Os(VIII)-Catalyzed Oxidation of Some Aliphatic Ketones by Sodium N-Chlorobenzenesulfonamide (Chloramine-B) in the Presence of Sodium Hydroxide: Kinetic Mechanistic Chemistry

Kinetics of oxidation of 2-propanone, 2-butanone, and 2-pentanone by chloramine-B (CAB) in presence of NaOH and OsO 4 catalyst has been investigated at 303 K. The reaction rate shows a first-order dependence each on [CAB] o and [Os(VIII)], fractional-order on [NaOH], and zero-order on [ketone] o . T...

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Published in:Synthesis and reactivity in inorganic, metal-organic, and nano-metal chemistry metal-organic, and nano-metal chemistry, 2011-07, Vol.41 (6), p.644-651
Main Authors: Vaz, Nirmala, Vinod, K. N., Puttaswamy
Format: Article
Language:English
Subjects:
catalysis
chloramine-B
Ketones
kinetics
Nanocomposites
Nanomaterials
Nanostructure
Os(VIII)
Oxidation
Reaction kinetics
Sodium
Sodium hydroxide
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Summary:Kinetics of oxidation of 2-propanone, 2-butanone, and 2-pentanone by chloramine-B (CAB) in presence of NaOH and OsO 4 catalyst has been investigated at 303 K. The reaction rate shows a first-order dependence each on [CAB] o and [Os(VIII)], fractional-order on [NaOH], and zero-order on [ketone] o . The solvent isotope effect k / (H 2 O) / k / (D 2 O) = 0.58. Activation parameters have been deduced. An isokinetic relation is obtained with β = 340 K. The rate of oxidation of ketones follows the order: 2-pentanone > 2-butanone > 2-propanone. The Os(VIII) catalyzed reactions are 7 to 9 fold faster than the uncatalyzed reactions. Suitable mechanism and rate law have been proposed.
ISSN:1553-3174
1553-3182
DOI:10.1080/15533174.2011.568455