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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 [(UO 2) 8O 2(OH) 12]·12H 2O formed upon corrosion of UO 2, 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 S 0 = 179.60 J mol -1 K -1 and C 0 P = 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 (UO 3· xH 2O, 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):
- SAND2019-8118J
Journal ID: ISSN 1463-9076; PPCPFQ; 677579
- Grant/Contract Number:
- AC04-94AL85000; NA0003525; NE0008788
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP (Print)
- Additional Journal Information:
- Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
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. doi:10.1039/C9CP04117F.
Weck, Philippe F., Jové-Colón, Carlos F., and Kim, Eunja. Tue .
"Structure–thermodynamics relationship of schoepite from first-principles". United States. doi:10.1039/C9CP04117F.
@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 (Print)},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {9}
}
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DOI: 10.1039/C9CP04117F
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