화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.113, No.19, 5540-5549, 2009
Kinetics and Mechanism of the Oxidation of Methylene Violet by Bromate at Acidic pH and the Dual Role of Bromide Ion
Methylene violet (MV+), a phenazine class of dye during oxidation by the bromate ion under acidic conditions, exhibited complex nonlinear behavior. The intricate kinetics of reaction of methylene violet [3-amino-7-(diethyleamino)-5-phenyl phenazium chloride, MV+] with acidic bromate was investigated using the stopped flow technique. Under excess acid and bromate concentration conditions, MV+ exhibited a very slow reaction initially but a very rapid reaction after an induction time. The reaction had first-order dependence on both H+ and BrO3-ions. The overall stoichiometric reaction is 2MV(+)+2BrO(3)(-)+H2O -> 2MP+2HON(CH2CH3)(2)+N2O+2H(+)+2Br(-) where MP is the 3,7-dioxo-5-phenyl phenazine. The active roles of various bromo and oxybromo species in the mechanism are discussed. The rapid kinetics of the direct reaction of bromine with MV+ is also reported. A 19-step mechanism, consistent with the experimental data and validated by simulations using Simkine-2, is proposed.