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采用反气相色谱法(IGC)表征了离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)在333~373 K 温度范围内的热力学参数。使用两组不同化学结构和性质的探针分子测定了[ BMIM]BF4与溶剂之间的相互作用力。根据探针分子的保留时间计算得到探针分子与[ BMIM]BF4之间的摩尔吸附焓、质量分数活度系数、Flory-Huggins相互作用参数和[ BMIM]BF4的溶解度参数。结果表明,所选溶剂中 n-C10、n-C11、n-C12、四氯化碳,环己烷和甲苯为[BMIM]BF4的不良溶剂;二氯甲烷、丙酮、氯仿、乙酸甲酯、乙醇、甲醇为[BMIM]BF4的良溶剂。运用外推法得到了[HMIM]BF4在室温(298.15K)时的溶解度参数为23.39(J/cm3)0.5。实验结果证明 IGC 法是一种简便准确的获得离子液体热力学参数的方法。本研究为离子液体的应用及相关工作提供了理论参考。

Thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([ BMIM ] BF4 )were determined via inverse gas chromatography( IGC). Two groups of solvents with different chemical natures and polarities were used to obtain information about[ BMIM]BF4-solvent interactions. The specific retention volume,molar heat of sorption,weight fraction activity coefficient,Flory-Huggins interaction param-eter as well as solubility parameter were also determined in a temperature range of 333-373 K. The results showed that the selected solvents n-C10 to n-C12,carbon tetrachloride,cyclohexane and toluene were poor sol-vents for[BMIM]BF4,while dichloromethane,acetone,chloroform,methyl acetate,ethanol and methanol were favorite solvents for[BMIM]BF4. In addition,the solubility parameter of[BMIM]BF4 was determined as 23. 39( J/cm3 )0. 5 by the extrapolation at 298 K. The experiment proved that IGC was a simple and accurate method to obtain the thermodynamic properties of ionic liquids. This study could be used as a reference to the application and research of the ionic liquids.

参考文献

[1] McLachlan F.;Mathews CJ.;Smith PJ.;Welton T..Palladium-catalyzed suzuki cross-coupling reactions in ambient temperature ionic liquids: Evidence for the importance of palladium imidazolylidene complexes[J].Organometallics,200325(25):5350-5357.
[2] Zhang H;Wu J;Zhang J;He JS.1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: A new and powerful nonderivatizing solvent for cellulose[J].Macromolecules,200520(20):8272-8277.
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