Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Studies on the kinetics and mechanism of redox decomposition of 1,2,6-trinitrotriamminecobalt(III) and 1,2,6-trinitrodiethylenetriaminecobalt(III) complexes in aqueous acid

  • 28 Accesses

  • 5 Citations

Summary

In aqueous acid media the title complexes undergo decomposition ultimately forming cobalt(II). Detailed analysis of the kinetic data reveals that the reactions proceed in two consecutive stages, the initial step being the faster one. Evidence has been presented that the initial faster step involves aquation releasing one NO 2 ligand and forming an aquodinitro complex, which subsequently undergoes a slower intramolecular redox decomposition into Co2+. Each step, on the other hand, has been found to consist of two concurrent paths,viz. spontaneous and acid catalysed, respectively. Activation parameters corresponding to all these specific rate constants have been evaluated and a plausible mechanism for the overall reaction has been proposed.

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

References

  1. (1)

    W. M. Latimer,The Oxidation States of the Elements and their Potentials in Aqueous Solutions, 2nd Edit., p. 213, Prentice-Hall, N.Y., 1952.

  2. (2)

    D. Klein and C. W. Moeller,Inorg. Chem., 4, 394 (1965).

  3. (3)

    W. C. Taylor, Jr. and C. W. Moeller,Inorg. Chem., 4, 398, (1965).

  4. (4)

    W. W. Wendlandt and J. P. Smith,The Thermal Properties of Transition Metal Ammine Complexes, Ch. 3–5, Elsevier, Amsterdam, 1967, and refs. therein.

  5. (5)

    S. Onodera,Bull. Chem. Soc. Jpn., 52, 911 (1979).

  6. (6)

    R. G. Linck in M. L. Tobe (Ed.),Reaction Mechanisms in Inorganic Chemistry, MTP. Int. Rev. Sci., Inorg. Chem. Ser. 1, Vol. 9, Ch. 8, 1972, and refs. therein.

  7. (7)

    G. C. Lalor,J. Chem. Soc. A, 1 (1966).

  8. (8)

    D. Banerjea,J. Inorg. Nucl. Chem., 29, 2795 (1967).

  9. (9)

    J. W. Moore and R. G. Pearson,Inorg. Chem., 3, 1334 (1964).

  10. (10)

    S. Balt and C. Dekkar,Inorg. Chem., 15, 1025 (1976).

  11. (11)

    H. Yoneda,Bull. Chem. Soc. Jpn., 31, 74 (1958).

  12. (12)

    H. Yoneda,Bull. Chem. Soc. Jpn., 30, 924 (1957).

  13. (13)

    S. Lum, W. D. Stanley and C. S. Garner,J. Inorg. Nucl. Chem., 35, 1293 (1973).

  14. (14)

    J. D. White, J. C. Sullivan and H. Taube,J. Am. Chem. Soc, 92, 4733 (1970).

  15. (15)

    P. Wilairat and C. S. Garner,J. Inorg. Nucl. Chem., 33, 1833 (1971).

  16. (16)

    M. C. Couldwell and D. A. House,J. Inorg. Nucl. Chem., 33, 2583 (1971).

  17. (17)

    G. Schlessinger,Inorg. Synth., 6, 189 (1960).

  18. (18)

    Y. Shibata and H. Sueda,J. Chem. Soc. Jpn., 30, 1243 (1915);Bull. Chem. Soc. Jpn., 12, 188 (1937); ibid.,13, 450 (1938).

  19. (19)

    A. V. Kiss and D. V. Czegledy,Z. anorg. Chem., 235, 407 (1938); M. Linhard and M. Weigel,Z. anorg Chem., 267, 113 (1951).

  20. (20)

    P. H. Crayton,Inorg. Synth., 7, 209 (1963).

  21. (21)

    P. H. Crayton and J. A. Mattern,J. Inorg. Nucl. Chem., 13, 248 (1960).

  22. (22)

    R. N. Banerjee and D. Banerjea,Indian J. Chem., 17A, 246 (1979).

  23. (23)

    S. Glasstone, K. J. Laidler and H. Eyring,The Theory of Rate Processes, McGraw-Hill, New York, 1941.

  24. (24)

    I. I. Cernjaev,Russ. J. Inorg. Chem. (Engl. Transl.),2, 1 (1957).

  25. (25)

    J. E. Leffler,J. Org. Chem., 20, 1202 (1955).

  26. (26)

    A. A. Frost and R. G. Pearson,Kinetics and Mechanism, 2nd Edit., Ch. 8, Wiley, New York, 1961.

Download references

Author information

Correspondence to Debabrata Banerjea.

Additional information

On leave from Agra College, Agra, India.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Banerjee, A.K., Misra, A., Basak, A.K. et al. Studies on the kinetics and mechanism of redox decomposition of 1,2,6-trinitrotriamminecobalt(III) and 1,2,6-trinitrodiethylenetriaminecobalt(III) complexes in aqueous acid. Transition Met Chem 7, 239–242 (1982). https://doi.org/10.1007/BF00618704

Download citation

Keywords

  • Cobalt
  • Inorganic Chemistry
  • Detailed Analysis
  • Acid Medium
  • Initial Step