Continuum reaction field calculation of dielectric constant and vapor pressures for water and carbon disulfide.

摘要

Continuum reaction field theory is applied to calculations of dielectric constant, contribution of intermolecular interactions to the free energy of a liquid, and heat of vaporization. Introduction of repulsive interactions and the use of one adjustable parameter, the free volume, enables prediction of vapor pressures. The calculations are illustrated for a simple nonpolar liquid, carbon disulfide, and for liquid water. It is shown that when Onsager's equation is rearranged to a quadratic equation, and a recently found value of the polarizability is employed, its solutions for liquid water yield good agreement with experimental values throughout the whole temperature range. The decrease of the dielectric constant with temperature is essentially linear with the inverse of absolute temperature, but there is additional significant decrease due to the decrease of density with temperature. The relatively high value of the heat of vaporization of liquid water is expressed in terms of large dipolar interaction of a water molecule with the environment, which is due to polarization effects.