Skip to main content
SpringerLink
Log in

Kinetic and mechanistic studies of oxidation of amine-N-polycarboxylates complexes of cobalt(II) by periodate ions in aqueous medium

  • Article
  • Published:
Journal of the Iranian Chemical Society Aims and scope Submit manuscript

Abstract

The kinetics and mechanism of interaction of periodate ion with [CoIIL(H2O)]2-n [L = trimethylenediaminetetraaceticacid (TMDTA)] and ethylene glycol bis(2-aminoethyl ether) N,N,N’,N’-tetraaceticacid (EGTA) have been studied spectrophotometrically by following an increase in absorbance at λmax = 550 nm in acetate buffer medium as a function of pH, ionic strength, temperature, various concentration of periodate and [CoIIL(H2O)]2-n under pseudo-first order conditions. The experimental observations have revealed that the intermediates having sufficiently high half life are produced during the course of both the reactions which finally get converted into a corresponding [CoIIIL(H2O)]3-n complexes as a final reaction product. The reaction is found to obey the general rate law Rate = (k2 [IO4 −] + k3 [IO4 −]2) [CoIIL(H2O)]2-n. This rate law is consistent with a four step mechanistic scheme (vide supra) where electron transfer proceeds through an inner sphere complex formation. The value of rate constant k2 is independent of pH over the entire pH range which suggest that unprotonated form of [CoIIL(H2O)]2-n is the only predominant species. The value of k2 is invariant to ionic strength variation in both the systems. The value of k3 is also found to be almost invariant to ionic strength in case of [CoIITMDTA(H2O)]2−-[IO4]− system but it decreases considerably in case of [CoIIEGTA(H2O)]2−-[IO4]− system with the corresponding decrease in ionic strength. The activation parameters have been computed and given in support of proposed mechanistic scheme.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Y. Salfab, J. Inorg. Nucl. Chem. 38 (1976) 2271.

    Google Scholar 

  2. Y. Sulfab, A.L. Abu-Shadi, Inorg. Chem. Acta 21 (1977) 115.

    CAS  Google Scholar 

  3. A.Y. Kasim, Y. Sulfab, Inorg. Chem. Acta 24 (1977) 247.

    CAS  Google Scholar 

  4. F.R. El-Eziri, Y. Sulfab, Inorg. Chem. Acta 25 (1977) 15.

    CAS  Google Scholar 

  5. G.J. Buist, in: C.H. Boneford, C.F.H. Tripper (Eds.), Comprehensive Chemical Kinetics, Elsevier, Amsterdam, 1972, pp. 435–456.

    Google Scholar 

  6. A. Indelli, F. Ferranti, F. Secco, J. Phys. Chem. 70 (1966) 631.

    CAS  Google Scholar 

  7. A.A. Abdel-Khalek, Y. Sulfab, J. Inorg. Nucl. Chem. 43 (1981) 3257.

    CAS  Google Scholar 

  8. M.A. Hussein, A.A. Abdel-Khalek, Y. Sulfab, J. Chem. Soc. Dalton Trans. (1983) 317.

  9. Y. Sulfab et al., Polyhedron 9 (1990) 99.

    Google Scholar 

  10. R.M. Naik, J. Sarkar, D.D. Chaturvedi, A. Verma, S.K. Singh Indian J. Chem. Sec. 42A (2003) 1639.

    Google Scholar 

  11. S.S. Anis, M.A. Mansour, Trans. Metal. Chem. 26 (2001) 695.

    CAS  Google Scholar 

  12. M.A. Mansour, Trans. Metal. Chem. 28 (2003) 276.

    CAS  Google Scholar 

  13. G.R. Babu, K. Ramakrishna, G. Venkateswarlu, P.V. Subba Rao, Indian J. Chem. 42A (2003) 1053.

    CAS  Google Scholar 

  14. F.S.H. Head, H.A. Standing, J. Chem. Soc. (1957) 1457.

  15. J.A. Wegh, R.E. Hasmm, Inorg. Chem. 7 (1968) 2431.

    Google Scholar 

  16. D.H. Huchital, R.J. Hodges, Inorg. Chem. Acta 12 (1973) 1004.

    CAS  Google Scholar 

  17. H.A. Mottala, H. Freiser, Anal. Chem. 39 (1967) 1294.

    Google Scholar 

  18. A.Y. Kasim, Y. Sulfab, Inorg. Chem. Acta 22 (1977) 169.

    CAS  Google Scholar 

  19. E. Norkus, A. Vas Kelis, A. Griguceviciene, G. Rohovskrs, H.S.J. Reklai, P. Norkus, Trans. Metal. Chem. 26 (2001) 465.

    CAS  Google Scholar 

  20. D.J.B. Galiford, J.M. Ottaway, Analyst 91 (1972) 415.

    Google Scholar 

  21. B.J. Buist, W.C.P. Hipperson, J.D. Lewis, J. Chem. Soc. A (1969) 307.

  22. D.S. Everhart, R.F. Evilia, Inorg. Chem. 14 (1975) 27.

    Google Scholar 

  23. L.L. Grazynski, B.J. Trzebiatowska, Coord. Chem. 10 (1980) 159.

    Google Scholar 

  24. S. Chabarek, A.E. Frost, M.A. Doran, N.J. Bicknell, J. Inorg. Nucl. Chem. 11 (1959) 184.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Lucknow University, Lucknow, 226 007, India

    R. M. Naik, A. Srivastava, A. K. Tiwari, S. B. S. Yadav & A. K. Verma

Authors
  1. R. M. Naik
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. Srivastava
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. K. Tiwari
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. B. S. Yadav
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. K. Verma
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to R. M. Naik.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Naik, R.M., Srivastava, A., Tiwari, A.K. et al. Kinetic and mechanistic studies of oxidation of amine-N-polycarboxylates complexes of cobalt(II) by periodate ions in aqueous medium. JICS 4, 63–71 (2007). https://doi.org/10.1007/BF03245804

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF03245804

Keywords

Search

Navigation