Energetics of metastudtite and implications for nuclear waste alteration

Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina; Curtius, Hildegard; Bosbach, Dirk; Navrotsky, Alexandra

doi:10.1073/pnas.1421144111

Title: Energetics of metastudtite and implications for nuclear waste alteration

Journal Article · Mon Nov 24 00:00:00 EST 2014 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1421144111· OSTI ID:1235149

Guo, Xiaofeng ^[1]; Ushakov, Sergey V. ^[2]; Labs, Sabrina ^[3]; Curtius, Hildegard ^[3]; Bosbach, Dirk ^[3]; Navrotsky, Alexandra ^[2]

Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture and Technology Organized Research Unit and, Department of Chemistry, University of California, Davis, CA 95616, and
Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture and Technology Organized Research Unit and
Institute of Energy and Climate Research (IEK-6), Nuclear Waste Management, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany

Metastudtite, (UO₂)O₂(H₂O)₂, is one of two known natural peroxide minerals, but little is established about its thermodynamic stability. In this work, its standard enthalpy of formation, $$-$$1,779.6 ± 1.9 kJ/mol, was obtained by high temperature oxide melt drop solution calorimetry. Decomposition of synthetic metastudtite was characterized by thermogravimetry and differential scanning calorimetry (DSC) with ex situ X-ray diffraction analysis. We observed four decomposition steps in oxygen atmosphere: water loss around 220 °C associated with an endothermic heat effect accompanied by amorphization; another water loss from 400 °C to 530 °C; oxygen loss from amorphous UO₃ to crystallize orthorhombic α-UO_2.9; and reduction to crystalline U₃O₈. This detailed characterization allowed calculation of formation enthalpy from heat effects on decomposition measured by DSC and by transposed temperature drop calorimetry, and both these values agree with that from drop solution calorimetry. The data explain the irreversible transformation from studtite to metastudtite, the conditions under which metastudtite may form, and its significant role in the oxidation, corrosion, and dissolution of nuclear fuel in contact with water.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: DESC0001089; SC0001089

OSTI ID:: 1235149

Alternate ID(s):: OSTI ID: 1210536

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 111 Journal Issue: 50; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 53 works

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materials and chemistry by design
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Title: Energetics of metastudtite and implications for nuclear waste alteration

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