Skip to main content
SpringerLink
Log in

Enthalpies of Solution and Enthalpies of Solvation in Water: The Anion Effect in Ionic Liquids with Common 1-Ethyl-3-methyl-imidazolium Cation

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Thermochemical studies of ionic liquids (ILs) in aqueous solution were carried out using solution calorimetry. Heat effects of dissolution in water at 298.15 K and molar limiting enthalpies of solution were measured for ILs having a common cation, 1-ethyl-3-methyl-imidazolium, connected with different anions: diethylphosphate, ethylsulfate, tetracyanoborate, thiocyanate, and trifluoroacetate. Molar enthalpies of solvation of ILs in water were derived from experimental data for solution and vaporization enthalpies. Enthalpic data were correlated with ionic liquid specific parameters and descriptors. The best correlation was observed with hydrogen-bonding interaction energies. This result confirmed that hydrogen bonding is one of the main types of intermolecular interactions inherent for ILs in aqueous solutions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Welton, T.: Room temperature ionic liquids. Solvents for synthesis and catalysis. Chem. Rev. 99, 2071–2083 (1999)

    Article  CAS  Google Scholar 

  2. Plechkova, N.V., Seddon, K.R.: Applications of ionic liquids in the chemical industry. Chem. Soc. Rev. 37, 123–150 (2008)

    Article  CAS  Google Scholar 

  3. McFarlane, J., Ridenour, W.B., Luo, H., Hunt, R.D., DePaoli, D.W., Ren, R.X.: Room temperature ionic liquids for separating organics from produced water. Sep. Sci. Technol. 40, 1245–1265 (2005)

    Article  CAS  Google Scholar 

  4. Freire, M.G., Catarina, M.S., Neves, S.J.: Mutual solubilities of water and hydrophobic ionic liquids. J. Phys. Chem. B 111, 13082–13089 (2007)

    Article  CAS  Google Scholar 

  5. Huddleston, J.G., Visser, A.E., Reichert, W.M., Willauer, H.D., Broker, G.A., Rogers, R.D.: Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation. Green Chem. 3, 156–164 (2001)

    Article  CAS  Google Scholar 

  6. Kurnia, K.A., Pinho, S.P., Coutinho, J.A.P.: Designing ionic liquids for absorptive cooling. Green Chem. 16, 3741–3745 (2014)

    Article  CAS  Google Scholar 

  7. Waliszewski, D., Stepniak, I., Piekarski, H., Lewandowski, A.: Heat capacities of ionic liquids and their heats of solution in molecular liquids. Thermochim. Acta 433, 149–152 (2005)

    Article  CAS  Google Scholar 

  8. Domanska, U., Królikowski, M., Pobudkowska, A., Bochenska, P.: Solubility of ionic liquids in water and octan-1-ol and octan-1-ol/water, or 2-phenylethanol/water partition coefficients. J. Chem. Thermodyn. 55, 225–233 (2012)

    Article  CAS  Google Scholar 

  9. Anthony, J.L., Maginn, E.J., Brennecke, J.F.: Solution thermodynamics of imidazolium-based ionic liquids and water. J. Phys. Chem. B 105, 10942–10949 (2001)

    Article  CAS  Google Scholar 

  10. Freire, M.G., Carvalho, P.J., Gardas, R.L., Marrucho, I.M., Santos, L.M.N.B.F., Coutinho, J.A.P.: Mutual solubilities of water and the [C n mim][Tf2N] hydrophobic ionic liquids. J. Phys. Chem. B 112, 1604–1610 (2008)

    Article  CAS  Google Scholar 

  11. Freire, M.G., Neves, C.M.S.S., Shimizu, K., Bernardes, C.E.S., Marrucho, I.M., Coutinho, J.A.P., Lopes, J.N.C., Rebelo, L.P.N.: Mutual solubility of water and structural/positional isomers of N-alkylpyridinium-based ionic liquids. J. Phys. Chem. B 114, 15925–15934 (2010)

    Article  CAS  Google Scholar 

  12. Martins, M.A.R., Neves, C.M.S.S., Kurnia, K.A., Luís, A., Santos, L.M.N.B.F., Freire, M.G., Pinho, S.P., Coutinho, J.A.P.: Impact of the cation symmetry on the mutual solubilities between water and imidazolium-based ionic liquids. Fluid Phase Equilib. 375, 161–167 (2014)

