Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Stefan-Meier-Str. 21, 79104 Freiburg, Germany.
Chemphyschem. 2010 Nov 15;11(16):3425-31. doi: 10.1002/cphc.201000614.
Modeling of the temperature-dependent liquid entropy of ionic liquids (ILs) with great accuracy using COSMO-RS is demonstrated. The minimum structures of eight IL ion pairs are investigated and the entropy, calculated from ion pairs, is found to differ on average only 2% from the available experimental values (119 data points). For calculations with single ions, the average error amounts to 2.6% and stronger-coordinating ions tend to give higher deviations. Additionally, the first parameterization of the standard liquid entropy for ILs is presented in the context of traditional volume-based thermodynamics (S(l)(0)=1.585 kJ mol(-1) K(-1) nm(-3)·r(m)(3)+14.09 J mol(-1) K(-1)), which sheds light on the statistical treatment of ionic interactions. The findings provide the first direct access to accurate predictions of liquid entropies of ILs, which are tedious and time-consuming to measure.
利用 COSMO-RS 非常精确地对离子液体 (ILs) 的温度相关液体熵进行建模。研究了八种 IL 离子对的最小结构，发现从离子对计算出的熵平均仅与可用实验值（119 个数据点）相差 2%。对于单个离子的计算，平均误差为 2.6%，并且强配位离子往往会产生更高的偏差。此外，还提出了传统基于体积的热力学中 ILs 标准液体熵的第一个参数化 (S(l)(0)=1.585 kJ mol(-1) K(-1) nm(-3)·r(m)(3)+14.09 J mol(-1) K(-1))，这为离子相互作用的统计处理提供了启示。这些发现为直接准确预测 ILs 的液体熵提供了首次尝试，因为这些熵的测量既繁琐又耗时。
