Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions

Kirkegaard, Marie C.; Ambrogio, Michael W.; Miskowiec, Andrew J.; Shields, Ashley E.; Niedziela, Jennifer L.; Spano, Tyler L.; Anderson, Brian B.

doi:10.1016/j.jnucmat.2019.151889

Title: Characterizing the degradation of [(UO₂F₂)(H₂O)]₇ 4H₂O under humid conditions

Abstract

Under humid conditions, uranyl fluoride ([(UO₂F₂)(H₂O)]₇·4H₂O) undergoes a loss of fluorine to form a uranyl hydroxide species, which can be further hydrated to form a uranyl peroxide species. X-ray diffraction data of the uranyl peroxide product is presented for the first time. In addition, the temperature and humidity conditions under which these reactions occur have been clarified by a 220-day experiment using microRaman spectroscopy to track chemical changes in individual particles of uranyl fluoride. At 25 and 35^°C, uranyl fluoride is found to be stable at 32% relative humidity but not stable at and above 59% relative humidity. We show that water vapor pressure is the driving factor in formation of both the hydroxide and peroxide products. The kinetics of the transformation from uranyl fluoride into uranyl hydroxide is consistent with a denucleation reaction following the absorption of water molecules.

Authors:

Kirkegaard, Marie C. ^[1];

^[2];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: 2019-11-18

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1607037

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Nuclear Materials

Additional Journal Information:: Journal Volume: 529; Journal Issue: C; Journal ID: ISSN 0022-3115

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; uranyl flouride; uranyl hydroxide; uranyl peroxide; uranium; raman spectroscopy; x-ray diffraction; relative humidity; degradation

Citation Formats


                    Kirkegaard, Marie C., Ambrogio, Michael W., Miskowiec, Andrew J., Shields, Ashley E., Niedziela, Jennifer L., Spano, Tyler L., and Anderson, Brian B. Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions.  United States: N. p., 2019. 
Web.  doi:10.1016/j.jnucmat.2019.151889.

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                    Kirkegaard, Marie C., Ambrogio, Michael W., Miskowiec, Andrew J., Shields, Ashley E., Niedziela, Jennifer L., Spano, Tyler L., & Anderson, Brian B. Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions.  United States.  https://doi.org/10.1016/j.jnucmat.2019.151889

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                    Kirkegaard, Marie C., Ambrogio, Michael W., Miskowiec, Andrew J., Shields, Ashley E., Niedziela, Jennifer L., Spano, Tyler L., and Anderson, Brian B. Mon .  
"Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions".  United States.  https://doi.org/10.1016/j.jnucmat.2019.151889.  https://www.osti.gov/servlets/purl/1607037.

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@article{osti_1607037,

  title        = {Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions},

  author       = {Kirkegaard, Marie C. and Ambrogio, Michael W. and Miskowiec, Andrew J. and Shields, Ashley E. and Niedziela, Jennifer L. and Spano, Tyler L. and Anderson, Brian B.},

  abstractNote = {Under humid conditions, uranyl fluoride ([(UO2F2)(H2O)]7·4H2O) undergoes a loss of fluorine to form a uranyl hydroxide species, which can be further hydrated to form a uranyl peroxide species. X-ray diffraction data of the uranyl peroxide product is presented for the first time. In addition, the temperature and humidity conditions under which these reactions occur have been clarified by a 220-day experiment using microRaman spectroscopy to track chemical changes in individual particles of uranyl fluoride. At 25 and 35°C, uranyl fluoride is found to be stable at 32% relative humidity but not stable at and above 59% relative humidity. We show that water vapor pressure is the driving factor in formation of both the hydroxide and peroxide products. The kinetics of the transformation from uranyl fluoride into uranyl hydroxide is consistent with a denucleation reaction following the absorption of water molecules.},

  doi          = {10.1016/j.jnucmat.2019.151889},

  journal      = {Journal of Nuclear Materials},

  number       = C,

  volume       = 529,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

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Title: Characterizing the degradation of [(UO2F2)(H2O)]7 4H2O under humid conditions

Abstract

Citation Formats

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide journal, May 2018

Formation of a uranyl hydroxide hydrate via hydration of [(UO 2 F 2 )(H 2 O)] 7 ·4H 2 O journal, January 2019

Humidity fixed points of binary saturated aqueous solutions journal, January 1977

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Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral journal, July 2003

Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite journal, January 2012

Energetics of metastudtite and implications for nuclear waste alteration journal, November 2014

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Comparative study of relativistic density functional methods applied to actinide species AcO 2 2+ and AcF 6 for Ac = U, Np: Comparative Study of Relativistic Density Functional Methods journal, April 2002

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Influence of temperature on water vapour sorption isotherms and kinetics of hardened cement paste and concrete journal, February 2017

Title: Characterizing the degradation of [(UO₂F₂)(H₂O)]₇ 4H₂O under humid conditions

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide
journal, May 2018

Formation of a uranyl hydroxide hydrate via hydration of [(UO ₂ F ₂ )(H ₂ O)] ₇ ·4H ₂ O
journal, January 2019

Humidity fixed points of binary saturated aqueous solutions
journal, January 1977

New Equations for Computing Vapor Pressure and Enhancement Factor
journal, December 1981

A Perfect Smoother
journal, July 2003

Parametric Time Warping
journal, January 2004

Generalized Gradient Approximation Made Simple
journal, October 1996

Chemical accuracy for the van der Waals density functional
journal, December 2009

Van der Waals density functionals applied to solids
journal, May 2011

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Studtite, [(UO ₂ )(O ₂ )(H ₂ O) ₂ ](H ₂ O) ₂ : The first structure of a peroxide mineral
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Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite
journal, January 2012

Energetics of metastudtite and implications for nuclear waste alteration
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Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U ₂ O ₇
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Comparative study of relativistic density functional methods applied to actinide species AcO ₂ ²⁺ and AcF ₆ for Ac = U, Np: Comparative Study of Relativistic Density Functional Methods
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