毛细管气相色谱法测定[bmmim][NTf2]中的无限稀释活度系数?

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采用毛细管气相色谱法,应用3根不同膜厚的1-丁基-2,3-二甲基咪唑双(三氟甲烷磺酰)亚胺盐([bmmim][NTf2],1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide)离子液体壁涂毛细管柱,分别在40、50和60℃下测定了60种有机物的保留时间。使用改进方程计算得到了60种有机物在[bmmim][NTf2]中的无限稀释活度系数,并通过无限稀释活度系数计算得到了无限稀释选择性系数、容量因子等热力学参数。通过线性拟合求得[bmmim][NTf2]的LSER模型关联参数,发现最显著的作用力是偶极/极化作用和氢键碱性,且[NTf2]?的氢键碱性小于[dca]?,与[PF6]?相近,同时验证了咪唑阳离子的2位H被甲基取代后,氢键酸性明显降低。此外,探讨了将[bmmim][NTf2]用于乙腈-乙醇、丙酮-环己烷、苯-环己烷、甲苯-甲基环己烷等难分离体系分离的可行性。 Using capillary gas chromatography, three different concentrations of 1-butyl-2,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide ([bmmim] [NTf2] , 3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide (IMC) was applied to the capillary column. The retention time of 60 organic compounds was measured at 40, 50 and 60 ℃, respectively. The infinite dilution activity coefficients of 60 organic compounds in [bmmim] [NTf2] were calculated using the improved equation and the thermodynamic parameters such as infinite dilution selectivity coefficient and capacity factor were calculated by the infinite dilution activity coefficient. The linear correlation was used to derive the LSER model parameters for [bmmim] [NTf2]. The most significant forces were found to be dipole / polarization and hydrogen bond basicity, and the hydrogen bond basicity of [NTf2]? Was less than [dca ] ?, which is similar to [PF6] ?, and at the same time it is verified that the hydrogen bond acidity is significantly reduced after the 2-position H of imidazolium cation is substituted by methyl. In addition, the feasibility of using [bmmim] [NTf2] for the separation of difficult separation systems such as acetonitrile-ethanol, acetone-cyclohexane, benzene-cyclohexane and toluene-methylcyclohexane was discussed.
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