MOLECULAR PRINCIPLE OF CORRESPONDING STATES FOR VISCOSITY AND THERMAL CONDUCTIVITY OF FLUID MIXTURES

Conformal solution theory is developed for the viscosity and thermal conductivity of fluid mixtures. The procedure involves expanding the transport coefficient for the mixture about the value for an ideal solution, using groupings of the potential parameters and molecular mass as expansion coefficients. The parameters for the ideal solution are chosen so as to annul the first-order term in this expansion, thus encouraging rapid convergence. This yields mixing rules (similar to those of the van der Waals 1 theory for thermodynamic properties) for the potential parameters and molecular mass of the reference fluid. Reference fluid properties are obtained from pure fluid corresponding states correlations

By making calculations for dilute gas mixtures and comparing with Chapman-Enskog theory, it is found that the first-order theory works well for mixtures of quite widely different energy parameters (ε) and molecular masses; it is more sensitive to the size difference of the molecular components, however. For cryogenic liquid mixtures composed of simple liquids good results are obtained using two-parameter corresponding states for the reference fluid. For polyatomic fluids it is necessary to use a three-parameter corresponding states approach for the pure fluids. A method of introducing a third parameter, while retaining the simplicity of having only two independent variables, is used for such fluids. Good results are obtained for a variety of binary mixtures. The method is of particular value for multicomponent fluids. Thus, without fitting any parameters from ternary data the theory predicts viscosities for the system carbon tetrachloride/n-hexane/benzene over the full composition range with a standard deviation of only 1.69%.