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Demixing in liquids: approaches based on simple equations of state

Abstract : The demixing transition in partially miscible liquid mixtures is investigated within the framework of the simple van der Waals (vdW)-type equations of state (EOS) approaches. Two approximations for the excluded volume free energy have been considered. One is a modified vdW expression (denoted as vdW here). The other is the well known MansooriCarnahanStarlingLeland (MCSL) excess free energy for hard sphere fluid mixtures (MCSL). In order to adopt an universal representation, we suggest to rescale the physical quantities such as the temperature, pressure and density by the critical parameters of the liquidvapour (LV) transition of the monodisperse fluid. We compare phase diagrams from the two theories and the theoretical predictions with available simulation results of binary LennardJones mixtures. For the systems studied, the two theoretical approaches give qualitatively similar LV and liquidliquid (LL) phase diagrams. The MCSL EOS is able to predict in a semi-quantitative way the LL phase diagram.
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Yanlong Li, Hong Xu. Demixing in liquids: approaches based on simple equations of state. Physics and Chemistry of Liquids, Taylor & Francis, 2013, 51 (4), pp.433-446. ⟨10.1080/00319104.2012.722063⟩. ⟨hal-01517071⟩



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