Effect of temperature on the complexation of triscarbonatouranyl(VI) with calcium and magnesium in NaCl aqueous solution.
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| Title: | Effect of temperature on the complexation of triscarbonatouranyl(VI) with calcium and magnesium in NaCl aqueous solution. |
|---|---|
| Authors: | Shang, Chengming1 (AUTHOR), Reiller, Pascal E.1 (AUTHOR) pascal.reiller@cea.fr |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. 12/14/2021, Vol. 50 Issue 46, p17165-17180. 16p. |
| Subjects: | Alkaline earth ions, Radioactive waste repositories, Temperature effect, Magnesium, Salt, Radioactive wastes |
| Abstract: | The complex formation of triscarbonatouranyl(VI) UO2(CO3)34− with the alkaline earth metal ions Mg2+ and Ca2+ in 0.10 mol kgw−1 NaCl was studied at variable temperatures: 5–30 °C for Mg2+ and 10–50 °C for Ca2+. Under appropriate conditions, the ternary complexes (MnUO2(CO3)3(4−2n)− with n = 1 for Mg, n = {1; 2} for Ca) were identified by time-resolved laser-induced luminescence spectrometry. Their pure spectral components at 50 °C for CanUO2(CO3)3(4−2n)− and 30 °C for MgUO2(CO3)32− were recovered by multivariate curve resolution alternating least-squares analysis. Approximation models were tested to fit the experimental data—the equilibrium constants of complexation measured at different temperatures—and deduce the thermodynamic functions, i.e., enthalpy, entropy, and heat capacity. The weak influence of temperature on complexation constants induces large uncertainties in terms of thermodynamic functions. Assuming the enthalpy is constant with temperature using the Van't Hoff equation, the first stepwise complexation of UO2(CO3)34− by Ca2+ is estimated to be slightly endothermic, with , while the second stepwise complexation of CaUO2(CO3)32− by Ca2+ with is slightly exothermic,. In contrast to Ca2+, the complexation of UO2(CO3)34− by Mg2+ is slightly exothermic, with. These values are not significantly different from zero inasmuch as the uncertainties are important due to a weak dependence of log10 K° values. The entropic character of the complexation is verified as for the first stepwise complexation of UO2(CO3)34− by Ca2+, for the second stepwise complexation of CaUO2(CO3)32− by Ca2+, and for the complexation of UO2(CO3)34− by Mg2+. The energetics of complexation and sensitivity analysis of the model estimates with temperature are discussed. The uranium speciation in the case of the safety of nuclear waste management, using the present thermodynamic functions, provides support to the assessment of underground nuclear waste repositories. [ABSTRACT FROM AUTHOR] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
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| Header | DbId: egs DbLabel: Engineering Source An: 153879126 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Effect of temperature on the complexation of triscarbonatouranyl(VI) with calcium and magnesium in NaCl aqueous solution. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Shang%2C+Chengming%22">Shang, Chengming</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Reiller%2C+Pascal+E%2E%22">Reiller, Pascal E.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> pascal.reiller@cea.fr</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 12/14/2021, Vol. 50 Issue 46, p17165-17180. 16p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Alkaline+earth+ions%22">Alkaline earth ions</searchLink><br /><searchLink fieldCode="DE" term="%22Radioactive+waste+repositories%22">Radioactive waste repositories</searchLink><br /><searchLink fieldCode="DE" term="%22Temperature+effect%22">Temperature effect</searchLink><br /><searchLink fieldCode="DE" term="%22Magnesium%22">Magnesium</searchLink><br /><searchLink fieldCode="DE" term="%22Salt%22">Salt</searchLink><br /><searchLink fieldCode="DE" term="%22Radioactive+wastes%22">Radioactive wastes</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The complex formation of triscarbonatouranyl(VI) UO2(CO3)34− with the alkaline earth metal ions Mg2+ and Ca2+ in 0.10 mol kgw−1 NaCl was studied at variable temperatures: 5–30 °C for Mg2+ and 10–50 °C for Ca2+. Under appropriate conditions, the ternary complexes (MnUO2(CO3)3(4−2n)− with n = 1 for Mg, n = {1; 2} for Ca) were identified by time-resolved laser-induced luminescence spectrometry. Their pure spectral components at 50 °C for CanUO2(CO3)3(4−2n)− and 30 °C for MgUO2(CO3)32− were recovered by multivariate curve resolution alternating least-squares analysis. Approximation models were tested to fit the experimental data—the equilibrium constants of complexation measured at different temperatures—and deduce the thermodynamic functions, i.e., enthalpy, entropy, and heat capacity. The weak influence of temperature on complexation constants induces large uncertainties in terms of thermodynamic functions. Assuming the enthalpy is constant with temperature using the Van't Hoff equation, the first stepwise complexation of UO2(CO3)34− by Ca2+ is estimated to be slightly endothermic, with , while the second stepwise complexation of CaUO2(CO3)32− by Ca2+ with is slightly exothermic,. In contrast to Ca2+, the complexation of UO2(CO3)34− by Mg2+ is slightly exothermic, with. These values are not significantly different from zero inasmuch as the uncertainties are important due to a weak dependence of log10 K° values. The entropic character of the complexation is verified as for the first stepwise complexation of UO2(CO3)34− by Ca2+, for the second stepwise complexation of CaUO2(CO3)32− by Ca2+, and for the complexation of UO2(CO3)34− by Mg2+. The energetics of complexation and sensitivity analysis of the model estimates with temperature are discussed. The uranium speciation in the case of the safety of nuclear waste management, using the present thermodynamic functions, provides support to the assessment of underground nuclear waste repositories. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/d1dt03204f Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 16 StartPage: 17165 Subjects: – SubjectFull: Alkaline earth ions Type: general – SubjectFull: Radioactive waste repositories Type: general – SubjectFull: Temperature effect Type: general – SubjectFull: Magnesium Type: general – SubjectFull: Salt Type: general – SubjectFull: Radioactive wastes Type: general Titles: – TitleFull: Effect of temperature on the complexation of triscarbonatouranyl(VI) with calcium and magnesium in NaCl aqueous solution. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Shang, Chengming – PersonEntity: Name: NameFull: Reiller, Pascal E. IsPartOfRelationships: – BibEntity: Dates: – D: 14 M: 12 Text: 12/14/2021 Type: published Y: 2021 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 50 – Type: issue Value: 46 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
| ResultId | 1 |
