Correlation of the transport properties of simple fluids at low temperatures and high pressures based on the generalized Eucken relation and the molecular dynamics of hard sphere fluid

Abstract

A generalized correlation is developed for the viscosity and thermal conductivity of isotropic fluids under high pressures (up to 200 MPa) and low temperatures (down to 85 K). Two known observations have been taken into consideration in the development of the correlation. First, the Alder correction factors for the Enskog theory values of transport coefficients obtained from molecular dynamics simulations for hard sphere fluids are incorporated. The inclusion of these corrections in the theory makes it possible to describe correctly the density dependence of the hard sphere viscosity and thermal conductivity at high pressures. The hydrodynamic “cage” effect, which is manifested in the molecular motions of dense fluid systems, is thus correctly accounted for. Second, the generalized Eucken relation, which relates the thermal conductivity to the viscosity, is incorporated. As a consequence, an internally consistent correlation is obtained, which can adequately predict the behavior of the thermal conductivity from given values of viscosity. Tests on simple fluids, such as argon, krypton, etc., show that the correlation is valid within a few percent for the entire fluid range where experimental data are available for comparison, and also along the vapor-liquid saturation line, with the exclusion of the critical region. Furthermore, since the variables appearing in the theory are in reduced form, a corresponding states correlation is established for isotropic fluids.