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Mn(II) Catalyzed Oxidation of Atenolol by Cerium(IV) in Aqueous Sulfuric Acid Medium: A Spectrophotometer Aided Kinetic, Mechanistic and Thermodynamic Study

  • Ram Gopal Amballa EMAIL logo , Chandra Sekhar Veeravalli , Ravi Kumar Ganta , Raghu Babu Korupolu and Annapurna Nowduri


The kinetics and mechanism of manganese(II) catalyzed oxidation of atenolol by cerium(IV) sulfate in aqueous H2SO4 at a constant ionic strength of 0.50 mol dm-3 was studied spectrophotometrically. The reaction showed first order kinetics in cerium(IV) whereas fractional order in both manganese(II) and atenolol. Addition of products showed no effect on the rate of the reaction. The main product, 2-(4-(2-hydroxy-3-oxopropoxy)phenyl)acetamide, was identified with the aid of IR and mass spectral data. Stoichiometry with respect to the drug substrate and reagent was established as 2:1. Added H2SO4, SO42− and HSO4 showed negligible effect on the rate of the reaction. HCe(SO4)3 was found to be the predominant reactive species under the specified experimental conditions. The rate constants (k), catalytic constant (kc) and equilibrium constant (K6) for the proposed mechanism were determined. The kinetic and thermodynamic activation parameters were computed for both the slow rate determining step and complex forming equilibrium step.


The corresponding author is grateful to UGC-SERO, Hyderabad for awarding teacher fellowship under FDP, XII plan of UGC, New Delhi. The author thanks the Department of Pharmacy for providing IR and MS facilities. The author is also grateful to all the faculty members of Department of Engineering Chemistry, AUCE (A) for providing general lab facilities and for all the support extended.




where, kc=catalytic constant; x=order with respect to the catalyst.

The catalytic constant may be calculated from the following equation,


A2: Rate law derivation


Consider sulfuric acid dissociation,






Since, [Mn(II)]<1, and [Mn(II)][H+]<<1

Hence, K5K6[Mn(II)][H+] may be neglected


Re-writing equation (1),





Writing the reciprocal,


Neglecting the term containing inverse square of [H+] and writing the remaining three terms,



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The online version of this article offers supplementary material (

Received: 2017-5-11
Accepted: 2017-8-21
Published Online: 2017-10-6
Published in Print: 2018-2-23

©2018 Walter de Gruyter GmbH, Berlin/Boston

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