Vibrational spectroscopy of uranium tetrafluoride hydrates

DeVore, Michael A.; Villa-Aleman, Eliel; Felder, Justin B.; Yeon, Jeongho; zur Loye, Hans-Conrad; Wellons, Matthew S.

doi:10.1016/j.vibspec.2021.103277

Vibrational spectroscopy of uranium tetrafluoride hydrates

Journal Article · Thu Jun 24 00:00:00 EDT 2021 · Vibrational Spectroscopy

DOI:https://doi.org/10.1016/j.vibspec.2021.103277· OSTI ID:1807892

^[1]; Villa-Aleman, Eliel ^[1]; Felder, Justin B. ^[2]; Yeon, Jeongho ^[2]; zur Loye, Hans-Conrad ^[2]; Wellons, Matthew S. ^[1]

Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Univ. of South Carolina, Columbia, SC (United States)

Uranium tetrafluoride (UF₄) is an important intermediate in the production of UF6 and nuclear fuel. Historical characterization of UF₄ with Raman spectroscopy was plagued with ambiguity until the first accurate Raman spectrum was published by our group in 2016. Although generally considered to be relatively stable, UF₄ can hydrolyze to form numerous UF₄ hydrates that may play a role in future uranium waste forms. In contrast to anhydrous UF₄, the hydrates, with their OH stretch and HOH bending modes, can be spectroscopically characterized by the type and degree of water bonding in the crystal lattice, which can yield additional information about their crystal structure. Herein, vibrational spectroscopy (Raman and infrared) was used to characterize three different UF₄ hydrates: UF₄(H₂O)_0.33, U₃F₁₂(H₂O), and UF₄(H₂O)_2.5. Spectra show the different hydrates vary in the number of observed bands, full-width half-maximum of the bands, and band intensity. These differences are due to varying interactions between the OH stretch and HOH bending modes with UF₄ and the polymeric UF₄ structure in the crystal lattice. These vibrational data, in combination with spectral fitting and crystallographic structures measured with powder X-ray diffraction and single crystal X-ray diffraction, provide unique details on the location of water molecules in the crystal lattice of hydrated UF₄, and provide an interesting contrast to the vibrational spectra of anhydrous UF₄.

View Accepted Manuscript (DOE)

Research Organization:: Savannah River Site (SRS), Aiken, SC (United States); Savannah River National Lab (SRNL), Aiken, SC (United States)

Sponsoring Organization:: USDOE Office of Environmental Management (EM)

Grant/Contract Number:: AC09-08SR22470

OSTI ID:: 1807892

Alternate ID(s):: OSTI ID: 1864849

Report Number(s):: SRNL--STI-2020-00530

Journal Information:: Vibrational Spectroscopy, Journal Name: Vibrational Spectroscopy Vol. 115; ISSN 0924-2031

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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