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Citation: Song Wen-Yu, Li Hong-Bian, Liu Hong-Mei. Kinetics and Mechanism of Iridium (III) Catalyzed Oxidation of Isobutyl Alcohol by Cerium(IV) in Aqueous Sulphuric Acid Medium[J]. Acta Physico-Chimica Sinica, ;2004, 20(08): 801-805. doi: 10.3866/PKU.WHXB20040804 shu

Kinetics and Mechanism of Iridium (III) Catalyzed Oxidation of Isobutyl Alcohol by Cerium(IV) in Aqueous Sulphuric Acid Medium

1.
College of Chemistry and Environmental Science, Hebei University, Baoding　071002

Received Date: 5 January 2004
Available Online: 15 August 2004

The kinetics of iridium(III) catalyzed oxidation of isobutyl alcohol by cerium(III) in aqueous sulphuric acid medium has been investigated by titrimetric technique in the temperature range of 25～40 ℃.The reaction order of [Ce(IV)] was found to be unity and that in isobutyl alcohol to be positive fractional. It was found that the pseudo first order ([(CH3)2CHCH2OH] >> [Ce(IV)]) rate constants kobs increases with the increase of [Ir(III)] and [H＋],but decreases with the increase of [HSO4-].Under the protection of nitrogen the reaction system does not induce polymerization of acrylamide indicating no generation of free radicals. Formatoin of a dinuclear complex involving the oxidant, catalyst and the substrate before the rate-determining step has been proposed in the reaction mechanism, and the rate equation derived from the mechanism can explain all experimental observations. From the hydrogensulphate dependence, Ce(SO4)2＋ has been found as the kinetically active species. The pre-equilibrium constants, rate constants of the rate-determining step together with the parameters were evaluated.
- Iridium(III) ion;Cerium(IV) ion;Isobutyl alcohol;Catalyst;Kinetics and mechanism
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