In this work, the vapor–liquid equilibrium (VLE) and excess molar enthalpy (HE) of three binary mixtures, namely, ethylbenzene + γ-valerolactone (GVL), cyclohexene + GVL, and cyclohexene + ethylbenzene, were measured. VLE data were measured at 35.0 and 70.0 kPa for the GVL-containing mixtures and at 70.0 and 101.3 kPa for the ethylbenzene + cyclohexene mixture. Vapor pressures of the pure components were measured and correlated using an extended Antoine equation, which aligned well with the literature data. The HE values were experimentally determined at 298.15 K. All the binary mixtures exhibited positive HE, indicating endothermic mixing. Including HE data in the regression of binary interaction parameters (BIPs) was essential for accurate modeling; omitting these data led to inaccurate results, such as an incorrectly negative calculated HE. All three studied mixtures showed no azeotrope formation. Correlative models such as Wilson, NRTL, and UNIQUAC accurately represented the experimental VLE and HE data. In contrast, predictive group-contribution models UNIFAC and UNIFAC-Dortmund did not adequately reproduce the VLE and HE of the GVL-containing mixtures, mainly due to insufficient group parameters for GVL’s structure. COSMO-RS predictions improved when experimental vapor pressure data were included in compound properties. The VLE data were confirmed to be thermodynamically consistent upon verification using the Van Ness and L–W tests.
Wibowo et al. (Mon,) studied this question.