In Situ Determination of Speciation and Local Structure of NaCl–SrCl2 and LiF–ZrF4 Molten Salts

Lynch, Timothy J.; Birkner, Nancy R.; Christian, Matthew S.; Wrubel, Jacob A.; Schorne-Pinto, Juliano; Van Veelen, Arjen; Bargar, John R.; Besmann, Theodore M.; Brinkman, Kyle S.; Chiu, Wilson K. S.

doi:10.1021/acs.jpcb.1c07552

Title: In Situ Determination of Speciation and Local Structure of NaCl–SrCl₂ and LiF–ZrF₄ Molten Salts

Journal Article · 09 February 2022 · Journal of Physical Chemistry. B

DOI: https://doi.org/10.1021/acs.jpcb.1c07552 · OSTI ID:2205489

Lynch, Timothy J. ^[1]; Birkner, Nancy R. ^[2];

^[3]; Wrubel, Jacob A. ^[4];

^[3]; Van Veelen, Arjen ^[5];

^[5]; Besmann, Theodore M. ^[3];

^[2];

^[4]

Univ. of Connecticut, Storrs, CT (United States); University of Connecticut
Clemson Univ., SC (United States)
Univ. of South Carolina, Columbia, SC (United States)
Univ. of Connecticut, Storrs, CT (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Understanding the local environment of the metal atoms in salt melts is important for modeling the properties of melts and predicting their behavior and thus helping enable the development of technologies such as molten salt reactors and solar-thermal power systems and new approaches to recycling rare-earth metals. Toward that end, we have developed an in situ approach for measuring the coordination of metals in molten salt coupling X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Our approach was demonstrated for two salt mixtures (1.9 and 5 mol % SrCl₂ in NaCl, 0.8 and 5 mol % ZrF₄ in LiF) at up to 1100 °C. Near-edge (X-ray absorption near-edge structure, XANES) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The EXAFS response was modeled using ab initio FEFF calculations. Strontium’s first shell is observed to be coordinated with chlorine (Sr²⁺–Cl^–) and zirconium’s first shell is coordinated by fluorine (Zr⁴⁺–F^–), both having coordination numbers that decrease with increasing temperature. Multiple zirconium complexes are believed to be present in the melt, which may interfere and distort the EXAFS spectra and result in an anomalously low zirconium first shell coordination number. Finally, the use of boron nitride (BN) powder as a salt diluent for XAFS measurements was found to not interfere with measurements and thus can be used for investigations of such systems.

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Research Organization:: Univ. of Connecticut, Storrs, CT (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: EE0008302; NE0008772

OSTI ID:: 2205489

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 7 Vol. 126; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Raman spectroscopy
anions
extended X-ray absorption fine structure
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Title: In Situ Determination of Speciation and Local Structure of NaCl–SrCl2 and LiF–ZrF4 Molten Salts

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Title: In Situ Determination of Speciation and Local Structure of NaCl–SrCl₂ and LiF–ZrF₄ Molten Salts