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

Abstract

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.

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [6];  [6];  [7];  [6];  [4];  [5];  [8];  [7]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
  2. Univ. of California, Davis, CA (United States); Nuclear Research Center (Israel)
  3. Univ. of California, Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
  4. Univ. of California, Berkeley, CA (United States)
  5. Univ. of Chicago, IL (United States)
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  7. Univ. of California, Davis, CA (United States)
  8. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
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 Org.:
USDOE
OSTI Identifier:
1243177
Report Number(s):
PNNL-SA-113798
Journal ID: ISSN 1477-9226; 47956; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 11; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

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, and Navrotsky, Alexandra. U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO4, CrUO4 and FeUO4. United States: N. p., 2016. Web. doi:10.1039/C6DT00066E.
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. U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO4, CrUO4 and FeUO4. United States. https://doi.org/10.1039/C6DT00066E
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, and Navrotsky, Alexandra. 2016. "U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO4, CrUO4 and FeUO4". United States. https://doi.org/10.1039/C6DT00066E.
@article{osti_1243177,
title = {U(v) in Metal Uranates. A Combined Experimental And Theoretical Study of MgUO4, CrUO4 and FeUO4},
author = {Guo, Xiaofeng and Tiferet, Eitan and Qi, Liang and Solomon, J. and Lanzirotti, Anthony and Newville, Mathew and Engelhard, Mark H. and Kukkadapu, Ravi K. and Wu, Di and Ilton, Eugene S. and Asta, Mark D. and Sutton, Steve and Xu, Hongwu and Navrotsky, Alexandra},
abstractNote = {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.},
doi = {10.1039/C6DT00066E},
url = {https://www.osti.gov/biblio/1243177}, journal = {Dalton Transactions},
issn = {1477-9226},
number = 11,
volume = 45,
place = {United States},
year = {Tue Feb 02 00:00:00 EST 2016},
month = {Tue Feb 02 00:00:00 EST 2016}
}

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Works referencing / citing this record: