Skip to main content
Log in

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

  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. 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).

  2. V. Lakshmi and E.V. Sundaram, J. Indian Chem. Soc., 55, 567 (1978); Indian J. Chem., 15A, 612 (1977).

  3. C.S. Reddy and E.V. Sundaram, J. Indian Chem. Soc., 62, 209 (1985).

    Google Scholar 

  4. V. Avasthi and A.C. Chatterji, Z. Phys. Chem. (Leipzig), 245, 154 (1970); 249, 17 (1972).

  5. S. Anandan and R. Gopalan, J. Indian Chem. Soc., 62, 216 (1985).

  6. 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).

  7. S. Srivastava, Oxidation Comm., 15, 37 (1992); 17, 282 (1994).

    Google Scholar 

  8. F. Feigl, Spot tests in Organic Analysis, Elsevier, New York, 1996.

    Google Scholar 

  9. N. Venkatasubramanian and V. Thiagarajan, Can. J. Chem., 47, 694 (1969).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints 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

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1006929504333

Keywords

Navigation