Liquid–Vapor Interface of Aqueous Ethylene Glycol Solutions: A Molecular Dynamics Study

While the organic constituent in an aqueous binary solution enriches its liquid–vapor (l–v) interface, the extent of enrichment can depend nonlinearly on its mole fraction. A microscopic quantification and rationalization of this behavior are crucial to understand the dependence of properties such as surface tension and evaporation rate of the solution on its composition. Extensive all-atom molecular dynamics simulations of aqueous ethylene glycol (EG) solutions show that the composition of the solution at the l–v interface deviates the most from that in the bulk solution at an EG mole fraction of 0.3. The population of EG molecules with their central C–C dihedral in the gauche conformation was found to be higher at the l–v interface than that in the bulk solution to facilitate the orientation of its hydrophobic methyl groups toward the vapor phase. Free energy calculations reveal that in dilute EG solutions, an EG molecule is most stable at the l–v interface. The behavior of vapor pressure in aqueous EG solutions is ideal and follows Raoult’s law, while in contrast, the aqueous solution of dimethyl sulfoxide does not. A rationale for the same is provided through the orientational distribution of interfacial water molecules in the respective solutions.