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毛细管气相色谱法测定[bmmim][NTf2]中的无限稀释活度系数

Measurements of Infinite Dilution Activity Coefficients of Ionic Liquid [bmmim][NTf_2] Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns
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摘要 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。 This paper was mainly to investigate the distribution behaviors of 60 organic compounds in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [bmmim][NTf2] at the temperature of 313.15, 323.15 and 333.15 K. The static-wall-coated open-tubular(WCOT) columns with three different wall thicknesses were used to measure the retention time by gas chromatograph and the data of infinite dilution activity coefficients(γ∞) were calculated by the revised equation. In addition, selectivity coefficients and capacity factors were calculated from the determined γ∞ values. The linear solvation energy relationship(LSER) model regression constants of [bmmim][NTf2] were obtained by linear fitting. The results show that the dominant interactions are hydrogen-bond asicity and dipolarity/polarizability,and the hydrogen-bond basicity of [NTf2]^- is weaker than [dca]^- and similar to [PF6]^-. Meanwhile, hydrogen-bond acidity would decrease when ?-H of imidazolyl is substituted by methyl. At last, the feasibility of [bmmim][NTf2] used as extractants for mixtures which are hard to separate such as acetonitrile-ethanol, acetone-cyclohexane, benzene-cyclohexane and toluene-methyl cyclohexane mixtures was investigated.
出处 《高校化学工程学报》 EI CAS CSCD 北大核心 2015年第6期1297-1305,共9页 Journal of Chemical Engineering of Chinese Universities
基金 国家自然科学基金(21436010 21222601 91434115) 浙江省自然科学基金(LR13B060001) 教育部新世纪优秀人才支持计划(NCET-13-0524)资助
关键词 无限稀释活度系数 离子液体 毛细管柱 线性溶剂化能模型 气相色谱法 infinite dilution activity coefficients ionic liquid static-wall-coated open-tubular columns linear solvation energy relationship model gas chromatography
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