AbstractA study has been made of the second virial coefficients of binary gas mixtures containing one or two polar components. Methods for calculating these coefficients are presented. The interaction coefficient Bij for a polar‐polar interaction cannot be calculated with the Stockmayer potential with pure component parameters only; such calculations tend to underestimate the strong forces of attraction between dissimilar polar molecules. It is shown that the characteristic distance for the reduced dipole moment for two dissimilar polar molecules is less than the arithmetic average of the distance parameter of the similar molecules by an amount which can be related to the enthalpy of complex formation. When this corrected collision diameter is used in the Stockmayer potential, good results can be obtained for interaction coefficient Bij. In the case of a polar‐nonpolar mixture the coefficient Bij depends on dispersion and on induction forces. Techniques are proposed for estimating these forces from pure component parameters, and it is shown that for accurate calculation of Bij it is necessary to correct for the displacement of the dipole from the center of the polar molecule. The paper concludes with some illustrations of how these ideas may be applied to typical chemical engineering problems.