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.
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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