthracene, m-cresol, and p-nitrophenol in enhanced-fluidity liquid mixtures of ethanol/H2O/CO2 were studied. The effect of mixture composition and temperature variation on the measured diffusion coefficients was studied. In a mixture containing 0.61/0.39 mole ratio ethanol/H2O, the diffusion coefficients of the four solutes increased comparably either by adding 30 mol % CO2 or by changing the temperature of the mixture from 25 to 60 °C. The experimental data were compared to that predicted by the Stokes−Einstein and the Wilke−Chang relations. Often, the experimental diffusion coefficients were greater than those predicted by these mass transport relations. However, the Eyring relationship was useful in describing the variation of diffusion coefficients as a function of temperature change for all of the ethanol/H2O/CO2 mixtures tested.