Thermodynamic modeling of aqueous and mixed-solvent alkali chloride solutions using an ion-pairing equation of state

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria Pub Date : 2024-09-16 DOI:10.1016/j.fluid.2024.114231

Abtin Raeispour Shirazi , Fufang Yang , Tri Dat Ngo , Nicolas Ferrando , Olivier Bernard , Jean-Pierre Simonin , Jean-Charles de Hemptinne

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引用次数: 0

Abstract

In this work, the Binding-MSA (BiMSA) theory is implemented in an equation of state for the first time. The proposed model, BiMSA-electrolyte polar perturbed chain statistical associating fluid Theory (BiMSA-ePPC-SAFT), is applied to aqueous and mixed solvent electrolyte systems (water + methanol and water + ethanol) to investigate the impact of ion pairs. In a first step, a comparison is made between the Bjerrum and Wertheim theories for the calculation of the ion-ion association strength. The results obtained show that the Bjerrum theory is more successful in describing the association of ions especially in mixed solvent systems. In a second step, different types of relative static permittivity (RSP) models are implemented and compared. The obtained results reveal that using the Bjerrum theory with a volume-dependent RSP yields an ion-ion association strength that strongly changes with salinity. The models are further analyzed focusing on the relative importance of the various types of association (ion-solvent, solvent-solvent, solvent-cosolvent and cosolvent-cosolvent). It was observed that in an aqueous solution, ion-solvent and solvent-solvent association bonds are stronger and more important than those of ion pairing. However, for the mixed solvent systems, in high alcohol concentration, ion pairs exhibit the strongest bond.

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利用离子配对状态方程建立氯化碱水溶液和混合溶剂溶液的热力学模型

在这项研究中，首次在状态方程中应用了结合-MSA（BiMSA）理论。所提出的模型，即 BiMSA-电解质极性扰动链统计关联流体理论（BiMSA-ePPC-SAFT），被应用于水性和混合溶剂电解质体系（水+甲醇和水+乙醇），以研究离子对的影响。首先，比较了 Bjerrum 和 Wertheim 理论对离子-离子结合强度的计算。结果表明，Bjerrum 理论在描述离子结合方面更为成功，尤其是在混合溶剂体系中。第二步，实施并比较了不同类型的相对静态介电常数（RSP）模型。结果表明，使用 Bjerrum 理论和与体积相关的 RSP，离子与离子的结合强度会随着盐度的变化而强烈变化。对模型的进一步分析侧重于各种类型关联（离子-溶剂、溶剂-溶剂、溶剂-共溶剂和共溶剂-共溶剂）的相对重要性。结果表明，在水溶液中，离子-溶剂和溶剂-溶剂的关联键比离子配对的关联键更强、更重要。然而，对于混合溶剂体系，在高浓度酒精中，离子对的结合力最强。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

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.