Cyclic voltammetric study of acid hydrolysis of tris(bipyridine) chromium(II): a critical appraisal of CV determination of kinetic parameters

Cyclic voltammetry has been exploited to reinvestigate discrepancies in the reported rate constant for the reaction:[Formula: see text]which follows electrode reduction of the substitution inert [Formula: see text]. It is shown that the problems arise from oversimplified treatment of residual currents when estimating the anodic peak current, ia. A "two scan" procedure for estimating the background currents is introduced which appears to resolve discrepancies. The kinetic studies were extended to a methyl-substituted bipyridine. Since ring methylation has very little effect on kf, it appears that the aquation reaction is initiated by a rate-determining step which requires a minimum of bipyridine rearrangement.