Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Warsaw, Poland.
J Phys Chem B. 2011 Jun 9;115(22):7397-404. doi: 10.1021/jp202872t. Epub 2011 May 18.
The activity coefficients at infinite dilution, γ13(∞), for 44 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, tetrahydrofuran, ethers, and ketones in the ionic liquid (IL) N-hexyl-3-methylpyridinium tosylate (p-toluenesulfonate), [HM3Py][TOS], were determined by gas-liquid chromatography at temperatures from 338.15 to 368.15 K. The densities of [HM3Py][TOS] as a function of temperature have been measured at temperatures higher than the melting temperature and were extrapolated to T = 298.15 K. The gas-liquid partition coefficients, K(L) were calculated for all solutes. The partial molar excess Gibbs energies ΔG1(E,∞), enthalpies ΔH1(E,∞), and entropies ΔS1(E,∞) at infinite dilution were calculated from the experimental γ13(∞) values obtained over the temperature range. The selectivities for different separation problems including n-heptane/benzene, cyclohexane/benzene, and n-heptane/thiophene were calculated from γ13(∞) and compared to literature values for tosylate-based ILs, or hexyl-substituted cations of ILs, or pyridynium-based IL, or N-methyl-2-pyrrolidinone (NMP), and sulfolane.
在无限稀释条件下，44 种溶质（包括烷烃、环烷烃、烯烃、炔烃、芳烃、醇类、水、噻吩、四氢呋喃、醚类和酮类）在离子液体 N-己基-3-甲基吡啶对甲苯磺酸盐（[HM3Py][TOS]）中的活度系数γ13(∞)，通过气相色谱法在 338.15 至 368.15 K 的温度范围内进行了测定。[HM3Py][TOS]的密度作为温度的函数，在高于熔点的温度下进行了测量，并外推到 T = 298.15 K。所有溶质的气液分配系数 K(L)都进行了计算。从实验获得的 γ13(∞)值范围内，计算了无限稀释下的偏摩尔过剩吉布斯自由能 ΔG1(E,∞)、焓 ΔH1(E,∞)和熵 ΔS1(E,∞)。从 γ13(∞)值计算了不同分离问题的选择性，包括正庚烷/苯、环己烷/苯和正庚烷/噻吩，并与基于 tosylate 的离子液体、或 IL 的己基取代阳离子、或基于 pyridynium 的离子液体、或 N-甲基-2-吡咯烷酮（NMP）和环丁砜的文献值进行了比较。
