Legendre Ru(VI)-Catalyzed Oxidation of Alcohols by Hexacyanoferrate(III). Computational analysis of mixed kinetic order
2006 - A.E. Mucientes, H. Herrero, O. Sánchez
International Journal of Chemical Kinetics 38, 153-158 (2006).
authors IMACI
Abtract
The title reaction shows a mixed kinetic order with respect to hexacyanoferrate(III). The reaction tends to be single zero order at high [Fe(CN)] and single first order at low [Fe(CN)]. For this reason, the decay of the absorbance of hexacyanoferrate(III) at 420 nm changes from linear to exponential as the reaction proceeds. This change of order has also been observed in the initial moments of the reaction. The dependence of the reaction rate on [Fe(CN)] has been obtained, by computational methods, at t = 0 and at any subsequent time during the course of the reaction. The coincidence of both equations would indicate that none of the substances produced in the reaction acts as an activator or inhibitor. The mixed order is due to the comparable rates of complex decomposition and catalyst regeneration steps. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 153-158, 2006