    Article  CAS  Google Scholar 

  13. Freire, M.G., Neves, C.M.S.S., Ventura, S.P.M., Pratas, M.J., Marrucho, I.M., Oliveira, J., Coutinho, J.A.P., Fernandes, A.M.: Solubility of non-aromatic ionic liquids in water and correlation using a QSPR approach. Fluid Phase Equilib. 294, 234–240 (2010)

    Article  CAS  Google Scholar 

  14. Neves, C.M.S.S., Rodrigues, A.R., Kurnia, K.A., Esperanca, J.M.S.S., Freire, M.G., Joao, A.P., Coutinho, J.A.P.: Solubility of non-aromatic hexafluorophosphate-based salts and ionic liquids in water determined by electrical conductivity. Fluid Phase Equilib. 358, 50–55 (2013)

    Article  CAS  Google Scholar 

  15. Królikowska, M., Karpinska, M., Zawadzki, M.: Phase equilibria study of (ionic liquid + water) binary mixtures. Fluid Phase Equilib. 354, 66–74 (2013)

    Article  Google Scholar 

  16. Krolikowska, M.: (Solid + liquid) and (liquid + liquid) phase equilibria of (IL + water) binary systems. The influence of the ionic liquid structure on mutual solubility. Fluid Phase Equilib. 361, 273–281 (2014)

    Article  CAS  Google Scholar 

  17. Zhao, Y., Chen, Z., Wang, J., Zhuo, K.: Solution thermodynamics of some imidazolium-based ionic liquids in water and aliphatic alcohols. Z. Phys. Chem. 223, 857–868 (2009)

    Article  CAS  Google Scholar 

  18. Ficke, L.E.: Rodrı´guez, H., Brennecke, J.F.: heat capacities and excess enthalpies of 1-ethyl-3-methylimidazolium-based ionic liquids and water. J. Chem. Eng. Data 53, 2112–2119 (2008)

    Article  CAS  Google Scholar 

  19. Ficke, L.E., Novak, R.R., Brennecke, J.F.: Thermodynamic and thermophysical properties of ionic liquid + water systems. J. Chem. Eng. Data 55, 4946–4950 (2010)

    Article  CAS  Google Scholar 

  20. Krolikowska, M., Paduszynski, K., Hofman, T., Antonowicz, J.: Heat capacities and excess enthalpies of the (N-hexylisoquinolinium thiocyanate ionic liquid + water) binary systems. J. Chem. Thermodyn. 55, 144–150 (2012)

    Article  CAS  Google Scholar 

  21. Krolikowska, M., Paduszynski, K., Zawadzki, M.: Measurements, correlations, and predictions of thermodynamic properties of N-octylisoquinolinium thiocyanate ionic liquid and its aqueous solutions. J. Chem. Eng. Data 58, 285–293 (2013)

    Article  CAS  Google Scholar 

  22. Krolikowska, M., Zawadzki, M., Krolikowski, M.: Physicochemical and thermodynamic study on aqueous solutions of dicyanamide-based ionic liquids. J. Chem. Thermodyn. 70, 127–137 (2014)

    Article  CAS  Google Scholar 

  23. Bothe, H., Cammenga, H.K.: Calorimetric investigation of aqueous caffeine solutions and molecular association of caffeine. Thermochim. Acta 69, 235–252 (1983)

    Article  CAS  Google Scholar 

  24. Sabbah, R., An, X.W., Chickos, J.S., Leitao, M.L.P., Roux, M.V., Torres, L.A.: Reference materials for calorimetry and differential thermal analysis. Thermochim. Acta 331, 93–204 (1999)

    Article  CAS  Google Scholar 

  25. Yermalayeu, A.V., Zaitsau, D.H., Emel’yanenko, V.N., Verevkin, S.P.: Thermochemistry of ammonium based ionic liquids: thiocyanates—experiments and computations. J. Solution Chem. (2015). doi:10.1007/s10953-015-0316-2

    Google Scholar 

  26. Hallén, D., Nilsson, S.-O., Rothschild, W., Wadsö, I.: Enthalpies and heat capacities for n-alkan-1-ols in H2O and D2O. J. Chem. Thermodyn. 18, 429–442 (1986)

    Article  Google Scholar 

  27. Solomonov, B.N., Varfolomeev, M.A., Nagrimanov, R.N., Novikov, V.B., Zaitsau, D.H., Verevkin, S.P.: Solution calorimetry as a complementary tool for the determination of enthalpies of vaporization and sublimation of low volatile compounds at 298.15 K. Thermochim. Acta 589, 164–173 (2014)

