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Thermodynamics of cesium complexes formation with 18-crown-6 in ionic liquids

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Abstract

Thermodynamic data for cesium complexes formation with 18-crown-6 (18C6, L) [Cs(18C6)]+ in N-butyl-4-methyl-pyridinium tetrafluoroborate ([BMPy][BF4], I), in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4], II) and in 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN)2], III) were measured with NMR 133Cs technique at 23–50 °C. The stability of cesium complex in RTILs is estimated to be in the range between water and DMFA. Stability constants for [Cs(18C6)]+ are found to decrease as temperature is increasing. The following values for lgK(Cs+L) and ΔH(Cs+L) at 23 °C are determined: 2.6 (0.3), −47(1) kJ/mol (RTIL I); 2.8(0.3), −80(3) kJ/mol (RTIL II) and 3.03 (0.08), −47(2) kJ/mol (RTIL III). It is demonstrated that enthalpy change promotes complex formation while the corresponding change of entropy is negative and provides decomposition of [Cs(18C6)]+.

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Acknowledgements

The authors would like to thank the Russian Foundation for Basic Research (Grant 07-08-00246) and the Academy of Science of Finland for their financial support of the work. We also wish to express our gratitude to Päivi Joensuu for assistance in sample analysis.

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Authors and Affiliations

  1. State Research Institute of Reagents and High Purity Substances (IREA), Bogorodskii val 3, 107258, Moscow, Russia

    A. G. Vendilo

  2. Finnish Institute of Occupational Health, Aapistie 1, 90220, Oulu, Finland

    H. Rönkkömäki

  3. Department of Chemistry, University of Oulu, P.O. Box 3000, 90014, Oulu, Finland

    M. Hannu-Kuure, M. Lajunen, J. Asikkala, P. Oksman & L. H. J. Lajunen

  4. Zelinsky Institute of Organic Chemistry RAS, Leninsky pr. 47, 119991, Moscow, Russia

    V. G. Krasovsky & E. A. Chernikova

  5. Finnish Institute of Occupational Health, Arinatie 3, 00370, Helsinki, Finland

    T. Tuomi

  6. Department of Physical and Colloid Chemistry, Moscow State University of Food Technologies, Volokolamskoye Sh.11, 125080, Moscow, Russia

    K. I. Popov

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  1. A. G. Vendilo
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  2. H. Rönkkömäki
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  8. P. Oksman
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  9. L. H. J. Lajunen
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Corresponding author

Correspondence to H. Rönkkömäki.

Additional information

Partly the summary of data is published in Mendeleev Communications (2009), V. 19, p. XX.

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Vendilo, A.G., Rönkkömäki, H., Hannu-Kuure, M. et al. Thermodynamics of cesium complexes formation with 18-crown-6 in ionic liquids. J Incl Phenom Macrocycl Chem 66, 223–230 (2010). https://doi.org/10.1007/s10847-009-9600-3

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