立方状态方程与不适合液液平衡的 gE 模型相结合能否预测液液平衡?

IF 2.8 3区 工程技术 Q3 CHEMISTRY, PHYSICAL Fluid Phase Equilibria Pub Date : 2024-10-12 DOI:10.1016/j.fluid.2024.114249
Romain Privat , Jean-Noël Jaubert , Georgios M. Kontogeorgis
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引用次数: 0

摘要

在现代版本的立方状态方程(EoS)中,EoS 参数的混合规则是通过使用休伦-维达尔法(Huron-Vidal)或零参考压力法(ZRP)的活度系数模型推导出来的。事实上,威尔逊的活度系数模型无法预测液液平衡(LLE),因此本文试图回答这样一个问题:如果将威尔逊模型与立方 EoS 相耦合,得到的模型是否能够预测 LLE?我们的研究表明,虽然威尔逊模型在数学上无法预测不稳定液相,但威尔逊-EoS 模型(即包含威尔逊模型的 EoS)却并非如此。然而,研究还表明,Wilson-EoS 预测 LLE 的能力不仅取决于所选择的方法(Huron-Vidal 或 ZRP),还取决于混合物的特征(如共容比、临界吸引力参数比、二元相互作用参数等)。
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Can liquid-liquid equilibria be predicted by the combination of a cubic equation of state and a gE model not suitable for liquid-liquid equilibria?
In modern versions of cubic equations of state (EoS), the mixing rules for EoS parameters are derived from an activity coefficient model using either the Huron-Vidal or the Zero Reference Pressure (ZRP) approach. As it is a fact that Wilson's activity coefficient model cannot predict liquid-liquid equilibria (LLE), this article attempts to answer the question: if Wilson's model is coupled with a cubic EoS, is the resulting model capable of predicting LLE?
This question is actually becoming increasingly important as recent EoS rely on such a coupling (e.g., the tc-PR EoS). We show that although Wilson's model is mathematically unable to predict instable liquid phases, this is not true for Wilson-EoS models (i.e., EoS incorporating Wilson's model). However, it is also shown that the capacity of Wilson-EoS to predict LLE depends not only on the approach chosen (Huron-Vidal or ZRP) but also on mixture characteristics (such as the ratio of covolumes, the ratio of critical attractive parameters, the binary interaction parameters etc.).
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来源期刊
Fluid Phase Equilibria
Fluid Phase Equilibria 工程技术-工程:化工
CiteScore
5.30
自引率
15.40%
发文量
223
审稿时长
53 days
期刊介绍: Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results. Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.
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