Effects of an applied electric field on the vapor-liquid equilibria of water, methanol, and dimethyl ether.
Gibbs ensemble Monte Carlo simulations are employed to examine the influence of moderately strong electric fields on the vapor-liquid coexistence curves and on structural and energetic properties of the saturated phases of water, methanol, and dimethyl ether. The application of an electric field of 0.1 V/A increases the critical temperature and normal boiling point by approximately 3% compared to the zero field case for all three compounds, whereas the critical density is found to decrease by 1% for methanol and dimethly ether and by 3% for water. For the special case of an electric field applied in only the liquid phase, these effects are magnified with a 4% increase in T(C) and a 13% decrease in rho(C). For the case of an electric field in only the vapor phase, the opposite effect is seen with a 4% decrease in T(C) and a 12% increase in rho(C). Structural analysis shows very little change in the radial distribution functions, but greatly increased orientational ordering with the application of an electric field. The orientational ordering effect is stronger in the liquid phase than in the vapor phase. An examination of the energetics reveals that, in the presence of an electric field, the interactions with the first and second solvation shells become less favorable but these are outweighed by a larger increase in the favorable long-range interactions with more distant molecules and the field.
Maerzke
Katie A
KA
Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
Siepmann
J Ilja
JI