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用动态光散射法(DLS)测定离子液体[EMIM][N(CN)2]、[EMIM][NTf2]和[HMIM][NTf2]与丙酮和乙醇混合物的二元扩散系数。

Binary diffusion coefficients for mixtures of ionic liquids [EMIM][N(CN)2], [EMIM][NTf2], and [HMIM][NTf2] with acetone and ethanol by dynamic light scattering (DLS).

机构信息

Erlangen Graduate School in Advanced Optical Technologies (SAOT), University of Erlangen-Nuremberg, Paul-Gordan-Straße 6, D-91052 Erlangen, Germany.

出版信息

J Phys Chem B. 2013 Feb 28;117(8):2429-37. doi: 10.1021/jp306116h. Epub 2013 Feb 15.

Abstract

Mutual diffusivities for binary mixtures of the ionic liquids (ILs) [EMIM][N(CN)2] (1-ethyl-3-methylimidazolium dicyanimide), [EMIM][NTf2] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), and [HMIM][NTf2] (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) with acetone and ethanol were studied in dependence on composition in the temperature range from 283.15 to 323.15 K, applying dynamic light scattering (DLS). The influence of experimental parameters on the achievable uncertainties was analyzed to ensure the acquisition of accurate data in adequate measurement times. For all probed systems, increasing binary diffusion coefficients were found for increasing temperatures. The systematic variation of anion and cation of the investigated ILs as well as a comparison with the literature data demonstrates the considerable influence of different ions on the resulting binary diffusion coefficients. Mutual diffusivities were found to be lower for the mixtures with ethanol than for those with acetone, which could be related to the formation of hydrogen bonds between ethanol and the ions. Most of the investigated IL solvent mixtures show increasing binary diffusion coefficients with increasing solvent concentration. For the mixtures of [EMIM][NTf2] with ethanol, however, a minimum of the mutual diffusivities was found in the ethanol mole fraction range from 0.7 to 0.8, which may hint at the vicinity of a critical demixing point. The viscosity of the pure ILs turned out to be no reliable indicator for the mutual diffusivity in mixtures with the same solvent.

摘要

离子液体(ILs)[EMIM][N(CN)2](1-乙基-3-甲基咪唑二氰胺)、[EMIM][NTf2](1-乙基-3-甲基咪唑双(三氟甲基磺酰基)亚胺)和[HMIM][NTf2](1-己基-3-甲基咪唑双(三氟甲基磺酰基)亚胺)与丙酮和乙醇的二元混合物的互扩散系数随温度在 283.15 至 323.15 K 范围内的变化关系进行了研究,应用了动态光散射(DLS)方法。分析了实验参数对可达到的不确定度的影响,以确保在足够的测量时间内获得准确的数据。对于所有被探测的系统,随着温度的升高,二元扩散系数都有所增加。所研究的 IL 的阴离子和阳离子的系统变化以及与文献数据的比较表明,不同离子对最终的二元扩散系数有相当大的影响。对于与乙醇的混合物,互扩散系数比与丙酮的混合物要低,这可能与乙醇和离子之间形成氢键有关。在所研究的大多数 IL 溶剂混合物中,随着溶剂浓度的增加,二元扩散系数增加。然而,对于[EMIM][NTf2]与乙醇的混合物,在乙醇摩尔分数范围从 0.7 到 0.8 时发现互扩散系数出现最小值,这可能暗示着接近临界分相点。纯 IL 的粘度并不是与相同溶剂混合时互扩散系数的可靠指标。

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