Transport coefficients of dense fluids of molecules interacting according to a square well potential

Abstract

A simplified kinetic theory is described for spherical molecules interacting according to a square well potential. The statistical premises of this theory correspond closely to those of Longuet-Higgins' and Pople's theory of dense fluids of rigid spheres. The thermal conductivity λ, shear viscosity η and bulk viscosity κ are predicted to be in the ratio where k is Boltzmann's constant and m the mass of a molecule. To calculate any of these coefficients absolutely requires independent information about the equilibrium pair distribution. This may be obtained from the self-diffusion constant D, whose value is also given by the theory. For argon the measured value of D leads to a theoretical value for η which is in good agreement with experiment; for this liquid however the observed ratio κ:η is very much smaller than predicted.