Molecular simulation of binary phase diagrams from the osmotic equilibrium method: vapour pressure and activity in water–ethanol mixtures

Michael Bley 1 Magali Duvail 1 Philippe Guilbaud 2 Christophe Penisson 3 Johannes Theisen 4, 5 Jean Christophe Gabriel 6 Jean-François Dufrêche 1
1 LMCT - Modélisation Mésoscopique et Chimie Théorique
ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
2 DRCP - Département RadioChimie et Procédés
3 ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
4 L2IA - Ions aux Interfaces Actives
ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
5 LTSM - Tri ionique par les Systèmes Moléculaires auto-assemblés
ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
6 DRF (CEA) - Direction de Recherche Fondamentale (CEA)
Abstract : Herein, an approach for simulating phase diagrams of binary mixtures is presented, where a bulk liquid and its corresponding vapour phase are simulated by means of molecular dynamics using explicit polarisation. Time-averaged density profiles for the pure compounds and mixtures at different mole fractions provide information about the spatial distribution in the bulk liquid and the amount of evaporated species in the adjacent vapour phase. The activities in the liquid phase are calculated from the mean vapour phase densities at a given composition, providing a good qualitative agreement compared to experimental data and the precision of the method follows a previously developed Poisson model of evaporation. With the Redlich–Kister approach for the activities in a binary mixture, the directly obtained activities are fitted providing corrected activity coefficients of the two species. This method is applied to ethanol water mixtures at different mole fractions. The obtained structural data are in good agreement with experimental data and time-averaged density profiles provide a detailed insight into the composition of the liquid–vapour interface. An azeotropic point is obtained for an excess concentration of ethanol at 87% as percentage by mass compared to the experimental value of 95%.
Keywords : Molecular dynamics vapour–liquid equilibria binary mixture azeotrope activity coefficient
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Michael Bley, Magali Duvail, Philippe Guilbaud, Christophe Penisson, Johannes Theisen, et al.. Molecular simulation of binary phase diagrams from the osmotic equilibrium method: vapour pressure and activity in water–ethanol mixtures. Molecular Physics, Taylor & Francis, 2018, 116 (15-16), pp.2009-2021. ⟨10.1080/00268976.2018.1444209⟩. ⟨cea-01760168⟩

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