水溶液中非常规离子无限稀释摩尔电导率的基团贡献法  

Group Contribution Method for Infinite Dilution Molar Conductivity of Unconventional Ions in Water

作　　者：万仁 宋璠 彭昌军[1] 刘洪来[1] WAN Ren;SONG Fan;PENG Changjun;LIU Honglai(School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学与分子工程学院,上海200237

出　　处：《高等学校化学学报》2021年第12期3672-3679,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22078086)资助.

摘　　要：非常规离子是指伴随离子液体(ILs)不断创制而出现的离子,其最大特点是具有可设计性.当ILs处于无限稀释状态时,最为重要的传递性质是单个离子的无限稀释摩尔电导率(λ∞B),其能反映离子的溶剂化作用,是联系不同传递性质的重要纽带.建立了基团贡献法预测咪唑类阳离子和季铵类阳离子的无限稀释摩尔电导率模型(λ∞B-GCM),获得了咪唑中心离子[Im]、烷基铵[N]、甲基[—CH3]、亚甲基[—CH2—]、环氢[ring-H]、醚基[—O—]和羟基[—OH]等基团对无限稀释摩尔电导率的贡献值.建立的λ∞B-GCM不仅能反映不同基团对无限稀释摩尔电导率的影响,还能体现温度对无限稀释摩尔电导率的影响.研究结果表明,GCM预测的lnλ∞B含有超过70%的数据点的绝对相对偏差小于2%,绝对相对偏差超过5%的数据点不足1%,总的平均绝对相对偏差为1.57%,说明采用基团贡献法预测非常规阳离子无限稀释摩尔电导率是一种简单可靠的方法.Unconventional ions refer to ions that have been appear with the continuous creation of ionic liquids(ILs),and their most attractive feature is that they can be designed.When ILs are in an infinite dilution state,the most important transfer property is the infinite dilution molar conductivity(λ∞B)of a single ion,which re⁃flects the solvation of the ion and is an important link between different transfer properties.The group contribu⁃tion method(GCM)was established to predict the infinite dilution molar conductivity model(λ∞B-GCM)of imid⁃azole cations and quaternary ammonium cations,and obtain the contributions of the imidazole central ion[Im],alkylammonium[N],methyl[-CH3],methyl[-CH2-],ring hydrogen[ring-H],ether group[-O-],hydroxyl group[-OH]and other groups to the infinite dilution molar conductivity.The establishedλ∞B-GCM can not only reflect the influence of different groups on the infinite dilution molar conductivity,but also reveal the relationship between the temperature and the infinite dilution molar conductivity.The results showed that more than 70%of data points predicted lnλ∞B by GCM produced an absolute relative deviation of less than 2%,less than 1%of data points with an absolute relative deviation of more than 5%and the total average absolute relative deviation was 1.57%.Overall,λ∞B-GCM is a simple and reliable method to predict the infinite dilution molar conductivity of unconventional cations.

关 键 词：无限稀释摩尔电导率 基团贡献法 非常规离子 离子液体 

分 类 号：O645.16[理学—物理化学]