Abstract
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.
Similar content being viewed by others
References
R. Natarajan and N. Venkatasubramanian, Tetrahedron Lett., 57, 5021 (1969); Indian J. Chem., 17A, 257 (1979); Internat. J. Chem. Kinet., 8, 205 (1974); Tetrahedron, 30, 2785 (1974).
V. Lakshmi and E.V. Sundaram, J. Indian Chem. Soc., 55, 567 (1978); Indian J. Chem., 15A, 612 (1977).
C.S. Reddy and E.V. Sundaram, J. Indian Chem. Soc., 62, 209 (1985).
V. Avasthi and A.C. Chatterji, Z. Phys. Chem. (Leipzig), 245, 154 (1970); 249, 17 (1972).
S. Anandan and R. Gopalan, J. Indian Chem. Soc., 62, 216 (1985).
B. Singh and S. Srivastava, Oxidation Comm., 12, 140 (1989) J. Indian Chem. Soc., 65, 844 (1988); React. Kinet. Catal. Lett., 39, 243 (1989); Transition Met. Chem., 16, 466 (1991); J. Indian Chem. Soc., 69, 335 (1992).
S. Srivastava, Oxidation Comm., 15, 37 (1992); 17, 282 (1994).
F. Feigl, Spot tests in Organic Analysis, Elsevier, New York, 1996.
N. Venkatasubramanian and V. Thiagarajan, Can. J. Chem., 47, 694 (1969).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Srivastava, S. Kinetics and mechanism of rhodium(III) catalysed oxidation of polyhydric alcohols by acidified potassium bromate. Transition Metal Chemistry 24, 683–685 (1999). https://doi.org/10.1023/A:1006929504333
Issue Date:
DOI: https://doi.org/10.1023/A:1006929504333