1971 Volume 44 Issue 10 Pages 2600-2602
The oxidation of s-butyl alcohol by Ce(IV) in dilute nitric acid medium has been studied. The reaction is of first order with respect to Ce(IV)but of fractional order with respect to s-butyl alcohol. A plot of inverse of alcohol concentration against inverse of observed first order rate constant gave a straight line which did not pass through the origin. This suggests an intermediate Ce(IV)-alcohol complex formation. By repeating this procedure at different temperatures the formation constants of the complex and the thermodynamic parameters for the complex formation process have been evaluated. Hydrogen, nitrate, and sulphate ions decrease the rate of oxidation. The results have been explained on the basis of equilibrium Ce4++H2O\oversetKh\ ightleftarrows Ce(OH)3++H+ and assuming Ce(OH)3+ as the reactive species of Ce(IV). From the slope-intercept of straight line obtained between inverse of observed rate constant and [H+], value of Kh=6.19 at 35°C has been evaluated in dilute nitric acid at μ=2.55 M. A mechanism in which the first step is the rapid reversible formation of a complex between Ce(IV) and Substrate followed byα–C–H bond rupture in the rate determining step has been suggested.
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