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离子液体中对生物降解起关键作用的功能基团:对气体溶解度的影响。

The presence of functional groups key for biodegradation in ionic liquids: effect on gas solubility.

机构信息

Laboratoire de Thermodynamique des Solutions et des Polymères, CNRS/Université Blaise Pascal, Clermont-Ferrand, 24 avenue des Landais, Aubière Cedex, France.

出版信息

ChemSusChem. 2010 Mar 22;3(3):377-85. doi: 10.1002/cssc.200900241.

Abstract

The effect of the incorporation of either ester or ester and ether functions into the side chain of an 1-alkyl-3-methylimidazolium cation on the physico-chemical properties of ionic liquids containing bis(trifluoromethylsulfonyl)imide or octylsulfate anions is studied. It is believed that the introduction of an ester function into the cation of the ionic liquids greatly increases their biodegradability. The density of three such ionic liquids is measured as a function of temperature, and the solubility of four gases-carbon dioxide, ethane, methane, and hydrogen-is determined between 303 K and 343 K and at pressures close to atmospheric level. Carbon dioxide is the most soluble gas, followed by ethane and methane; the mole fraction solubilities vary from 1.8 x 10(-3) to 3.7 x 10(-2). These solubilities are of the same order of magnitude as those determined for alkylimidazolium-based ionic liquids. The chemical modification of the alkyl side chain does not result in a significant change of the solvation properties of the ionic liquid. All of the solubilities decrease with increasing temperature, corresponding to an exothermal solvation process. From the variation of this property with temperature, the thermodynamic functions of solvation (Gibbs energy, enthalpy, and entropy) are calculated and provide information about the solute-solvent interactions and the molecular structure of the solutions.

摘要

研究了在 1-烷基-3-甲基咪唑阳离子的侧链中引入酯基或酯基和醚基官能团对含有双(三氟甲基磺酰基)亚胺或辛基硫酸盐阴离子的离子液体的物理化学性质的影响。据信,在离子液体的阳离子中引入酯基会大大提高其生物降解性。测量了三种这样的离子液体的密度作为温度的函数,并在接近大气水平的压力下确定了四种气体-二氧化碳、乙烷、甲烷和氢气-在 303 K 至 343 K 之间的溶解度。二氧化碳是最易溶解的气体,其次是乙烷和甲烷;摩尔分数溶解度从 1.8 x 10(-3)到 3.7 x 10(-2)不等。这些溶解度与基于烷基咪唑的离子液体所确定的溶解度处于同一数量级。烷基侧链的化学修饰不会导致离子液体的溶剂化性质发生显著变化。所有的溶解度都随温度的升高而降低,对应于一个放热的溶剂化过程。从该性质随温度的变化,可以计算出溶剂化的热力学函数(吉布斯能量、焓和熵),并提供有关溶质-溶剂相互作用和溶液的分子结构的信息。

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