Domańska U, Królikowska M
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland ; Thermodynamic Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban, 4001 South Africa.
J Solution Chem. 2012 Sep;41(8):1422-1445. doi: 10.1007/s10953-012-9875-7. Epub 2012 Aug 21.
Densities and viscosities have been determined for binary mixtures of the ionic liquids (ILs) 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-butyl-4-methylpyridinium thiocyanate [BMPy][SCN], or 1-butyl-1-methylpyrrolidinium thiocyanate [BMPYR][SCN], or 1-butyl-1-methylpiperidinium thiocyanate [BMPIP][SCN] with water over wide range of temperatures (298.15-348.15) K and ambient pressure. The thermal properties of [BMPy][SCN], i.e. glass transition temperature and the heat capacity at glass transition, have been measured using a differential scanning microcalorimetry, DSC. The decomposition of [BMPy][SCN] was detected. The density and viscosity correlations for these systems have been made using an empirical second-order polynomial and by the Vogel-Fulcher-Tammann equation, respectively. The concentration dependences have been described by polynomials. The excess molar volumes and deviations in viscosity have been calculated from the experimental values and were correlated by Redlich-Kister polynomial expansions. The variations of these parameters, with compositions of the mixtures and temperature, have been discussed in terms of molecular interactions. A qualitative analysis of the trend of properties with composition and temperature was performed. Further, the excess partial molar volumes, [Formula: see text] and [Formula: see text], were calculated and discussed. The isobaric expansivities (coefficient of thermal expansion), α, and the excess isobaric expansivities, α(E), were determined for four ILs and their mixtures with water. The results indicate that the interactions of thiocyanate ILs with water is not as strong as with alcohols, which is shown by the positive/slightly negative excess molar volumes in these binary systems. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10953-012-9875-7) contains supplementary material, which is available to authorized users.
已测定了离子液体(ILs)1 - 丁基 - 3 - 甲基咪唑硫氰酸盐[BMIM][SCN]、1 - 丁基 - 4 - 甲基吡啶硫氰酸盐[BMPy][SCN]、1 - 丁基 - 1 - 甲基吡咯烷硫氰酸盐[BMPYR][SCN]或1 - 丁基 - 1 - 甲基哌啶硫氰酸盐[BMPIP][SCN]与水在较宽温度范围(298.15 - 348.15)K及环境压力下的二元混合物的密度和粘度。使用差示扫描量热法(DSC)测量了[BMPy][SCN]的热性质,即玻璃化转变温度和玻璃化转变时的热容。检测到了[BMPy][SCN]的分解。这些体系的密度和粘度相关性分别使用经验二阶多项式和Vogel - Fulcher - Tammann方程建立。浓度依赖性用多项式描述。由实验值计算了过量摩尔体积和粘度偏差,并通过Redlich - Kister多项式展开进行关联。根据分子间相互作用讨论了这些参数随混合物组成和温度的变化。对性质随组成和温度的趋势进行了定性分析。此外,计算并讨论了过量偏摩尔体积[公式:见原文]和[公式:见原文]。测定了四种离子液体及其与水的混合物的等压膨胀系数(热膨胀系数)α和过量等压膨胀系数α(E)。结果表明,硫氰酸盐离子液体与水的相互作用不如与醇类的相互作用强,这在这些二元体系中过量摩尔体积为正/略为负得到体现。电子补充材料:本文的在线版本(doi:10.1007/sl0953 - 012 - 9875 - 7)包含补充材料,授权用户可获取。