Enthalpies of Mixing of Halogenated Methanes and Their Interpretation. I. Dihalogenated Methanes

Abstract

indicates the energetic effects in solutions of simple molecules can be described by the partition function with the aid of one mixture parameter, the value of which is consistent with that for the pure component interaction (Winnick, 1972).The description of polar-nonpolar liquid mixture enthalpy is not quite so successful as that for polar-polar mixtures. However, for those systems with weakly repulsive unlike interaction energies (negative win , Table I), the excess Gibbs energy prediction agrees with experiment. These mixtures are much less ordered than those with strong mutual attraction. Thus, the semi-random theory used here accurately represented the excess entropy.The failure of both the polar-polar and polar-nonpolar treatments for the chloroform-alcohol systems is due in part to the induction effect of each species on the other. To include the 1-2 and the 2-1 induction effects as well as the permanent dipole interaction would require two additional terms, similar to 20, in eq 16. It is felt the extra empiricism involved is not