Temperature‐Dependent Prediction of the Liquid Entropy of Ionic Liquids |
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| Authors: | Dr Ulrich Preiss Dr Vladimir N Emel'yanenko Prof Dr Sergey P Verevkin Dr Daniel Himmel Dr Yauheni U Paulechka Prof Dr Ingo Krossing |
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| Institution: | 1. Freiburger Materialforschungszentrum (FMF), Universit?t Freiburg, Stefan‐Meier‐Str. 21, 79104 Freiburg (Germany), Fax: (+49)?761?203?6001;2. Department of Physical Chemistry, University of Rostock, Dr.‐Lorenz‐Weg 1, 18059 Rostock (Germany);3. Institut für Anorganische und Analytische Chemie, Universit?t Freiburg, Albertstr. 21, 79104 Freiburg (Germany);4. Chemical Faculty, Belarusian State University, Leningradskaya 14, 220030 Minsk (Belarus) |
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| Abstract: | 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 (Sl0=1.585 kJ mol?1 K?1 nm?3?rm3+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. |
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| Keywords: | computational chemistry ion pairs ionic liquids quantum chemistry thermodynamics |
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