Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures

article Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures published yes Xiaoyu Wang author 8dff9c62-32b0-11ee-9fa8-fc73025e10f3 Bingqing Cheng author cbe3cda4-d82c-11eb-8dc7-8ff94289fcc90000-0002-3584-9632 BiCh department GradSch department An azeotrope is a constant boiling point mixture, and its behavior is important for fluid separation processes. Predicting azeotropes from atomistic simulations is difficult due to the complexities and convergence problems of Monte Carlo and free-energy perturbation techniques. Here, we present a methodology for predicting the azeotropes of binary mixtures, which computes the compositional dependence of chemical potentials from molecular dynamics simulations using the S0 method and employs experimental boiling point and vaporization enthalpy data. Using this methodology, we reproduce the azeotropes, or lack thereof, in five case studies, including ethanol/water, ethanol/isooctane, methanol/water, hydrazine/water, and acetone/chloroform mixtures. We find that it is crucial to use the experimental boiling point and vaporization enthalpy for reliable azeotrope predictions, as empirical force fields are not accurate enough for these quantities. Finally, we use regular solution models to rationalize the azeotropes and reveal that they tend to form when the mixture components have similar boiling points and strong interactions. AIP Publishing2024 eng Journal of Chemical Physics 0021-9606 1089-7690 2405.02216 39007379 00128181910001610.1063/5.0217232 1613 https://github.com/Xiaoyu-Wang-Stone/Azeotrope_S0 Wang X, Cheng B. Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures. Journal of Chemical Physics. 2024;161(3). doi:<a href="https://doi.org/10.1063/5.0217232">10.1063/5.0217232</a> X. Wang, B. Cheng, Journal of Chemical Physics 161 (2024). Wang, Xiaoyu, and Bingqing Cheng. “Integrating Molecular Dynamics Simulations and Experimental Data for Azeotrope Predictions in Binary Mixtures.” Journal of Chemical Physics. AIP Publishing, 2024. <a href="https://doi.org/10.1063/5.0217232">https://doi.org/10.1063/5.0217232</a>. Wang, Xiaoyu, and Bingqing Cheng. “Integrating Molecular Dynamics Simulations and Experimental Data for Azeotrope Predictions in Binary Mixtures.” Journal of Chemical Physics, vol. 161, no. 3, 034111, AIP Publishing, 2024, doi:<a href="https://doi.org/10.1063/5.0217232">10.1063/5.0217232</a>. Wang X, Cheng B. 2024. Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures. Journal of Chemical Physics. 161(3), 034111. Wang, X., & Cheng, B. (2024). Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures. Journal of Chemical Physics. AIP Publishing. <a href="https://doi.org/10.1063/5.0217232">https://doi.org/10.1063/5.0217232</a> X. Wang and B. Cheng, “Integrating molecular dynamics simulations and experimental data for azeotrope predictions in binary mixtures,” Journal of Chemical Physics, vol. 161, no. 3. AIP Publishing, 2024. 172782024-07-21T22:01:00Z2026-08-07T10:38:59Z