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Mechanism of Oxidation of Ketorolac by Hexacyanoferrate(III) in Aqueous Alkali: A Thermodynamics and Kinetics Study

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Abstract

The kinetics of the oxidation of ketorolac by hexacyanoferrate(III) (HCF) in aqueous alkaline medium at a constant ionic strength of 0.75 mol·dm−3 was studied spectrophotometrically at 300 K. A plausible mechanism was proposed and the rate law was derived. The mechanism of oxidation of ketorolac (KET) in alkaline medium has been shown to proceed via a KET-HCF complex, which decomposes in a slow step followed by other fast steps to give the products. The main oxidative product was identified as (2,3-dihydro-1-hydroxy-1H-pyrrolizin-5-yl-)(phenyl)methanone and is characterized by its LC–ESI–MS spectrum. Thermodynamic parameters of various equilibria of the mechanism were calculated and activation parameters ΔH ≠, ΔS ≠, ΔG ≠ and log10 A were found to be 29.9 kJ·mol−1, −220 J·K−1·mol−1, 96 kJ·mol−1 and 2.70 respectively.

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Acknowledgments

The authors are grateful to the Principal, Karnatak Science College, Dharwad, Karnataka, India for providing the necessary facilities to carry out this work. They also thank the Raptakos Brett and Co., Microlabs Ltd. KLAB, Mumbai, India for providing the free sample of Ketorolac.

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  1. Department of Chemistry, Karnatak Science College, Dharwad, 580 001, Karnataka, India

    Seema S. Badi & Suresh M. Tuwar

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  1. Seema S. Badi
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Correspondence to Suresh M. Tuwar.

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Badi, S.S., Tuwar, S.M. Mechanism of Oxidation of Ketorolac by Hexacyanoferrate(III) in Aqueous Alkali: A Thermodynamics and Kinetics Study. J Solution Chem 43, 916–929 (2014). https://doi.org/10.1007/s10953-014-0177-0

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