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评估具有极性溶剂的离子液体的热物理性质:两种不同离子的离子液体家族的对比研究。

Evaluation of thermophysical properties of ionic liquids with polar solvent: a comparable study of two families of ionic liquids with various ions.

机构信息

Department of Chemistry, Sri Venkateswara University , Tirupati 517 502, India.

出版信息

J Phys Chem B. 2013 Oct 17;117(41):12535-48. doi: 10.1021/jp403813g. Epub 2013 Oct 3.

Abstract

In this work, we explore and compare the role of the ion effect on the thermophysical properties of two families of ionic liquids (ILs), namely, tetra-alkyl ammonium cation R4N with hydroxide OH anion and 1-alkyl-3-methyl imidazolium cation amim with different anions (chloride, methyl sulfate, and tetrafluoroborate), with polar solvent such as dimethylsulfoxide (DMSO) in the temperature range from 25 to 40 °C and over the whole concentration range of ILs. Two families of ILs, namely, tetramethyl ammonium hydroxide [(CH3)4N][OH] (TMAH), tetraethyl ammonium hydroxide [(C2H5)4N][OH] (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N][OH] (TPAH), and tetrabutyl ammonium hydroxide [(C4H9)4N][OH] (TBAH) from ammonium-based ILs and 1-ethyl-3-methylimidazolium chloride [Emim][Cl], 1-ethyl-3-methylimidazolium methylsulfate [Emim][MeSO4], 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4], and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) from imidazolium family of ILs, are used in the present study. To address the molecular interactions of ILs with DMSO, densities (ρ), ultrasonic sound velocities (u), and viscosities (η) have been measured over the entire composition range and at four temperatures, 25, 30, 35, and 40 °C, under atmospheric pressure. From these experimental data, the excess molar volume (V(E)), the deviation in isentropic compressibility (Δκs), and the deviation in viscosity (Δη) were calculated and were adequately correlated by using the Redlich-Kister polynomial equation. The measured and predicted data were interpreted on the basis of intermolecular interactions and structural effects between like and unlike molecules upon mixing. The hydrogen-bonding features between ammonium-based ILs and DMSO were analyzed using molecular modeling program by HyperChem 7.

摘要

在这项工作中,我们探索并比较了离子效应对两类离子液体(ILs)的热物理性质的影响,这两类 ILs 分别是带有氢氧根(OH-)阴离子的四烷基铵阳离子[R4N]+和带有不同阴离子(氯化物、甲基硫酸盐和四氟硼酸盐)的 1-烷基-3-甲基咪唑阳离子[amim]+,以及极性溶剂二甲亚砜(DMSO)。在 25 至 40°C 的温度范围内和整个 ILs 浓度范围内,我们研究了两类 ILs,即四甲基氢氧化铵[(CH3)4N][OH](TMAH)、四乙基氢氧化铵[(C2H5)4N][OH](TEAH)、四丙基氢氧化铵[(C3H7)4N][OH](TPAH)和四丁基氢氧化铵[(C4H9)4N][OH](TBAH),它们是铵基 ILs 的一部分,以及 1-乙基-3-甲基咪唑氯化物[Emim][Cl]、1-乙基-3-甲基咪唑甲基硫酸盐[Emim][MeSO4]、1-丁基-3-甲基咪唑四氟硼酸盐[Bmim][BF4]和 1-丁基-3-甲基咪唑氯化物([Bmim][Cl]),来自咪唑啉基 ILs。在本研究中,我们使用了这些 ILs。为了解决 ILs 与 DMSO 的分子相互作用,我们在整个组成范围内和四个温度(25、30、35 和 40°C)下测量了密度(ρ)、超声波速度(u)和粘度(η),在大气压下进行。从这些实验数据中,我们计算了过量摩尔体积(V(E))、等熵压缩率偏差(Δκs)和粘度偏差(Δη),并使用 Redlich-Kister 多项式方程进行了充分关联。通过使用 HyperChem 7 程序的分子建模程序,我们分析了铵基 ILs 和 DMSO 之间的氢键特征。

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