Structure–thermodynamics relationship of schoepite from first-principles
Abstract
The relationship between the structure and thermodynamic properties of schoepite, an important uranyl phase with formula [(UO2)8O2(OH)12]·12H2O formed upon corrosion of UO2, has been investigated within the framework of density functional perturbation theory (DFPT). Experimental crystallographic lattice parameters are well reproduced in this study using standard DFT. Phonon calculations within the quasi-harmonic approximation predict standard molar entropy and isobaric heat capacity of S0 = 179.60 J mol-1 K-1 and C0P = 157.4 J mol-1 K-1 at 298.15 K, i.e., ~6% and ~4% larger than existing DFPT-D2 calculations. The computed variation of the standard molar isobaric heat capacity with water content from schoepite (UO3·xH2O, x = 2.25) to dehydrated schoepite (x = 1) is predicted to be essentially linear along isotherms ranging from 100 to 500 K. Finally, these findings have important implications for the dehydration of layered uranyl corrosion phases and hygroscopic materials.
- Authors:
-
[1];
[2]
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of Nevada, Las Vegas, NV (United States). Dept. of Physics and Astronomy
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)
- OSTI Identifier:
- 1574710
- Alternate Identifier(s):
- OSTI ID: 1568931
- Report Number(s):
- SAND-2019-8118J
Journal ID: ISSN 1463-9076; PPCPFQ; 677579; TRN: US2100018
- Grant/Contract Number:
- AC04-94AL85000; NA0003525; NE0008788
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 46; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Weck, Philippe F., Jové-Colón, Carlos F., and Kim, Eunja. Structure–thermodynamics relationship of schoepite from first-principles. United States: N. p., 2019.
Web. doi:10.1039/C9CP04117F.
Weck, Philippe F., Jové-Colón, Carlos F., & Kim, Eunja. Structure–thermodynamics relationship of schoepite from first-principles. United States. https://doi.org/10.1039/C9CP04117F
Weck, Philippe F., Jové-Colón, Carlos F., and Kim, Eunja. Tue .
"Structure–thermodynamics relationship of schoepite from first-principles". United States. https://doi.org/10.1039/C9CP04117F. https://www.osti.gov/servlets/purl/1574710.
@article{osti_1574710,
title = {Structure–thermodynamics relationship of schoepite from first-principles},
author = {Weck, Philippe F. and Jové-Colón, Carlos F. and Kim, Eunja},
abstractNote = {The relationship between the structure and thermodynamic properties of schoepite, an important uranyl phase with formula [(UO2)8O2(OH)12]·12H2O formed upon corrosion of UO2, has been investigated within the framework of density functional perturbation theory (DFPT). Experimental crystallographic lattice parameters are well reproduced in this study using standard DFT. Phonon calculations within the quasi-harmonic approximation predict standard molar entropy and isobaric heat capacity of S0 = 179.60 J mol-1 K-1 and C0P = 157.4 J mol-1 K-1 at 298.15 K, i.e., ~6% and ~4% larger than existing DFPT-D2 calculations. The computed variation of the standard molar isobaric heat capacity with water content from schoepite (UO3·xH2O, x = 2.25) to dehydrated schoepite (x = 1) is predicted to be essentially linear along isotherms ranging from 100 to 500 K. Finally, these findings have important implications for the dehydration of layered uranyl corrosion phases and hygroscopic materials.},
doi = {10.1039/C9CP04117F},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 46,
volume = 21,
place = {United States},
year = {2019},
month = {9}
}
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Works referenced in this record:
Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements
journal, June 2011
- Shvareva, Tatiana Y.; Fein, Jeremy B.; Navrotsky, Alexandra
- Industrial & Engineering Chemistry Research, Vol. 51, Issue 2
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Nuclear Fuel in a Reactor Accident
journal, March 2012
- Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra
- Science, Vol. 335, Issue 6073
The crystal structure of uranyl-oxide mineral schoepite, [(UO2)4O (OH)6]( H2O)6, revisited
journal, May 2018
- Plášil, J.
- Journal of Geosciences
Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite
journal, January 2012
- Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
- Dalton Transactions, Vol. 41, Issue 32
Layered uranium( vi ) hydroxides: structural and thermodynamic properties of dehydrated schoepite α-UO 2 (OH) 2
journal, January 2014
- Weck, Philippe F.; Kim, Eunja
- Dalton Trans., Vol. 43, Issue 45
Derivation of Wachtman's Equation for the Temperature Dependence of Elastic Moduli of Oxide Compounds
journal, April 1966
- Anderson, Orson L.
- Physical Review, Vol. 144, Issue 2
Formation of primary yields of hydrogen peroxide and molecular hydrogen (GH2O2 and GH2) in the .gamma. radiolysis of neutral aqueous solutions
journal, December 1971
- Draganic, Z. D.; Draganic, I. G.
