Russian Journal of Physical Chemistry A

, Volume 93, Issue 1, pp 48–58 | Cite as

Comparative Study of Kinetic and Mechanistic Study of Oxidation of L-Alanine and L-Proline by Sodium Periodate Catalyzed by Osmium(VIII) in Micromolar Concentrations

  • Madhu Gupta
  • Amrita SrivastavaEmail author
  • Sheila Srivastava


The kinetics of oxidation of two aliphatic α-amino acids (AA), namely, alanine and proline by NaIO4 has been investigated in alkaline medium in the presence of osmium(VIII) catalyst at a constant ionic strength of 1.0 mol dm–3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions have a first order with respect both to [Os(VIII)] and [NaIO4], and fractional order with respect to both [L-alanine] (Ala) and [L-proline](Pro). The reaction show negligible effect of dielectric constant and ionic strength of medium. Increasing [OH] concentration was found to decrease the oxidation rates while mercuric acetate acts as scavenger for both the reactions. A plausible oxidation mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of intermediate complexes between AA and Os(VIII) before the rate-controlling step. Kinetic investigations have revealed that the order of reactivity is Pro > Ala. The complex thus formed reacts with the oxidant [NaIO4] by an inner-sphere mechanism with formation of the oxidation products of the amino acids which were identified as the corresponding carboxylic compounds, ammonium ion and carbon dioxide. The activation parameters of the first order rate constants were evaluated and discussed.


α-amino acids [NaIO4kinetics mechanism oxidation osmium(VIII) catalyst 



The authors are thankful to the Head, Department of Chemistry, University of Lucknow, Lucknow, for providing necessary laboratory facilities, spectral, elemental and biological activity data. Authors wish to thank reviewers for greatly improving the paper.


None of the authors of the above manuscript has declared any conflict of interest which may arise from being named as an author in the manuscript.


  1. 1.
    A. K. Das, Coord. Chem. Rev. 213, 307 (2001).CrossRefGoogle Scholar
  2. 2.
    G. H. Hugar and S. T. Nandibewoor, Trans. Met Chem. 19, 215 (1994).CrossRefGoogle Scholar
  3. 3.
    S. Srivastava and M. Gupta, Bull. Catal. Soc. India 14, 1 (2015).Google Scholar
  4. 4.
    S. M. Tuwar, S. T. Nandibewoor, and J. R. Raju, Indian J. Chem 30, 158 (1991).Google Scholar
  5. 5.
    M. C. Day and J. Selbin, Theoretical Inorganic Chemistry, 2nd ed. (Van Nustrand Reinhold, New York, 1964), p. 138.Google Scholar
  6. 6.
    L. Maros, I. Molnar-Perel, E. Schissel, and V. Szerdahelyi, J. Chem. Soc. Perkin Trans. 11, 39 (1980).CrossRefGoogle Scholar
  7. 7.
    V. A. Morab, S. M. Tuwar, S. T. Nandibewoor, and J. R. Raju, J. Indian Chem. Soc. 69, 862 (1992).Google Scholar
  8. 8.
    R. Pascual, A. H. Miguel, and E. Callie, Can. J. Chem. 67, 634 (1989).CrossRefGoogle Scholar
  9. 9.
    M. P. Rao, B. S. Sethuram, and N. N. Rao, J. Indian Chem. Soc. 57, 149 (1980).Google Scholar
  10. 10.
    G. Dahlgren and D. K. Reed, J. Am. Chem. Soc. 71, 1380 (1967).CrossRefGoogle Scholar
  11. 11.
    G. J. Buist, A. Bunton, and W. C. P. Hipperson, J. Chem. Soc. B, 2128 (1971).Google Scholar
  12. 12.
    G. H. Jeffery, J. Bassett, J. Mendham, and R. C. Denny, Vogel’s Textbook of Quantitative Chemical Analysis, 5th ed. (ELBS Longman, Essex UK, 1996), p. 455.Google Scholar
  13. 13.
    A. I. Vogel, A Text Book of Practical Organic Chemistry Including Quantitative Organic Analysis (ELBS Longman, Essex, UK, 1973), p. 332.Google Scholar
  14. 14.
    G. K. Vemulapalli, Physical Chemistry (Prentice-Hall, Englewood Cliffs, NJ, 1997), p. 734.Google Scholar
  15. 15.
    B. Sethuram, Some Aspects of Electron Transfer Reactions Involving Organic Molecules (Allied, New Delhi, 2003), p. 78.Google Scholar
  16. 16.
    T. S. Kiran, D. C. Hiremath, and S. T. Nandibewoor, Z. Phys. Chem. 221, 501 (2007).CrossRefGoogle Scholar
  17. 17.
    R. Chang, Physical Chemistry with Applications to Biological Systems (Macmillan, New York, 1981), p. 326.Google Scholar
  18. 18.
    V. C. Seregar, C. V. Hiremath, and S. T. Nandibewoor, Z. Phys. Chem. 220, 615 (2006).CrossRefGoogle Scholar
  19. 19.
    V. B. List, R. A. Lerner, and C. F. Barbes, J. Am. Chem. Soc. 122, 2395 (2000).CrossRefGoogle Scholar
  20. 20.
    D. L. Kamble and S. T. Nandibewoor, J. Phys. Org. Chem. 11, 171 (1998).CrossRefGoogle Scholar
  21. 21.
    J. K. Laidler, Chemical Kinetics, 3rd ed. (Pearson Education, New Delhi, India, 2004).Google Scholar
  22. 22.
    N. Sutin, Ann. ReV. Phys. Chem. 17, 119 (1966).CrossRefGoogle Scholar
  23. 23.
    M. Lancaster and R. S. Murray, J. Chem. Soc., A, 2755 (1971).Google Scholar
  24. 24.
    S. K. Upadhyay and M. C. Agrawal, Indian J. Chem. A 15, 709 (1977).Google Scholar
  25. 25.
    S. A. Farokhi and S. T. Nandibewoor, Tetrahedron 59, 7595 (2003).CrossRefGoogle Scholar
  26. 26.
    B. Sethuram, Some Aspects of Electron Transfer Reactions Involving Organic Molecules (Allied, New Delhi, 2003), p. 78.Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • Madhu Gupta
    • 1
  • Amrita Srivastava
    • 1
    Email author
  • Sheila Srivastava
    • 2
  1. 1.Department of Chemistry, University of LucknowLucknowIndia
  2. 2.Chemical Laboratories, Feroze Gandhi CollegeRaebareliIndia

Personalised recommendations