The reduction of chloro-, bromo-and iodopentacyanocobaltate(III) anions by aquatitanium(III) has been studied in aqueous solution with ionic strength, I = 1.0moldm -3 (LiC1, KBr or KI) at T= 25 ~ The dependence of the observed second-order rate constant, /Cobs, on IN +] has been investigated over the acid range 0.005-0.100 mol dm 3 and is of the general limiting form: kobs ~ ko + k[H +] 1, where k o is appreciable in all cases and k is a composite rate constant. Using values of K a (associated with the Ti m hydrolytic equilibrium constant), obtained from the kinetic data for the TiI"/Co nl redox reactions, and comparison of the rate constants obtained with those for the corresponding V II reductions of the same Co In complexes, it is concluded that the Ti m reductions of these halopentacyanocobaltate(III) complexes proceed via an outer-sphere mechanism.
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