Abstract: | Safranine‐O, a dye of the phenazinium class, was found to exhibit intricate kinetics during its reaction with bromate at low pH conditions. Under conditions of excess concentrations of acid and bromate, safranine‐O (SA+) initially depleted very slowly (k = (3.9 ± 0.3) × 10?4 M?3 s?1) but after an induction time, the reaction occurred swiftly. Bromide exhibited a dual role in the reaction mechanism, both as an autocatalyst and as an inhibitor. The added bromide increased the initial rate of depletion of SA+, but delayed the transition to rapid reaction. The overall stiochiometric reaction was found to be 6SA+ + 4 BrO3 ? = 6SP + 3N2O + 3H2O + 6H+ + 4Br?, where SP is 3‐amino‐7‐oxo‐2,8‐dimethyl‐5‐phenylphenazine. The fast kinetics of the reaction between aqueous bromine and safranine‐O (k = (2.2 ± 0.1) × 103 M?1 s?1) are also reported in this paper A 17‐step mechanism, consistent with the overall reaction dynamics and supported by simulations, is proposed and the role of various bromo and oxybromo species is also discussed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 542–549, 2002 |