Kinetics and mechanism of oxidation of ferrocyanide by N-bromosuccinimide in aqueous acidic solution

The kinetics of oxidation of ferrocyanide by N-bromosuccinimide (NBS) has been studied spectrophotometrically in aqueous acidic medium over temperature range 20-35 degrees C, pH = 2.8-4.3, and ionic strength = 0.10-0.50 mol dm(-3) over a range of [Fe2+] and [NBS]. The reaction exhibited first order dependence on both reactants and increased with increasing pH, [NBS], and [Fe2+]. The rate of oxidation obeys the rate law: d[Fe3+]/dt = [Fe(CN)(6)](4-)[HNBS+]/(k(2) + k(3)/[H+]). An outersphere mechanism has been proposed for the oxidation pathway of both protonated and deprotonated ferrocyanide species. Addition of both succinimide and mercuric acetate to the reaction mixture has no effect on the reaction rate under the experimental conditions. Mercuric acetate was added to the reaction mixture to act as scavenger for any bromide formed to ensure that the oxidation is entirely due to NBS oxidation.