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Density functional theoretical study on the preferential selectivity of macrocyclic dicyclohexano-18-crown-6 for Sr+2 ion over Th+4 ion during extraction from an aqueous phase to organic phases with different dielectric constants

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Abstract

The preferential selectivity of dicyclohexano-18-crown-6 (DCH18C6) for bivalent Sr+2 ion over tetravalent Th+4 ion was investigated using generalized gradient approximated (GGA) BP86 and the hybrid B3LYP density functional, employing split valence plus polarization (SV(P)) and triple-zeta valence plus polarization (TZVP) basis sets in conjunction with the COSMO (conductor-like screening model) solvation approach. The calculated theoretical selectivity of DCH18C6 for Sr+2 ion over Th+4 ion was found to be in accord with the selectivity for Sr+2 ion over Th+4 ion observed when performing liquid–liquid extraction experiments in different organic solvents. While 1:1(M:L) stoichiometric complexation reactions can be used to predict the preferential selectivity of Sr2+ ion over Th4+ ion, the results obtained are not consistent with the experimental results observed upon increasing the dielectric constant of the solvent. The calculated theoretical gas-phase data for the free energy of complexation, ∆G, fail to explain the selectivity for Sr+2 ion over Th+4 ion. However, when 1:2 (M:L) stoichiometric complexation reactions (reported in previous X-ray crystallography studies) are considered, correct and consistent results for the selectivity for Sr+2 ion over a wide range of dielectric constants are predicted. The distribution constant for Sr2+ and Th4+ ions was found to gradually increase with increasing dielectric constant of the organic solvent, and was found to be highest in nitrobenzene. The selectivity data calculated from ∆∆G ext are in excellent agreement with the results obtained from solvent extraction experiments.

Experimentally observed separation factors and theoretically predicted values of ΔΔG ext for Sr2+ ion over Th4+ ion with DCH18C6 in a nitrate medium. Solvent extraction with DCH18C6/nitrobenzene shows high selectivity and a high separation factor for Sr2+ over Th4+. DFT was successfully adopted to model the extraction mechanism of Sr2+/Th4+. The free energy of extraction ΔΔG ext failed to predict the experimental selectivity of Sr2+ over Th4+ for 1:1 stoichiometric complexation, but was able to predict this selectivity for 1:2 stoichiometric complexation with Th4+ ion. The ΔΔG ext values for the preferential selection of Sr2+ over Th4+ increase with increasing dielectric constant of the solvent

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Acknowledgments

The Computer Division at Bhabha Atomic Research Centre is acknowledged for allowing us to use the Anupam supercomputing facility.

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Authors and Affiliations

  1. Chemical Engineering Division, Chemical Engineering Group, Bhabha Atomic Research Centre, Mumbai, 400 085, India

    A. Boda, J. M. Joshi, Sk. M. Ali, K. T. Shenoy & S. K. Ghosh

  2. Homi Bhabha National Institute, Mumbai, 400 085, India

    A. Boda & Sk. M. Ali

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  1. A. Boda
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  2. J. M. Joshi
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  3. Sk. M. Ali
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  4. K. T. Shenoy
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  5. S. K. Ghosh
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Correspondence to Sk. M. Ali.

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Boda, A., Joshi, J.M., Ali, S.M. et al. Density functional theoretical study on the preferential selectivity of macrocyclic dicyclohexano-18-crown-6 for Sr+2 ion over Th+4 ion during extraction from an aqueous phase to organic phases with different dielectric constants. J Mol Model 19, 5277–5291 (2013). https://doi.org/10.1007/s00894-013-2015-5

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  • DOI: https://doi.org/10.1007/s00894-013-2015-5

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