Share This Article:

Peculiar Concentration Dependence of H/D Exchange Reaction in 1-Butyl-3-methylimidazolium Tetrafluoroborate-D2O Mixtures

Abstract Full-Text HTML Download Download as PDF (Size:264KB) PP. 70-76
DOI: 10.4236/ojpc.2011.13010    4,337 Downloads   8,886 Views   Citations


We have investigated the H/D exchange reaction between heavy water and an ionic liquid, 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4]), throughout the whole concentration region as a function of D2O mol% at room temperature. We expected that the extent of the H/D reaction would increase linearly with increasing content of D2O, but the results show an extended N-shaped behavior having a small maximum at around 40 mol% and the reaction becomes very slow at a specific concentration around 80 mol%. We found that this non-linear concentration dependence correlates with the pD dependence of the solutions.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

H. Abe, N. Hatano, Y. Ima, S. Ohta, A. Shimizu and Y. Yoshimura, "Peculiar Concentration Dependence of H/D Exchange Reaction in 1-Butyl-3-methylimidazolium Tetrafluoroborate-D2O Mixtures," Open Journal of Physical Chemistry, Vol. 1 No. 3, 2011, pp. 70-76. doi: 10.4236/ojpc.2011.13010.


[1] T. Welton, “Ionic Liquids in Synthesis,” Wiley-VCH, Weinheim, 2002.
[2] R. D. Rogers, K. R. Seddon and S. Volkov, “Green Industrial Applications of Ionic Liquids,” NATO Science Series, Springer, New York, 2002.
[3] Y. Jeon, J. Sung, D. Kim, C. Seo, H. Cheong, Y. Ouchi, R. Ozawa and H. Hamaguchi, “Structural Change of 1-Butyl-3-methylimidazolium Tetrafluoroborate + Water Mixtures Studied by Infrared Vibrational Spectroscopy,” The Journal of Physical Chemistry B, Vol. 112, No. 3, 2008, pp. 923-928. doi:10.1021/jp0746650
[4] L. Cammarata, S. G. Kazarian, P. A. Salter and T. Welton, “Molecular States of Water in Room Temperature Ionic Liquids,” Physical Chemistry Chemical Physics, Vol. 3, 2001, pp. 5192-5200. doi:10.1039/b106900d
[5] Y. Yoshimura, T. Goto, H. Abe and Y. Imai, “Existence of Nearly-Free Hydrogen Bonds in an Ionic Liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) Ammonium Tetrafluoroborate-Water at 77 K,” The Journal of Physical Chemistry B, Vol. 113, No. 23, 2009, pp. 8091-8095. doi:10.1021/jp902125f
[6] Y. Yoshimura, H. Kimura, C. Okamoto, T. Miyashita, Y. Imai and H. Abe, “Glass Transition Behaviour of Ionic Liquid, 1-Butyl-3-methylimidazolium Tetrafluoroborate- H2O Mixed Solutions,” The Journal of Chemical Thermodynamics, Vol. 43, No. 3, 2011, pp. 410-412. doi:10.1016/j.jct.2010.10.010
[7] H. Jin, X. Li and M. Maroncelli, “Heterogeneous Solute Dynamics in Room Temperature Ionic Liquids,” The Journal of Physical Chemistry B, Vol. 111, 2007, pp. 13473-13478. doi:10.1021/jp077226+
[8] A. Paul, P. Kumar and A. Samanta, “How Transparent Are the Imidazolium Ionic Liquids? A Case Study with 1-Methyl-3-butylimidazolium Hexafluorophosphate, [b- mim][PF6],” Chemical Physics Letters, Vol. 402, No. 4-6, 2005, pp. 375-379. doi:10.1016/j.cplett.2004.12.060
[9] Z. Hu and C. Margulis, “Heterogeneity in a Room- Temperature Ionic Liquid: Persistent Local Environments and the Red-Edge Effect,” Proceedings of the National Academy of Sciences of the United States of America, Vol. 103, No. 4, 2006, pp. 831-836. doi:10.1073/pnas.0507364103
[10] M. Moreno, F. Castiglione, A. Mele, C. Pasqui and G. Raos, “Interaction of Water with the Model Ionic Liquid [bmim][BF4]: Molecular Dynamics Simulations and Comparison with NMR Data,” The Journal of Physical Chemistry B, Vol. 112, No. 26, 2008, pp. 7826-7836. doi:10.1021/jp800383g
[11] W. Jiang, Y. Wang and G. A. Voth, “Molecular Dynamics Simulation of Nanostructural Organization in Ionic Liquid/Water Mixtures,” The Journal of Physical Chemistry B, Vol. 111, No. 18, 2007, pp. 4812-4818. doi:10.1021/jp067142l
[12] M. Nakakoshi, S. Ishihara, H. Utsumi, H. Seki, Y. Koga and K. Nishikawa, “Anomalous Dynamic Behavior of Ions and Water Molecules in Dilute Aqueous Solution of 1-Butyl-3-methylimidazolium Bromide Studied by NMR,” Chemical Physics Letters, Vol. 427, No. 1-3, 2006, pp. 87-90. doi:10.1016/j.cplett.2006.06.052
[13] Y. Yasaka, C. Wakai, N. Matubayashi and M. Nakahara, “Slowdown of H/D Exchange Reaction Rate and Water Dynamics in Ionic Liquids: Deactivation of Solitary Water Solvated by Small Anions in 1-Butyl-3-methyl- imidazolium Chloride,” The Journal of Physical Chemistry A, Vol. 111, No. 4, 2007, pp. 541-543. doi:10.1021/jp0673720
