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Kinetics and mechanism of cerium(IV) oxidation of primary and secondary alcohols catalysed by chromium(III)

✍ Scribed by Laxman V. Nimbalkar; Anant M. Chavan; Gavisiddappa S. Gokavi

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
115 KB
Volume
11
Category
Article
ISSN
0894-3230

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✦ Synopsis

The cerium(IV) oxidation of isobutanol, isoamyl alcohol isopropyl alcohol, and secondary butanol catalysed by chromium(III) was studied in sulphuric and perchloric acid mixture at 30 Β°C. The reaction was found to proceed with the formation of a chromium(IV) intermediate followed by its complexation with alcohol. The complex thus formed decomposed into an aldehyde or ketone by a two-electron hydride ion transfer. The formation constants for complexes were determined from Michaelis-Menten plots. The accelerating effect of [H ] on the reaction is attributed to the formation of active species, HCe(SO 4 ) 3 Γ€ and HAlcohol , of the oxidant and alcohol, respectively. The activation parameters were also determined and an isokinetic plot was found to be linear.

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