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High-resolution Measurement of Contact Ion-pair Structures in Aqueous RbCl Solutions from the Simultaneous Corefinement of their Rb and Cl K-edge XAFS and XRD Spectra

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Abstract

In concentrated solutions of aqueous RbCl, all of the Rb+ and Cl– ions exist as contact ion pairs. This full structural assessment is derived from the refinement of three independent experimental measurements: the Rb and Cl K-edge X-ray absorption fine structure (XAFS) and the X-ray diffraction spectra (XRD). This simultaneous refinement of the XAFS and XRD data provides high accuracy since each method probes the structure of different local regions about the ions with high sensitivity. At high RbCl concentration (6 mol·kg–1) the solution is dominated by Rb+–Cl– contact ion pairs yielding an average of 1.5 pairs at an Rb–Cl distance of 3.24 Å. Upon formation of these ion pairs, approximately 1.1 waters molecules are displaced from the Rb+ and 1.4 water molecules from Cl–. The hydration shells about both the cation and anion are also determined. These results greatly improve the understanding of monovalent ions and provide a basis for testing the Rb+–Cl– interaction potentials used in molecular dynamics (MD) simulation.

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Acknowledgments

VTP was supported by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under Grant Number 103.99-2013.19. Work by JLF was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The PNC/XSD facilities at the Advanced Photon Source, and research at these facilities, are supported by DOE/BES, the Canadian Light Source and its funding partners, the University of Washington, and the Advanced Photon Source. Use of the Advanced Photon Source, an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, was supported by the DOE under Contract No. DE-AC02-06CH11357. Dr. F. Baudelet is acknowledged for constructive discussion.

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Authors and Affiliations

  1. Center for Quantum Electronics, Institute of Physics, Vietnam Academy of Science and Technology, P.O. Box 429, Boho, 10000, Hanoi, Vietnam

    Van-Thai Pham

  2. Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP48, 91192, Gif-sur-Yvette, France

    Van-Thai Pham

  3. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99354, USA

    John L. Fulton

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  1. Van-Thai Pham
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  2. John L. Fulton
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Correspondence to Van-Thai Pham.

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Pham, VT., Fulton, J.L. High-resolution Measurement of Contact Ion-pair Structures in Aqueous RbCl Solutions from the Simultaneous Corefinement of their Rb and Cl K-edge XAFS and XRD Spectra. J Solution Chem 45, 1061–1070 (2016). https://doi.org/10.1007/s10953-016-0487-5

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  • DOI: https://doi.org/10.1007/s10953-016-0487-5

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