✍ Scribed by S. B. Jonnalagadda; M. Shezi; B. Pare
No coin nor oath required. For personal study only.
The kinetics and mechanism of the uncatalyzed and Ru(III)‐catalyzed oxidation of methylene violet (3‐amino‐7‐diethylamino‐5‐phenyl phenazinium chloride) (MV^+^) by acidic chlorite is reported. With excess concentrations of other reactants, both uncatalyzed and catalyzed reactions had pseudo‐first‐order kinetics with respect to MV^+^. The uncatalyzed reaction had first‐order dependence on chlorite and H^+^ concentrations, but the catalyzed reaction had first‐order dependence on both chlorite and catalyst, and a fractional order with respect to [H^+^]. The rate coefficient of the uncatalyzed reaction is (5.72 ± 0.19) M^−2^ s^−1^, while the catalytic constant for the catalyzed reaction is (22.4 ± 0.3) × 10^3^ M^−1^ s^−1^. The basic stoichiometric equation is as follows: 2MV^+^ + 7ClO~2~^−^ + 2H^+^ = 2P + CH~3~COOH + 4ClO~2~ + 3Cl^−^, where P^+^ = 3‐amino‐7‐ethylamino‐5‐phenyl phenazinium‐10‐N‐oxide. Stoichiometry is dependent on the initial concentration of chlorite present. Consistent with the experimental results, pertinent mechanisms are proposed. The proposed 15‐step mechanism is simulated using literature; experimental and estimated rate coefficients and the simulated plots agreed well with the experimental curves. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 294–303, 2003
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