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On the Mechanism of Oxygen Exchange Between Uranyl(VI) Oxygen and Water in Strongly Alkaline Solution as Studied by O-17 NMR Magnetization Transfer
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0002-7552-1076
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2010 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 49, no 11, 4928-4933 p.Article in journal (Refereed) Published
Abstract [en]

The mechanism, rate constant, and activation parameters for the exchange between uranyl(VI)) oxygen and water oxygen in tetramethyl ammonium hydroxide solution, TMA-OH, have been determined using O-17 NMR magnetization transfer technique. In the concentration range investigated, the predominant complex is UO2(OH)(4)(2-). The experimental rate equation, rate = k(ex)[TMA-OH](free)[U(VI)](2)(total) indicates that the exchange takes place via a binuclear complex or transition state with the stoichiometry [(UO2(OH)(4)(2-))(UO2(OH)(5)(3-)]. The rate-determining step most likely takes place between the axial "yl" oxygens and the equatorial hydroxides. The experimental Gibbs energy of activation, Delta G(double dagger) = 60.8 +/- 2.4 kJ/mol is in good agreement with the value, Delta A(double dagger) approximate to Delta G(double dagger) = 52.3 +/- 5.4 kJ/mol, found by Buhl and Schreckenbach in a recent Car-Parrinello molecular dynamics study, indicating that their proposed "shuttle" mechanism may be applicable also on the proposed binuclear transition state.

Place, publisher, year, edition, pages
2010. Vol. 49, no 11, 4928-4933 p.
Keyword [en]
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-27584DOI: 10.1021/ic9025624ISI: 000278110100035ScopusID: 2-s2.0-77953058608OAI: diva2:377463
QC 20101214Available from: 2010-12-14 Created: 2010-12-13 Last updated: 2010-12-14Bibliographically approved

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