Summary
The reduction of chloro-, bromo- and iodopentacyanocobaltate(III) anions by aquatitanium(III) has been studied in aqueous solution with ionic strength, I = 1.0 mol dm-3 (LiCl, KBr or KI) at T = 25 °C. The dependence of the observed second-order rate constant, k obs, on [H+] has been investigated over the acid range 0.005–0.100 mol dm −3 and is of the general limiting form: k obs ≈ k 0 + k[H +] −1, where k 0 is appreciable in all cases and k is a composite rate constant. Using values of K a (associated with the TiIII hydrolytic equilibrium constant), obtained from the kinetic data for the TiIII/CoIII redox reactions, and comparison of the rate constants obtained with those for the corresponding VII reductions of the same CoIII complexes, it is concluded that the TiIII reductions of these halopentacyanocobaltate(III) complexes proceed via an outer-sphere mechanism.
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Author to whom all correspondence should be directed, who is presently on leave of absence from Obafemi Awolowo University.
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Ojo, J.F., Olojo, O.O., Oyetunji, O.A. et al. The reductions of chloro-, bromo- and iodopentacyanocobaltate(III) anions by titanium(III) in aqueous acidic solution. Transition Met Chem 21, 123–126 (1996). https://doi.org/10.1007/BF00136540
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DOI: https://doi.org/10.1007/BF00136540