Kinetics and mechanism of rhodium(III) catalysed oxidation of polyhydric alcohols by acidified potassium bromate

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Chemical Laboratories, Feroze Gandhi College, Raebareli 229001, India [1 ]
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Transition Met Chem | / 6卷 / 683-685期
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The kinetics of the RhIII catalysed oxidation of ethylene glycol and glycerol by an acidified solution of KBrO3 in the presence of Hg(OAc)2 as a scavenger, have been studied in the 30-45°C range. The rate is first order in bromate and in RhIII but zero order with respect to the substrate and to HClO4. The influence of Hg(OAc)2, ionic strength and Cl- on the rate was found to be insignificant. A transient complex, formed between RhIII and bromate ion in a slow and rate determining step, reacts with the polyhydric alcohol to give the product in a series of fast steps, which lead to regeneration of the catalyst. Activation parameters have been calculated and a suitable mechanism is proposed.
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