[14] H. Maity, W. Kilim, J. N. Rumbley and S. W. Englander, “Protein Hydrogen Exchange Mechanism: Local Fluctuations,” Protein Science, Vol. 12, No. 1, 2003, pp. 153-160. doi:10.1110/ps.0225803
[15] C. K. Woodward and B. D. Hilton, “Hydrogen Exchange Kinetics and Internal Motions in Proteins and Nucleic Acids,” Annual Review of Biophysics & Bioengineering, Vol. 8, 1979, pp. 99-127.
[16] Y. Bai, J. S. Milne, L. Mayne and S. W. Englander, “Primary Structure Effects on Peptide Group Hydrogen Exchange,” Proteins: Structure, Function, and Bioinformatics, Vol. 17, No. 1, 1993, pp. 75-86. doi:10.1002/prot.340170110
[17] C. A. Wamser, “Equilibria in the System Boron Trifluo- ride-Water at 25?,” Journal of the American Chemical Society, Vol. 73, No. 1, 1951, pp. 409-416. doi:10.1021/ja01145a134
[18] M. Anbar and S. Guttmann, “The Isotopic Exchange of Fluoroboric Acid with Hydrofluoric Acid,” The Journal of Physical Chemistry, Vol. 64, No. 12, 1960, pp. 1896- 1899. doi:10.1021/j100841a021
[19] P. K. Glasoe and F. A. Long, “Use of Glass Electrodes to Measure Acidities in Deuterium Oxide,” The Journal of Physical Chemistry, Vol. 64, No. 1, 1960, pp. 188-190. doi:10.1021/j100830a521
[20] J. D. Holbrey and K. R. Seddon, “The Phase Behaviour of 1-Alkyl-3-methylimidazolium Tetrafluoroborates; Io- nic Liquids and Ionic Liquid Crystals,” Journal of the Chemical Society, Dalton Transactions, No. 13, 1999, pp. 2133-2140. doi:10.1039/a902818h
[21] J. A. Pople, W. G. Scheneider and H. J. Bernstein, “High- Resolution Nuclear Magnetic Resonance,” McGraw-Hill, New York, 1959.
[22] F. Franks, “Water, A Comprehensive Treatise,” Plenum Press, New York, 1972.
[23] J. M. Harvey, S. E. Jackson and M. C. R. Symons, “Interactions in Water-Alcohol Mixtures Studied by NMR and Infrared Spectroscopy,” Chemical Physics Letters, 1977, Vol. 47, No. 3, pp. 440-441. doi:10.1016/0009-2614(77)85011-2
[24] P. K. Kipkemboi, P. C. Kiprono and A. J. Easteal, “Proton Nuclear Magnetic Resonance Study of Water + t-Butyl Alcohol, Water + t-Butylamine and Water + t-Butyl Alcohol + t-Butylamine Mixtures,” Bulletin of the Chemical Society of Ethiopia, Vol. 16, 2002, pp. 187- 198.
[25] J. G. Huddleston, A. E. Visser, W. M. Reichert, H. D. Willauer, G. A. Broker and R. D. Rogers, “Charac- terization and Comparison of Hydrophilic and Hydro- phobic Room Temperature Ionic Liquids Incorporating the Imidazolium Cation,” Green Chemistry, Vol. 3, No. 4, 2001, pp. 156-164. doi:10.1039/b103275p
[26] M. Tseng, Y. Liang and Y. Chu, “Synthesis of Fused Tetrahydro-β-carbolinequinoxalinones in 1-n-Butyl-2,3- dimethylimidazolium Bis(trifluoromethylsulfonyl)imide ([bdmim][Tf2N]) and 1-n-Butyl-2,3-dimethylimidazolium Perfluorobutylsulfonate ([bdmim][PFBuSO3]) Ionic Liquids,” Tetrahedron Letters, Vol. 46, No. 36, 2005, pp. 6131-6136. doi:10.1016/j.tetlet.2005.06.153
[27] M. G. Freire, C. M. S. S. Neves, I. M. Marrucho, J. A. P. Coutinho and A. M. Fernandes, “Hydrolysis of Tetrafluoroborate and Hexafluorophosphate Counter Ions in Imidazolium-Based Ionic Liquids,” The Journal of Phy- sical Chemistry A, Vol. 114, No. 11, 2010, pp. 3744-3749. doi:10.1021/jp903292n
[28] T. L. Amyes, S. T. Diver, J. P. Richard, F. M. Rivas and K. Toth, “Formation and Stability of N-Heterocyclic Carbenes in Water: The Carbon Acid pKa of Imidazolium Cations in Aqueous Solution,” Journal of the American Chemical Society, Vol. 126, No. 13, 2004, pp. 4366-4374. doi:10.1021/ja039890j
[29] J. Dupont and J. Spencer, “On the Noninnocent Nature of 1,3-Dialkylimidazolium Ionic Liquids,” Angewandte Chemie International Edition, Vol. 43, No. 40, 2004, pp. 5296-5297. doi:10.1002/anie.200460431
[30] S. T. Handy and M. Okello, “The 2-Position of Imidazolium Ionic Liquids: Substitution and Exchange,” The Journal of Organic Chemistry, Vol. 70, No. 5, 2005, pp. 1915-1918. doi:10.1021/jo0480850
[31] O. Hollóczki, P. Terleczky, D. Szieberth, G. Mourgas, D. Gudat and L. Nyulászi, “Hydrolysis of Imidazole-2- ylidenes,” Journal of the American Chemical Society, Vol. 133, No. 4, 2011, pp. 780-789. doi:10.1021/ja103578y

comments powered by Disqus

Copyright © 2018 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.