Vapor–Liquid Equilibrium of Alcohol–n–Decane and Acetone–Ethanol Systems at 82.6 kPa: Experimental and Molecular Simulation Study

This work aims to offer insights for decision-making about the reliability of molecular simulation (MS) as a tool for predicting VLE in binary mixtures of 1-propanol or 1-butanol + n -decane and acetone + ethanol at 82.6 kPa through a systematic comparison with experimentally measured data. The thermodynamic consistency of experimental measurements is tested using the Herington and Fredenslund methods. The Gibbs-Configurational Bias Monte Carlo (CBMC) ensemble with NERD united-atom force fields has been used to estimate the VLE of the mixtures. Both systems show positive deviations from Raoult’s law and are well correlated using van Laar, Wilson, and NRTL models, with deviations in vapor and liquid phase compositions below 0.0141 and 0.0255, respectively. Although MS tends to overestimate the concentrations of 1-propanol and 1-butanol in both phases, the predicted bubble and dew point curves follow the expected trends of the experimental data, providing a fast and reliable tool for analyzing phase equilibrium behavior. A comparison with our equilibrium results and the PC-SAFT equation of state calculations is presented in this work together with the effectiveness and limitations of MS for analyzing the phase behavior of this type of binary mixture.