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Complexes of Hydrogen Peroxide with Dioxoactinide(VI) Species in Aqueous Carbonate and Bicarbonate Media. Formation of An(VI)–H2O2 Complexes |
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| Authors: | Mary E Thompson Kenneth L Nash James C Sullivan |
| Affiliation: | 1. Chemistry Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 USA
Faculty Research Participant, College of St. Catherine, St. Paul, Minnesota.;2. Chemistry Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 USA |
| Abstract: | The spectra for 1:1 complexes formed between triscarbonatouranium(VI) + H2O2 and triscarbanatoneptunium(VI) + H2O2 are presented. The respective rates of formation (25°C, 0.05 M NA2CO3) are 565 ± 41 M?1 s?1 and (2.19 ± .01) X 103 M?1 s?1. The corresponding activation parameters are ΔH* = 67.8 ± 3.2 kJ/m, 43.6 ± 2.0 kJ/m, ΔS* = 30 ± 11 J/m °K and ?36 ± 7 J/m °K, respectively. The U(VI) complex appears to be stable over a period of months while the Np(VI) complex is formed as a transient species that disappears via a complex process. |
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