U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO4, CrUO4 and FeUO4

Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang; Solomon, J.; Lanzirotti, Anthony; Newville, Mathew; Engelhard, Mark H.; Kukkadapu, Ravi K.; Wu, Di; Ilton, Eugene S.; Asta, Mark D.; Sutton, Steve; Xu, Hongwu; Navrotsky, Alexandra

doi:10.1039/C6DT00066E

Title: U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO₄, CrUO₄ and FeUO₄

Journal Article · Tue Feb 02 00:00:00 EST 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/C6DT00066E· OSTI ID:1243177

Guo, Xiaofeng ^[1]; Tiferet, Eitan ^[2]; Qi, Liang ^[3]; Solomon, J. ^[4]; Lanzirotti, Anthony ^[5]; Newville, Mathew ^[5]; Engelhard, Mark H. ^[6]; Kukkadapu, Ravi K. ^[6]; Wu, Di ^[7]; Ilton, Eugene S. ^[6]; Asta, Mark D. ^[4]; Sutton, Steve ^[5]; Xu, Hongwu ^[8]; Navrotsky, Alexandra ^[7]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Nuclear Research Center (Israel)
Univ. of California, Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of Chicago, IL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of California, Davis, CA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Pentavalent uranium can exist in aqueous solution, but its presence in the solid state is uncommon. Metal monouranates, MgUO₄, CrUO₄ and FeUO₄ were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and ⁵⁷Fe-Mössbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. Moreover, the presence of U⁵⁺ has been solidly confirmed in CrUO₄ and FeUO₄, which are thermodynamically stable compounds, and the origin and stability of U⁵⁺ in the system was elaborated by DFT. The structural and thermodynamic behaviour of U⁵⁺ elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1243177

Report Number(s):: PNNL-SA-113798; 47956; KP1704020

Journal Information:: Dalton Transactions, Vol. 45, Issue 11; ISSN 1477-9226

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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