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Kinetics and mechanism of ruthenium(III) catalyzed oxidation of iso-propanol by cerium(IV) in sulfuric acid media

Zhai Yong-Qing*, Bai Wei-Song, Yang Wen-Shu, Liu Hong-Mei, Liu Xue-Jing, Xu Hui-Man

The kinetics andmechanismof trace ruthenium(III) catalyzed oxidation of iso-propanol (IPA) by cerium(IV) in sulfuric acid media has been investigated by titrimetric technique of redox in the temperature range of 298- 313K. It is found that the reaction is of first-order with respect to Ce(IV), first-order with respect to Ru(III), and zero-order with respect to IPA. It is found that the observed rate constant kobs decreases with the increase of [HSO4 -] and [H+]. Under the protection of nitrogen, the reaction system can not initiate polymerization of acrylonitrile, indicating no generation of free radicals.On the basis of the experimental results, a reasonable mechanism has been proposed and the rate equations derived from the mechanismcan explain the experimental results.