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In situ spectroscopy of Sm(III) and Sm(II) in LiCl–KCl eutectic molten salt

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Abstract

Fiber optic-based Raman and UV–Vis spectroscopy systems were commissioned for use in an inert atmosphere for in situ analysis of high temperature molten salts. The speciation of samarium chloride was studied in the LiCl–KCl eutectic system at 500 °C. Raman and electronic absorption spectra indicated trivalent samarium forms an octahedral SmCl63− complex with two detectable Raman features. Metallothermic and electrolytic reduction of Sm(III) to Sm(II) in the alkali halide solution was carried out to investigate the coordination of Sm(II) in the same eutectic salt. Formation of the Sm(II) was confirmed using UV–Vis absorption spectroscopy. The resulting spectra are reported and discussed in terms of complex formation, inelastic scattering, and electronic absorption of the reduced Sm(II) ions. The Raman spectrum of metallothermically produced Sm(II) exhibited similar shift to the Raman spectrum of metallothermically reduced Nd(II).

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Acknowledgements

This work was supported by the United States Department of Energy (DOE) under Contracts DE-NE0008236 and DE-NE0008572, the DOE Office of Nuclear Energy's Nuclear Energy University Programs under award DE-NE0008889, and the United States Nuclear Regulatory Commission (NRC) under contracts NRC-HQ-13-G-38-0027 and 31310018M0032. VJS acknowledges the fellowship award from the NRC. Dr. Kenny Osborne and Ms. Nancy Hebron-Israel serve as the DOE and NRC award program managers, respectively. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1447692. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation, the U.S. Department of Energy, or the United States Government.

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  1. Chemical and Materials Engineering Department, University of Nevada, Reno, 1664 N Virginia St MS0388, Reno, NV, 89557-0388, USA

    Vickram J. Singh, Jeremy T. Moon, Christopher D. Bruneau & Dev Chidambaram

  2. Nevada Institute for Sustainability, University of Nevada, Reno, 1664 N Virginia St MS0388, Reno, NV, 89557-0388, USA

    Dev Chidambaram

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VJS: Conceptualization, methodology, formal analysis, investigation, writing—original draft, visualization JTM: Conceptualization, methodology, formal analysis, investigation, writing—original draft, visualization CDB: formal analysis, investigation DC: Conceptualization, writing—review and editing, supervision, project administration, funding acquisition.

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Correspondence to Dev Chidambaram.

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Singh, V.J., Moon, J.T., Bruneau, C.D. et al. In situ spectroscopy of Sm(III) and Sm(II) in LiCl–KCl eutectic molten salt. J Radioanal Nucl Chem 333, 641–650 (2024). https://doi.org/10.1007/s10967-023-09288-3

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