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Title: 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:
ORCiD logo [1];  [1]; ORCiD logo [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. 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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