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Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2] |
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| Authors: | Grant W. Wangila Robert B. Jordan |
| Affiliation: | a Department of Chemistry and Physics, University of Arkansas at Pine Bluff, Caine-Gilelland Hall 343, 1200 North University Drive, Mail Slot 4941, Pine Bluff, AR 71601, USA b University of Alberta, Chemistry Department, Edmonton, Alberta, Canada T6G 2G2 |
| Abstract: | The reaction of  with Co(dmgBF2)2(H2O)2 in 1.0 M HClO4/LiClO4 was found to be first-order in both reactants and the [H+] dependence of the second-order rate constant is given by k2obs = b/[H+], b at 25 °C is 9.23 ± 0.14 × 102 s−1. The [H+] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for  as Ka = 9.5 × 10−3 M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH2)5OH2+/+ were used to estimate an electron self-exchange rate constant of k22 = 1.7 × 10−4 M−1 s−1 for  . |
| Keywords: | Kinetic studies Hexaaquacobalt(III)perchlorate Reduction Cobaloxime [Co(dmgBF2)2(H2O)2] First-order reactions Second-order reactions |
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