Kinetics and Mechanism of Mn(II) Catalyzed Periodate Oxidation of p-anisidine: Effect of pH

*Rajneesh Dutt Kaushik  -  Department of Chemistry, Gurukul Kangri University, Haridwar (Uttarakhand),, India
Jaspal Singh  -  Department of Chemistry, Gurukul Kangri University, Haridwar (Uttarakhand),, India
M. Manila  -  Department of Chemistry, Gurukul Kangri University, Haridwar (Uttarakhand),, India
Manmeet Kaur  -  Department of Chemistry, Gurukul Kangri University, Haridwar (Uttarakhand),, India
Prabha Singh  -  Department of Chemistry, D. A. V. (P.G.) College, Muzaffarnagar (U.P.),, India
Received: 2 May 2014; Published: 28 Oct 2014.
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The stoichiometry for the initial part of the reaction, Mn(II) catalysed periodate oxidation of p-anisidine (PMA), has been found to be 1 mol of PMA consuming 2 mol of periodate ion. The kinetic-mechanistic study of reaction in acetone-water medium was made spectrophotometrically by noting the increase in the absorbance of reaction intermediate. Reaction is first order in reactants and catalyst each. A decrease in dielectric constant of the medium results in decrease in the rate of reaction suggesting an ion-dipole type interaction. Free radical scavengers do not affect the reaction rate. A special type of rate-pH profile shows a maximum at pH = 7.0. This pH effect also suggests the involvement of at least three differently reactive reactant species in the reaction and this fact has been considered by us while deriv-ing the rate law. Under pseudo first order conditions [IO4-] >> [PMA] and in agreement with the derived rate law, the 1/kcat versus [H+] plot passes through the minimum and the results can be fitted to the equation: 1/kcat = (K2 / k K3 K4 [H+]) + {(Kw + Kb K2) / k K3 K4 Kw} + Kb [H+] / k K3 K4 Kw, where kK3K4 is the empirical composite rate constant, Kw is ionic product of water, K2 is acid dissociation constant of H4IO6- and Kb is base dissociation constant of PMA. The experimental value of [H+]min is in good agreement with the value calculated by using the derived rate law equation and is character-istic of the substrate involved relating to the base dissociation constant of PMA. The value of thermo-dynamic parameters have been evaluated. © 2014 BCREC UNDIP. All rights reserved

Received: 2nd May 2014; Revised: 2nd July 2014; Accepted: 5th July 2014

How to Cite: Kaushik, R.D., Singh, J., Manila, M., Kaur, M., Singh, P. (2014). Kinetics and Mechanism of MnII Catalyzed Periodate Oxidation of p-anisidine: Effect of pH. Bulletin of Chemical Reaction En-gineering & Catalysis, 9(3): 182-191. (doi: 10.9767/bcrec.9.3.6823.182-191)


Keywords: and mechanism; MnII, periodate; p–anisidine; 4-methoxy-1,2-benzoquinone

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