Abstract
The non-Bornian solvation model has been applied to a theoretical consideration of the Gibbs free energy for the transfer of fluorinated anions, non-fluorinated cations, and non-fluorinated anions at the 2H,3H-decafluoropentane (DFP)/water (W) and 1,2-dichloroethane (DCE)/W interfaces. According to our previous experimental results, the fluorinated anions are more stable in DFP than DCE, while the non-fluorinated cations and anions are less stable in DFP. To understand this characteristic feature of DFP, energy decomposition analyses have been performed for the hypothetical transfer of ions at the DFP/DCE interface. In conclusion, the characteristics of DFP as a fluorous solvent should be explained in terms of the higher repulsive interaction of the solvent molecule with ions, particularly with non-fluorinated ions.
Similar content being viewed by others
References
I. T. Horváth and J. Rábai, Science, 1994, 266, 72.
R. L. Scott, J. Am. Chem. Soc., 1948, 70, 4090.
J. H. Hildebrand and D. R. F. Cochran, J. Am. Chem. Soc., 1949, 71, 22.
D.-W. Zhu, Synthesis, 1993, 953.
J. A. Gladysz and C. Emnet, “Handbook of Fluorous Chemistry”, ed. J. A. Gladysz, D. P. Curran, and I. T. Horváth, 2004, Chap. 3, WILEY-VCH, Weinheim.
H. Katano, Y. Kuroda, and K. Uematsu, J. Electroanal. Chem., 2017, 788, 232.
H. Katano, K. Uematsu, Y. Kuroda, and T. Osakai, J. Electroanal. Chem., 2017, 796, 82.
H. Katano, K. Uematsu, Y. Kuroda, and T. Osakai, Anal. Sci., 2019, 35, 1031.
K. Uematsu, J. Yamagata, H. Sakae, H. Katano, and T. Osakai, Anal. Sci., 2021, 37, 1707.
In this study, the formal and standard Gibbs energies of ion transfer are defined as those from W to non-aqueous phase according to the IUPAC recommendation: Z. Samec, Pure Appl. Chem., 2004, 76, 2147.
L. E. Kiss, I. Kövesdi, and J. Rábai, J. Fluorine Chem., 2001, 108, 95.
E.. de Wolf, P. Ruelle, J. van den Broeke, B.-J. Deelman, and G.. van Koten, J. Phys. Chem. B, 2004, 108, 1458.
T. Osakai, Y. Naito, K. Eda, and M. Yamamoto, J. Phys. Chem. B, 2015, 119, 13167.
A. Yamada, E. Yoshida, K. Eda, and T. Osakai, Anal. Sci., 2018, 34, 919.
R. S. Mulliken, J. Chem. Phys., 1955, 23, 1833.
B. H. Besler, K. M. Merz, and P. A. Kollman, J. Comput. Chem., 1990, 11, 431.
U. C. Singh and P. A. Kollman, J. Comput. Chem., 1984, 5, 129.
A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev., 1988, 88, 899.
B. Lee and F. M. Richards, J. Mol. Biol., 1971, 55, 379.
A. Shrake and J. A. Rupley, J. Mol. Biol., 1973, 79, 351.
K. Kitaura and K. Morokuma, Int. J. Quantum Chem., 1976, 10, 325.
H. Umeyama and K. Morokuma, J. Am. Chem. Soc., 1977, 99, 1316.
S.-H. Hwang, J.-R. Kim, S. D. Lee, H. Lee, H. S. Kim, and H. Kim, J. Ind. Eng. Chem., 2007, 13, 537.
S. A. Mumford and J. W. C. Phillips, J. Chem. Soc., 1950, 75.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Osakai, T., Kato, T., Eda, K. et al. A Theoretical Approach to the Fluorophilicity of Ions via the Gibbs Energy of Ion Transfer at the Fluorous Solvent/Water Interface. ANAL. SCI. 37, 1783–1787 (2021). https://doi.org/10.2116/analsci.21P178
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2116/analsci.21P178