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Journal of Physical Chemistry A, Vol.110, No.3, 831-842, 2006
Relations between transport coefficients and their density and temperature dependence
Nonequilibrium statistical mechanics via density fluctuation theory predicts relations between the bulk and shear viscosity, thermal conductivity, and self-diffusion coefficient of a fluid. In this Feature Article, we discuss such relations holding for fluids over wide ranges of density and temperature experimentally studied in the laboratory. It is discussed how such relations can be used to successfully compute the density and temperature dependence on the basis of intermolecular interaction potential models with the help of the modified free volume theory and the generic van der Waals equation of state once the parameters in them are determined at a low density or at a subcritical temperature. Although some approximations have been made to derive them, they represent a reliable molecular theory of transport coefficients over the entire density and temperature ranges of fluids-namely, gases and liquids-a theory hitherto unavailable in the kinetic theory of liquids and dense gases.Nonequilibrium statistical mechanics via density fluctuation theory predicts relations between the bulk and shear viscosity, thermal conductivity, and self-diffusion coefficient of a fluid. In this Feature Article, we discuss such relations holding for fluids over wide ranges of density and temperature experimentally studied in the laboratory. It is discussed how such relations can be used to successfully compute the density and temperature dependence on the basis of intermolecular interaction potential models with the help of the modified free volume theory and the generic van der Waals equation of state once the parameters in them are determined at a low density or at a subcritical temperature. Although some approximations have been made to derive them, they represent a reliable molecular theory of transport coefficients over the entire density and temperature ranges of fluids-namely, gases and liquids-a theory hitherto unavailable in the kinetic theory of liquids and dense gases.