- The Journal of Physical Chemistry, Vol. 75, Issue 26
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012
- Armstrong, C. R.; Nyman, M.; Shvareva, T.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
Thermochemistry of uranium compounds XVII. Standard molar enthalpy of formation at 298.15 K of dehydrated schoepite UO3 · 0.9H2O. Thermodynamics of (schoepite + dehydrated schoepite + water)
journal, November 1988
- O'Hare, P. A. G.; Lewis, Brett M.; Nguyen, Son N.
- The Journal of Chemical Thermodynamics, Vol. 20, Issue 11
683. Some aspects of the system uranium trioxide–water
journal, January 1956
- Dawson, J. K.; Wait, E.; Alcock, K.
- J. Chem. Soc., Vol. 0, Issue 0
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 46, Issue 11
Periodic Density Functional Theory Study of the Structure, Raman Spectrum, and Mechanical Properties of Schoepite Mineral
journal, March 2018
- Colmenero, Francisco; Cobos, Joaquín; Timón, Vicente
- Inorganic Chemistry, Vol. 57, Issue 8
Corrosion of commercial spent nuclear fuel. 2. Radiochemical analyses of metastudtite and leachates
journal, January 2005
- McNamara, Bruce; Hanson, Brady D.; Buck, Edgar C.
- Radiochimica Acta, Vol. 93, Issue 3
On the uranates of ammonium—II
journal, August 1963
- Debets, P. C.; Loopstra, B. O.
- Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 8
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite
journal, January 2005
- Hanson, Brady D.; McNamara, Bruce; Buck, Edgar C.
- Radiochimica Acta, Vol. 93, Issue 3
Temperature-Dependent Gibbs Free Energies of Reaction of Uranyl-Containing Materials Based on Density Functional Theory
journal, February 2018
- Colmenero, Francisco; Fernández, Ana María; Cobos, Joaquín
- The Journal of Physical Chemistry C, Vol. 122, Issue 10
Assessment of the Performance of DFT and DFT-D Methods for Describing Distance Dependence of Hydrogen-Bonded Interactions
journal, December 2010
- Thanthiriwatte, Kanchana S.; Hohenstein, Edward G.; Burns, Lori A.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 1
Alpha-radiolysis effects on UO2 alteration in water
journal, January 2001
- Sattonnay, G.; Ardois, C.; Corbel, C.
- Journal of Nuclear Materials, Vol. 288, Issue 1
Distinguishing among schoepite, [( UO 2 ) 8 O 2 ( OH ) 12 ]( H 2 O ) 12 , and related minerals by X-ray powder diffraction
journal, December 1997
- Finch, Robert J.; Hawthorne, Frank C.; Miller, Mark L.
- Powder Diffraction, Vol. 12, Issue 4
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
High-precision sampling for Brillouin-zone integration in metals
journal, August 1989
- Methfessel, M.; Paxton, A. T.
- Physical Review B, Vol. 40, Issue 6
On the mechanical stability of uranyl peroxide hydrates: implications for nuclear fuel degradation
journal, January 2015
- Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.
- RSC Advances, Vol. 5, Issue 96
On the role of strong electron correlations in the surface properties and chemistry of uranium dioxide
journal, January 2013
- Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
- Dalton Transactions, Vol. 42, Issue 13
The uranium trioxide-water system
journal, March 1973
- Hoekstra, H. R.; Siegel, S.
- Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 3
Periodic DFT Study of the Thermodynamic Properties and Stability of Schoepite and Metaschoepite Mineral Phases
journal, December 2018
- Colmenero, Francisco; Fernández, Ana María; Cobos, Joaquín
- ACS Earth and Space Chemistry, Vol. 3, Issue 1
Stability of Peroxide-Containing Uranyl Minerals
journal, November 2003
- Kubatko, K. -A. H.
- Science, Vol. 302, Issue 5648
Uncloaking the Thermodynamics of the Studtite to Metastudtite Shear-Induced Transformation
journal, July 2016
- Weck, Philippe F.; Kim, Eunja
- The Journal of Physical Chemistry C, Vol. 120, Issue 30
First-principles calculations of the ferroelastic transition between rutile-type and -type at high pressures
journal, October 2008
- Togo, Atsushi; Oba, Fumiyasu; Tanaka, Isao
- Physical Review B, Vol. 78, Issue 13
Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014
- Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
Monitoring bromide effect on radiolytic yields using in situ observations of uranyl oxide precipitation in the electron microscope
journal, January 2018
- Buck, Edgar C.; Wittman, Richard S.; Soderquist, Chuck. Z.
- RSC Advances, Vol. 8, Issue 33
Ab initio study of uranyl peroxides: Electronic factors behind the phase stability
journal, February 2007
- Ostanin, S.; Zeller, P.
- Physical Review B, Vol. 75, Issue 7
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
Stability of Peroxide-Containing Uranyl Minerals.
journal, February 2004
- Kubatko, Karrie-Ann Hughes; Helean, Katheryn B.; Navrotsky, Alexandra
- ChemInform, Vol. 35, Issue 8
Thermochemical data of pure substances
journal, March 1997
- Rumpf, Dr. -Ing. B.
- Veterinary Immunology and Immunopathology, Vol. 55, Issue 4