The kinetics of reductions of some chloropentakis(alkylamine)cobalt(III), aquapentakis(alkylamine)cobalt(III), and trans(O,Cl)-chloroaminoacidatodiethylenetriaminecobalt(III) ions by aquavanadium(II), or aquachromium(II) |
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| Affiliation: | 1. School of Water Resources and Environment, MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, China University of Geosciences (Beijing), Beijing 100083, China;2. Department of Environmental Engineering, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China;3. Land Resources Consolidation and Rehabilitation Center, China GEO-Engineering Corporation, Beijing 100093, China;1. MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, School of Water Resources and Environment, China University of Geosciences Beijing, Beijing 100083, PR China;2. School of Biological and Chemical Engineering, Panzhihua University, Panzhihua 617000, PR China;3. The Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Science (CAGS), Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey, Shijiazhuang 050061, PR China;4. St Edmund Hall, Queen''s Lane, Oxford OX1 4AR, UK;5. School of Engineering, The University of Edinburgh, The King''s Buildings, Edinburgh EH9 3JL, UK;6. School of Engineering, Computing and Mathematics, University of Plymouth, Drakes Circus, Plymouth PL4 8AA, UK |
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| Abstract: | ![]()
The rate of the reduction of chloropentakis(alkylamine)cobalt(III) ions, Co(Cl)(A)5staggered2+, (A5 = (NH3)5, trans-(NH2CH3)(NH3)4, (NH2CH3)5 and (n-NH2C3H7)5) by vanadium(II) decreases in the following order: (n-NH2C3H7)5 > (NH2CH3)5 >trans-(NH2CH3)(NH3)4 > (NH3)5. The similar result on the effect of alkylamines on the rate of the reductions of aquapentakis(alkylamine)cobalt(III) ions, Co(H2O)(A)5staggered3+ by vanadium(II) and chromium(II) was obtained. The rate constants of reductions of Co(Cl)(A)5staggered2+ by vanadium(II) could be correlated with the rate constants of the reaction of Co(Cl)(A)5staggered2+ with iron(II) by the equation of log kV = 1.3 log kFe + 3.6, where kV and kFe are the second-order rate constant of reductions by vanadium(II) and iron(II) respectively. The steric effect of the coordinated alkylamines on the rates of reductions of Co(Cl)(A)5staggered2+ and Co(H2O)(A)5staggered3+ by vanadium(II) and the reduction of Co(H2O)(A)5staggered2+ by chromium(II) is relatively small. The effects of concentrations of perchloric acid and N,N-dimethylformamide were examined for the reduction of trans-(O,Cl)Co(Cl)(gly)(dien)+ by vanadium(II), where gly and dien represent glycinate ion and diethylenetriamine respectively. An outer-sphere mechanism was suggested for the reductions of Co(Cl)(A)5staggered2+ and trans(O,Cl)Co(Cl)(gly)(dien)+ by vanadium(II) based on the experimental results obtained. |
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