The rates and mechanisms of water exchange of actinide aqua ions: A variable temperature {sup 17}O NMR study of U(H{sub 2}O){sub 10}{sup 4+}, UF(H{sub 2}O){sub 9}{sup 3+}, and Th(H{sub 2}O){sub 10}{sup 4+}
Journal Article
·
· Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
The rate constants and the activation parameters for the exchange between water solvent and [U(H{sub 2}O){sub 10}]{sup 4+} and [UF(H{sub 2}O){sub 9}]{sup 3+}, and a lower limit for the rate constant at room temperature for [Th(H{sub 2}O){sub 10}]{sup 4+}, were determined by {sup 17}O NMR spectroscopy in the temperature range 255--305 K. The experiments were made at different constant hydrogen ion concentrations, which varied between 0.16 and 0.8 mol kg{sup {minus}1}. The Th(IV) system was investigated using Tb{sup 3+} as a shift reagent. The following kinetic parameters at 25 C were obtained: k{sub ex} = (5.4 {+-} 0.6) 10{sup 6} x{sup {minus}1}, {Delta}H{sup double{underscore}dagger} = 34 {+-} 3 kJ mol{sup {minus}1}, {Delta}S{sup {double{underscore}dagger}} = {minus}16 {+-} 10 J mol{sup {minus}1} K{sup {minus}1} for U{sup 4+} (aq), k{sub ex} = (5.5 {+-} 0.7) 10{sup 6} x{sup {minus}1}, {Delta}H{sup {double{underscore}dagger}} = 34 {+-} 3 kJ mol{sup {minus}1}, {Delta}S{sup {double{underscore}dagger}} = 3 {+-} 15 J mol{sup {minus}1} K{sup {minus}1} for UF{sup 3+}(Iaq), and k{sub ex} > 5 10{sup 7} s{sup {minus}1} for Th{sup 4+}(aq), where the uncertainty is given at the 2{sigma}-level. This is the first experimental information on the kinetic parameters for the exchange of water for any M{sup 4+} ion. There is no information on the rates and mechanisms of ligand substitutions involving other mono-dentate ligands, hence the mechanistic interpretation of the data is by necessity provisional. The kinetic data and the known ground-state geometry with a coordination number of 10 {+-} 1 for the Th(IV) and U(IV) complexes suggest a dissociatively activated interchange mechanism. There is no noticeable effect of coordination of one fluoride or one hydroxide to U(IV) on the water exchange rate. This is unusual, for other metal ions there is a strong labilizing of coordinated water when a second ligand is bonded, e.g., in complexes of aluminum and some d-transition elements. In previous studies of the rates and mechanisms of ligand exchange in uranium (VI) systems the authors found a strong decrease in the lability of coordinated water in some fluoride containing complexes.
- Research Organization:
- Royal Inst. of Tech., Stockholm (SE)
- OSTI ID:
- 20017550
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 6 Vol. 104; ISSN 1089-5639; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- English
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