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Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite

The full crystal structure of the copper-uranyl tetrahydroxide mineral (vandenbrandeite), including the positions of the hydrogen atoms, is established by the first time from X-ray diffraction data taken from a natural crystal sample from the Musonoi Mine, Katanga Province, Democratic Republic of Co...

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Autores principales: Colmenero, Francisco, Plášil, Jakub, Cobos, Joaquín, Sejkora, Jiří, Timón, Vicente, Čejka, Jiří, Fernández, Ana María, Petříček, Václav
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9076244/
https://www.ncbi.nlm.nih.gov/pubmed/35542667
http://dx.doi.org/10.1039/c9ra09047a
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author Colmenero, Francisco
Plášil, Jakub
Cobos, Joaquín
Sejkora, Jiří
Timón, Vicente
Čejka, Jiří
Fernández, Ana María
Petříček, Václav
author_facet Colmenero, Francisco
Plášil, Jakub
Cobos, Joaquín
Sejkora, Jiří
Timón, Vicente
Čejka, Jiří
Fernández, Ana María
Petříček, Václav
author_sort Colmenero, Francisco
collection PubMed
description The full crystal structure of the copper-uranyl tetrahydroxide mineral (vandenbrandeite), including the positions of the hydrogen atoms, is established by the first time from X-ray diffraction data taken from a natural crystal sample from the Musonoi Mine, Katanga Province, Democratic Republic of Congo. The structure is verified using first-principles solid-state methods. From the optimized structure, the mechanical and dynamical stability of vandenbrandeite is studied and a rich set of mechanical properties are determined. The Raman spectrum is recorded from the natural sample and determined theoretically. Since both spectra have a high-degree of consistence, all spectral bands are rigorously assigned using a theoretical normal-coordinate analysis. Two bands in the Raman spectra, located at 2327 and 1604 cm(−1), are recognized as overtones and a band at 1554 cm(−1) is identified as a combination band. The fundamental thermodynamic functions of vandenbrandeite are computed as a function of temperature using phonon calculations. These properties, unknown so far, are key-parameters for the performance-assessment of geological repositories for storage of radioactive nuclear waste and for understanding the paragenetic sequence of minerals arising from the corrosion of uranium deposits. The thermodynamic functions are used here to determine the thermodynamic properties of formation of vandenbrandeite in terms of the elements and the Gibbs free-energies and reaction constants for a series of reactions involving vandenbrandeite and a representative subset of the most important secondary phases of spent nuclear fuel. Finally, from the thermodynamic data of these reactions, the relative stability of vandenbrandeite with respect to these phases as a function of temperature and in the presence of hydrogen peroxide is evaluated. Vandenbrandeite is shown to be highly stable under the simultaneous presence of water and hydrogen peroxide.
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spelling pubmed-90762442022-05-09 Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite Colmenero, Francisco Plášil, Jakub Cobos, Joaquín Sejkora, Jiří Timón, Vicente Čejka, Jiří Fernández, Ana María Petříček, Václav RSC Adv Chemistry The full crystal structure of the copper-uranyl tetrahydroxide mineral (vandenbrandeite), including the positions of the hydrogen atoms, is established by the first time from X-ray diffraction data taken from a natural crystal sample from the Musonoi Mine, Katanga Province, Democratic Republic of Congo. The structure is verified using first-principles solid-state methods. From the optimized structure, the mechanical and dynamical stability of vandenbrandeite is studied and a rich set of mechanical properties are determined. The Raman spectrum is recorded from the natural sample and determined theoretically. Since both spectra have a high-degree of consistence, all spectral bands are rigorously assigned using a theoretical normal-coordinate analysis. Two bands in the Raman spectra, located at 2327 and 1604 cm(−1), are recognized as overtones and a band at 1554 cm(−1) is identified as a combination band. The fundamental thermodynamic functions of vandenbrandeite are computed as a function of temperature using phonon calculations. These properties, unknown so far, are key-parameters for the performance-assessment of geological repositories for storage of radioactive nuclear waste and for understanding the paragenetic sequence of minerals arising from the corrosion of uranium deposits. The thermodynamic functions are used here to determine the thermodynamic properties of formation of vandenbrandeite in terms of the elements and the Gibbs free-energies and reaction constants for a series of reactions involving vandenbrandeite and a representative subset of the most important secondary phases of spent nuclear fuel. Finally, from the thermodynamic data of these reactions, the relative stability of vandenbrandeite with respect to these phases as a function of temperature and in the presence of hydrogen peroxide is evaluated. Vandenbrandeite is shown to be highly stable under the simultaneous presence of water and hydrogen peroxide. The Royal Society of Chemistry 2019-12-09 /pmc/articles/PMC9076244/ /pubmed/35542667 http://dx.doi.org/10.1039/c9ra09047a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Colmenero, Francisco
Plášil, Jakub
Cobos, Joaquín
Sejkora, Jiří
Timón, Vicente
Čejka, Jiří
Fernández, Ana María
Petříček, Václav
Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title_full Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title_fullStr Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title_full_unstemmed Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title_short Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
title_sort structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9076244/
https://www.ncbi.nlm.nih.gov/pubmed/35542667
http://dx.doi.org/10.1039/c9ra09047a
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