Vapour–liquid equilibrium using quantum chemical molecular dynamics simulation and radial distribution function analysis

Abstract Instead of the classical molecular simulation widely implemented for estimating the vapour–liquid equilibrium (VLE), a quantum chemical (QC) molecular dynamics simulation was applied to the VLE estimation in three typical systems that include a deep eutectic solvent (DES) and an ionic liquid (IL). In addition, a radial distribution function (RDF) was derived from the QC simulation to examine the molecular behaviour in the liquid phase. A mean absolute error of 2.72% was obtained from the QC simulation compared to the experimental data. The RDF analysis explains the relative volatility increase of the acetic acid and water binary system with the propyl acetate solvent. This analysis indicated that the DES mixture comprising glycerol and choline chloride facilitated the separation of water and i ‐propanol. The interaction between water and ethyl sulphate pair with the help of 1‐ethyl‐3‐methylimidazolium as an IL is stronger than that between ethanol and water, which explains how the IL improves ethanol and water separation in the vapour phase.