Direct determination of intermolecular potentials from gaseous transport coefficients alone

Abstract

Intermolecular pair-potential energy functions are given for all the unlike interactions of the monatomic gases. The potentials are obtained by direct inversion of experimental measurements of low density binary mixture viscosity and diffusion coefficients. In those cases where these data extend to sufficiently low temperatures to enable the potential well depth ε/k to be determined, the values obtained for this parameter are Kr-Xe 220 ± 5 K, Ar-Xe 170 ± 5 K, Ar-Kr 165 ± 10 K, Ne-Xe 70 ± 5 K, Ne-Kr 60 ⁺¹⁰ _-5 K, Ne-Ar 60 ± 5 K. For the systems He-Xe, He-Kr, He-Ar and He-Ne only the repulsive branch of the potential energy function is obtained. For all systems the potentials are shown to reproduce well other macroscopic data not used in their construction. The agreement with thermal diffusion data is particularly encouraging. The independent determination of this wide range of potentials provides a direct test of both the hypothesis that they are conformal and the validity of parameter mixing rules. Significant deviations from conformality are found at the extremes of small and large intermolecular separations. No simple combining rules reproduce the potential parameters quantitatively, but the direction in which empirical modifications should be made is clearly suggested.