Structure–thermodynamics relationship of schoepite from first-principles

Weck, Philippe F.; Jové-Colón, Carlos F.; Kim, Eunja

doi:10.1039/C9CP04117F

Structure–thermodynamics relationship of schoepite from first-principles

Journal Article · Tue Sep 24 04:00:00 EDT 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C9CP04117F· OSTI ID:1574710

^[1]; Jové-Colón, Carlos F. ^[1]; ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Nevada, Las Vegas, NV (United States). Dept. of Physics and Astronomy

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 C⁰_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 (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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1574710

Alternate ID(s):: OSTI ID: 1568931

Report Number(s):: SAND--2019-8118J; 677579

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 46 Vol. 21; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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