A mechanistic study based on kinetics of the oxidation of diethyl ketone by Ir (III) chloride in aqueous perchloric acid medium when cerium (IV) perchlorate is used as a catalyst


ABSTRACT:

This mechanistic study on the oxidation of diethyl ketone by Ir (III) chloride in aqueous perchloric acid medium when cerium (IV) perchlorate is used as a catalyst has been done at temperature range of 293 to 308 K under conditions such that, [Ir]T << [Ce (IV)]T << [CH3-CH2-CO-CH2-CH3] so that the reaction constants of different steps involved have been evaluated with great ease and accuracy the rate of reaction tends towards zero-order at higher concentration and first order at lower concentration with respect to ceric perchlorate and diethyl ketone. Order of reaction is unity with respect to [Ir (III)] in the concentration range studied. On increasing the concentrations of [H+ ] the rate decreases slightly. The effect of ionic strength and the dielectric constant on reaction rate has also been studied. The active species of oxidant is indicated to be Ce4+ and Ce (OH)3+. An intermediate involving the oxidant, catalyst and substrate has been proposed as being formed in pre-equilibrium steps. The calculation of activation parameters is done with tremendous analysis with respect to slow step of mechanism.

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