Thermodynamic evaluation of intermolecular interaction selectivity in separation of binary mixtures based on the activity coefficients at infinite dilution

Bakusele Kabane, Balungile Gasa, Nirmala Deenadayalu
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Abstract

Thermodynamic evaluation of deep eutectic solvents in separation of binary mixtures is increasing, and this is due to an easy preparation of deep eutectic solvents and their properties can be altered by different combinations of hydrogen bond acceptor to hydrogen bond donor. This study presents the intermolecular interactions between the prepared deep eutectic solvent with volatile organic solvents at different temperatures, T = (313.15 – 353.15) K and at atmospheric pressure. The investigated solvents were prepared by the combination of tetrabutylammonium acetate as hydrogen bond acceptor and ethylene glycol or diethylene glycol as hydrogen bond donor at a molar ratio of 1:3, respectively. The influence of hydrogen bond donor in separation of binary mixtures was evaluated and discussed. The intermolecular interactions of the prepared deep eutectic solvents with volatile organic solvents were evaluated based on the activity coefficients at infinite dilution values measured by the use of gas liquid chromatography. Excess thermodynamic properties at infinite dilution including excess enthalpies, Gibbs free energies and entropies were computed to further elucidate the interactions between the systems. Selectivity and capacity values were calculated to determine the feasibility of the solvents in separating industrial binary mixtures. The solvents were found promising for the separation of close boiling point mixtures comprising alcohols.
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基于无限稀释时的活性系数,对二元混合物分离过程中分子间相互作用选择性的热力学评估
在二元混合物的分离过程中,对深共晶溶剂的热力学评估越来越多,这是因为深共晶溶剂易于制备,而且其性质可通过氢键受体与氢键供体的不同组合而改变。本研究介绍了所制备的深共晶溶剂与挥发性有机溶剂在不同温度(T = (313.15 - 353.15) K)和常压下的分子间相互作用。所研究的溶剂是以四丁基醋酸铵为氢键受体,乙二醇或二甘醇为氢键供体,摩尔比分别为 1:3 的组合制备的。评估并讨论了氢键供体对分离二元混合物的影响。根据使用气相液相色谱法测量的无限稀释时的活性系数,评估了制备的深共晶溶剂与挥发性有机溶剂的分子间相互作用。计算了无限稀释时的过量热力学性质,包括过量热焓、吉布斯自由能和熵,以进一步阐明体系间的相互作用。通过计算选择性和容量值,确定了这些溶剂在分离工业二元混合物中的可行性。结果表明,这些溶剂在分离由醇类组成的沸点接近的混合物方面很有前景。
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