    Article  CAS  Google Scholar 

  28. Zaitseva, K.V., Varfolomeev, M.A., Solomonov, B.N.: Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis. Thermochim. Acta 535, 8–16 (2012)

    Article  CAS  Google Scholar 

  29. Sanahuja, A., Gómez-Estévez, J.L.: The influence of the extrapolation method on enthalpies of solution at infinite dilution. Thermochim. Acta 94, 223–279 (1985)

    Article  CAS  Google Scholar 

  30. Solomonov, B.N., Novikov, V.B., Mikhail, A., Varfolomeev, M.A., Klimovitskii, A.E.: Calorimetric determination of hydrogen-bonding enthalpy for neat aliphatic alcohols. J. Phys. Org. Chem. 18, 1132–1137 (2005)

    Article  CAS  Google Scholar 

  31. Zaitsau, D.H., Fumino, K., Emel’yanenko, V.N., Yermalayeu, A.V., Ludwig, R., Verevkin, S.P.: Structure–property relationships in ionic liquids: a study of the anion dependence in vaporization enthalpies of imidazolium-based ionic liquids. Chem. Phys. Chem 13, 1868–1876 (2012)

    CAS  Google Scholar 

  32. Grubbs, L.M., Acree, W.E., Abraham, M.H.: Mathematical correlations for describing enthalpies of solvation of organic vapors and gaseous solutes into ionic liquid solvents. Thermochim. Acta 509, 87–92 (2010)

    Article  CAS  Google Scholar 

  33. Grubbs, L.M., Acree, W.E., Abraham, M.H.: Correlation of enthalpies of solvation of organic vapors and gases in ionic liquid solvents using a group contribution version of the Abraham solvation parameter model. Thermochim. Acta 511, 96–101 (2010)

    Article  CAS  Google Scholar 

  34. Bensaid, Z., Mutelet, F., Bouroukba, M., Negadi, A.: Experimental and theoretical study of interaction between organic compounds and 1-(4-sulfobutyl)-3-methylimidazolium based ionic liquids. Fluid Phase Equilib. 378, 34–43 (2014)

    Article  CAS  Google Scholar 

  35. Symons, M.C.R.: Water structure: unique but not anomalous. Philos. Trans. R. Soc. Lond. 359, 1631–1646 (2001)

    Article  CAS  Google Scholar 

  36. Claudio, A.F.M., Swift, L., Hallett, J.P., Welton, T., Coutinho, J.A.P., Freire, M.G.: Extended scale for the hydrogen-bond basicity of ionic liquids. Phys. Chem. Chem. Phys. 16, 6593–6601 (2014)

    Article  CAS  Google Scholar 

  37. García-Miaja, G., Tronsoco, J., Romani, L.: Excess enthalpy, density, and heat capacity for binary systems of alkyl-imidazolium-based ionic liquids + water. J. Chem. Thermodyn. 41, 161–166 (2009)

    Article  Google Scholar 

Download references

Acknowledgments

This work has been performed according to the Russian Government Program of Competitive Growth of Kazan Federal University. Also, authors gratefully acknowledge the financial support by grant MK-7126.2015.3.

Author information

Authors and Affiliations

  1. Department of Physical Chemistry, Kazan Federal University, Kremlevskaya 18, Kazan, 420008, Russia

    Mikhail A. Varfolomeev, Artashes A. Khachatrian, Bulat S. Akhmadeev, Boris N. Solomonov & Sergey P. Verevkin

  2. Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, 18059, Rostock, Germany

    Andrei V. Yermalayeu & Sergey P. Verevkin

Authors
  1. Mikhail A. Varfolomeev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Artashes A. Khachatrian
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Bulat S. Akhmadeev
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Boris N. Solomonov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Andrei V. Yermalayeu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sergey P. Verevkin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mikhail A. Varfolomeev.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Varfolomeev, M.A., Khachatrian, A.A., Akhmadeev, B.S. et al. Enthalpies of Solution and Enthalpies of Solvation in Water: The Anion Effect in Ionic Liquids with Common 1-Ethyl-3-methyl-imidazolium Cation. J Solution Chem 44, 811–823 (2015). https://doi.org/10.1007/s10953-015-0328-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-015-0328-y

Keywords

Search

Navigation