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Article . 1985
License: CC BY
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Article . 1985
License: CC BY
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Article . 1985
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Kinetics and Mechanism of Oxidation of Alcohols by Ceric Ammonium Nitrate

Authors: DWARKA L. MATHUR; ANUPMA AGARWAL; KALYAN K. BANERJI;

Kinetics and Mechanism of Oxidation of Alcohols by Ceric Ammonium Nitrate

Abstract

Department of Chemistry, University of Jodhpur, Jodhpur-342 001 Manuscript received 24 May 1984, revised 1 March 1985, accepted 3 June 1985 The main product of the oxidation or secondary alcohol by ceric ammonium nitrate is the corresponding ketone. The reaction Is of first-order with respect to the oxidant but exhibit a Michaelis-Menten type kinetics with respect to the alcohol. The formation constants of the alcohol CeIV complex and Its thermodynamic parameters have been calculated. The rate of decomposition of the complex and the activation parameters have also been evaluated. The rates of decomposition of the complex correlate with Taft's σ* values with a low negative reaction constant. The oxidation induced polymerisation of acrylonitrile. The retardation of rate with increasing acidity has been explained on the formation or kinetically Inactive protonated alcohol. The protonated constants for the various alcohol have been calculated. The presence of a small primary kinetic isotope effect kH /kD -1.3, confirms that the rate-determining step Involves a C—H bond rupture in a non-symmetrical transition state.

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Keywords

ammonium, oxidation, acidity, alcohols

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