The rates of reduction of the dioxouranium(VI) ion by 4,4$\sp\prime$-dipropylsulfonate-2,2$\sp\prime$ bipyridinium radical anions (ZV$\sp-$ radicals) were determined in the presence of the synthetic polyelectrolytes polyvinylsulfate (PVS), polyacrylic acid (PAA), and polymaleic acid (PMA) using the pulse radiolysis technique. In aqueous PVS solutions the rates of reduction of U(VI) by ZV$\sp-$ radicals are interpreted to reflect territorial binding of U(VI) in the electrostatic field of PVS. In contrast to these results, rate data obtained in PAA and PMA solutions are consistent with the interpretation of site binding of a portion of U(VI) to the carboxylate groups. The specificity of U(VI) binding to PAA is suggested by kinetic experiments in which substitutionally - inert Ru(NH$\sb3$)$\sb6\sp{3+}$ is reduced by ZV$\sp-$ radicals in PAA solutions. Plausible mechanisms for these reactions are presented. / In addition, kinetic data for the reduction of the dioxoactinide(VI) ions, UO$\sb2\sp{2+}$, NpO$\sb2\sp{2+}$, and PuO$\sb2\sp{2+}$ by ZV$\sp-$ radicals were determined at pH 4.0. The measured rate parameters for the reduction of UO$\sb2\sp{2+}$ and NpO$\sb2\sp{2+}$ are in agreement with those predicted by Marcus theory for outer sphere electron transfer, after allowances are made for diffusion. / Source: Dissertation Abstracts International, Volume: 49-12, Section: B, page: 5300. / Major Professor: Gregory R. Choppin. / Thesis (Ph.D.)--The Florida State University, 1988.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77913 |
| Contributors | Pippin, Charles Gregory., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 153 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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