Collision Integrals for a Modified Stockmayer Potential

Abstract

Collision integrals were calculated for the modified Stockmayer potential E(r) = 4 epsilon [(sigma/r)(exp 12) - (sigma/r)(exp 6) - delta(sigma/r)(exp 3)], which may be applied to polar molecules. It was assumed that the colliding molecules maintain their same relative orientation during the encounter. Calculations of the integrals were made for a large reduced temperature range and for a range of delta from 0 to 10. The results agree with other work on non-polar interactions (delta = 0). However for polar interactions the only previously published calculations have been found to be in error and do not agree with this work. Assuming that the molecules interact as alined dipoles of maximum attraction, values for sigma, epsilon, and delta were determined for various polar molecules by a least squares fit of experimental viscosity data. Satisfactory results were obtained for slightly polar molecules, but not for more highly polar molecules such as NH3 or H2O. Therefore, it appears that the assumed model of molecules interacting at all times as alined dipoles of maximum attraction is not satisfactory for estimating trans- port properties of polar molecules.