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Structural and kinetic studies on uranyl(V) carbonate complex using C-13 NMR spectroscopy
KTH, Skolan för kemivetenskap (CHE), Kemi, Oorganisk kemi.
2005 (engelsk)Inngår i: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, nr 13, s. 4472-4474Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

We have measured C-13 NMR spectra of uranyl(V) carbonate complex in D2O solution containing 1.003 M Na-2 (CO3)-C-13 at various temperatures. Two singlet signals corresponding to free and coordinated CO32- were observed at 169.13 and 106.70 ppm, respectively. From the peak area ratio, the structure of the uranyl(V) carbonate complex was determined as [(UO2)-O-V(CO3)(3)](5-). Furthermore, kinetic analyses of the exchange reaction of free and coordinated CO32- in [(UO2)-O-V(CO3)(3)](5-) were carried out using 13C NMR line-broadening. As a result, the first-order rate constant at 298 K and the activation parameters for CO32- exchange reaction in [(UO2)-O-V(CO3)(3)](5-) were evaluated as 1.13 x 10(3) s(-1) and Delta H-not equal = 62.0 +/- 0.7 KJ(.)mol(-1), Delta S-not equal = 22 +/- 3 J(.)mol(-1.)K(-1), respectively. We suggest that the exchange follows a dissociative mechanism as in the corresponding [(UO2)-O-VI(CO3)(3)](4-) complex.

sted, utgiver, år, opplag, sider
2005. Vol. 44, nr 13, s. 4472-4474
Emneord [en]
NUCLEAR MAGNETIC-RESONANCE, LIGAND-EXCHANGE REACTIONS, AQUEOUS-SOLUTION, WATER EXCHANGE, URANIUM(V), REDUCTION, C-13, ACETYLACETONATE, SPECTROSCOPY, MECHANISMS
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Identifikatorer
URN: urn:nbn:se:kth:diva-37852DOI: 10.1021/ic050308xISI: 000229982700011Scopus ID: 2-s2.0-22544467767OAI: oai:DiVA.org:kth-37852DiVA, id: diva2:435401
Merknad
QC 20110818Tilgjengelig fra: 2011-08-18 Laget: 2011-08-18 Sist oppdatert: 2017-12-08bibliografisk kontrollert

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