Correlations for the Dielectric Constants of $\hbox {H}_{2}\hbox {S}$, $\hbox {SO}_{2}$, and $\hbox {SF}_{6}$

Abstract

A new method is developed for correlating the static dielectric constant of polar fluids over wide ranges of conditions where few experimental data exist. Molecular dynamics simulations are used to establish the temperature and density dependence of the Kirkwood g-factor, and also the functional form for the increase of the effective dipole moment with density. Most parameters in the model are obtained entirely from simulation; a single proportionality constant is adjusted to obtain agreement with the limited experimental data. The method is applied to hydrogen sulfide ($\hbox {H}_{2}\hbox {S}$) and sulfur dioxide $(\hbox {SO}_{2})$, both of which are important in geochemistry but have only a few dielectric data available. The resulting correlations agree well with the available liquid data, obey physical boundary conditions at low density and at high temperature, and interpolate in density and temperature in a physically reasonable manner. In addition, we present a more conventional correlation for the dielectric constant of sulfur hexafluoride, $\hbox {SF}_{6}$, where more data are available.