CO2 absorption using two morpholine protic ionic liquids: measurement, model, and quantum chemical calculation

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics Pub Date : 2024-05-06 DOI:10.1016/j.jct.2024.107322

Hongwei Jin, Xiaohan Li, Kangkang Li, Zhou Feng, Zhonghao Li, Hongzhi Xia, Shiqi Qu, Huanong Cheng, Yugang Li, Xinshun Tan, Shiqing Zheng

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引用次数: 0

Abstract

Two kinds of protic ionic liquids, N-methylmorpholinium formate ([NMMH][For]) and N-ethylmorpholinium formate ([NEMH][For]), were synthesized by the acid-base neutralization method. The solubility of carbon dioxide (CO₂) in the two ionic liquids was measured at temperatures of 298.15 to 338.15 K and pressures of up to 900 kPa. The solubility increases linearly with pressure, indicating that CO₂ is physically absorbed in ionic liquids. The solubility of CO₂ in [NEMH][For] is higher than that of [NMMH][For]. Absorption behavior was investigated by thermodynamic properties, such as the Henry's law constant, partial molar Gibbs free energy, partial molar enthalpy, and partial molar entropy. The Pitzer's model and the Soave-Redlich-Kwong (SRK) cubic equation of state were used to fit the solubility data, respectively. The Pitzer's model is found to have better prediction accuracy. The interaction of two protic ionic liquids with CO₂ was analyzed using quantum chemistry. The molecular mechanism of CO₂ absorption by two protic ionic liquids was explained from the microscopic point of view. CO₂ + [NEMH][For] has more hydrogen bonds and a higher interaction energy. The cation–anion interaction of [NEMH][For] diminishes in the presence of CO₂, resulting in an increase in the cation–anion distance. These factors result in higher solubility of CO₂ in [NEMH][For].

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使用两种吗啉质离子液体吸收二氧化碳：测量、模型和量子化学计算

采用酸碱中和法合成了两种原生离子液体，即 N-甲基吗啉甲酸盐（[NMMH][For]）和 N-乙基吗啉甲酸盐（[NEMH][For]）。在 298.15 至 338.15 K 的温度和高达 900 kPa 的压力下，测量了二氧化碳（CO2）在这两种离子液体中的溶解度。溶解度随压力呈线性增长，表明二氧化碳在离子液体中被物理吸收。二氧化碳在[NEMH][For]中的溶解度高于[NMMH][For]。通过亨利定律常数、部分摩尔吉布斯自由能、部分摩尔焓和部分摩尔熵等热力学性质研究了吸收行为。分别使用 Pitzer 模型和 Soave-Redlich-Kwong (SRK) 立方状态方程来拟合溶解度数据。结果发现，Pitzer 模型的预测精度更高。利用量子化学分析了两种质子离子液体与 CO2 的相互作用。从微观角度解释了两种质离子液体吸收 CO2 的分子机理。CO2 + [NEMH][For] 具有更多的氢键和更高的相互作用能。在 CO2 的存在下，[NEMH][For] 的阳离子-阴离子相互作用减弱，导致阳离子-阴离子距离增加。这些因素导致二氧化碳在[NEMH][For]中的溶解度更高。

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

Journal of Chemical Thermodynamics 工程技术-热力学

CiteScore

5.60

自引率

15.40%

发文量

199

审稿时长

79 days

期刊介绍： The Journal of Chemical Thermodynamics exists primarily for dissemination of significant new knowledge in experimental equilibrium thermodynamics and transport properties of chemical systems. The defining attributes of The Journal are the quality and relevance of the papers published. The Journal publishes work relating to gases, liquids, solids, polymers, mixtures, solutions and interfaces. Studies on systems with variability, such as biological or bio-based materials, gas hydrates, among others, will also be considered provided these are well characterized and reproducible where possible. Experimental methods should be described in sufficient detail to allow critical assessment of the accuracy claimed. Authors are encouraged to provide physical or chemical interpretations of the results. Articles can contain modelling sections providing representations of data or molecular insights into the properties or transformations studied. Theoretical papers on chemical thermodynamics using molecular theory or modelling are also considered. The Journal welcomes review articles in the field of chemical thermodynamics but prospective authors should first consult one of the Editors concerning the suitability of the proposed review. Contributions of a routine nature or reporting on uncharacterised materials are not accepted.