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Journal of Solution Chemistry

, Volume 19, Issue 11, pp 1073–1084 | Cite as

Kinetics of the solvolysis oftrans-dichlorotetra-(4-t-butylpyridine)-cobalt(III) ions in water +t-butyl alcohol mixtures

  • Kamal H. M. Halawani
  • Cecil F. Wells
Article

Abstract

Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (Cn+) going to the transition state [M(n+1)+...Cl] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, Cn+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl) from either source.

Key words

Solvolysis kinetics mixtures of water+cosolvent 

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References

  1. 1.
    C. N. Elgy and C. F. Wells,J. Chem. Soc. Dalton Trans. 2405 (1980); 1617 (1982);J. Chem. Soc. Faraday Trans. I 79, 2367, (1983);81, 2145; (1985).Google Scholar
  2. 2.
    I. M. Sidahmed and C. F. Wells,J. Chem. Soc. Dalton Trans. 1035 (1983); 1969 (1984); (1969); I. M. Sidahmed and A. M. Ismail,Trans. Metal Chem. 11, 288 (1986);12, 29 (1987).Google Scholar
  3. 3.
    I. M. Sidahmed and A. M. Ismail,Trans. Metal Chem. 12, 332, 449 (1987).Google Scholar
  4. 4.
    G. M. El-Subruiti, I. M. Sidahmed, and C. F. Wells,Int. J. Chem. Kin. (in press).Google Scholar
  5. 5.
    K. H. M. Halawani and C. F. Wells,J. Chem. Soc. Faraday Trans. I 88, 2999 (1989).Google Scholar
  6. 6.
    W. E. Jones, L. R. Carey, and T. W. Swaddle,Can. J. Chem. 50, 2739 (1972); D. A. Palmer and H. Kelm,Inorg. Chem. 16, 3139 (1977);Coord. Chem. Rev. 36, 39 1981); G. Daffner, D. A. Palmer, and H. Kelm.Inorg. Chim. Acta 45, L275 (1980); G. A. Lawrance and S. Suvichittanont,Austral. J. Chem. 33, 273 (1980);Inorg. Chim. Acta 44, L61 (1980); M. J. Sisley and T. W. Swaddle,Inorg. Chem. 20, 2799 (1981); G. A. Lawrance,Inorg. Chem. 21, 3687 (1982); Y. Kitamora and R. van Eldik,Ber. Bunsen Ges. Phys. Chem. 88, 418 (1984); G. A. Lawrance, K. Schneider, and R. van Eldik,Inorg. Chem. 23, 392 (1984); N. J. Curtis and G. A. Lawrance,Inorg. Chem. 25, 1033 (1986); P. A. Lay,Inorg. Chem. 26, 2144 (1987); N. J. Curtis, G. A. Lawrance, and R. van Eldik,Inorg. Chem. 28, 329 (1989).Google Scholar
  7. 7.
    W. G. Jackson and A. M. Sargeson,Inorg. Chem. 17, 1344 (1978); W. G. Jackson and C. M. Begbie,Inorg. Chim. Acta 60, 115 (1982).Google Scholar
  8. 8.
    J. Kenttämaa, E. Tommila, and M. Martti,Ann. Acad. Scient. Fennicae A, No. 93 (1959).Google Scholar
  9. 9.
    K. Nakanishi,Bull. Chem. Soc. Jpn. 33, 793 (1960).Google Scholar
  10. 10.
    G. Wada and S. Umeda,Bull. Chem. Soc. Jpn. 35, 1797 (1962).Google Scholar
  11. 11.
    J. Andreae, P. D. Edmonds, and J. F. McKellar, Acustica 15, 74 (1965); M. J. Blandamer,Introduction to Chemical Ultrasonics (Academic Press, London, 1973), Chap. 11.Google Scholar
  12. 12.
    G. S. Groves and C. F. Wells,J. Chem. Soc. Faraday Trans. I 78, 619 (1982); 81, 2475 (1985);Trans. Metal Chem. 11, 20 (1986);Int. J. Chem. Kin. 18, 529 (1986); G. S. Groves, A. F. M. Nazer, and C. F. Wells,J. Chem. Soc. Faraday Trans. I 83, 1119 (1987); G. S. Groves, K. H. M. Halawani, and C. F. Wells,J. Solution Chem. 16, 399 (1987).Google Scholar
  13. 13.
    A. E. Eid and C. F. Wells,J. Chem. Soc. Faraday Trans. I 77, 1621 (1981); 79, 253 (1983); 81, 1401 (1985); 82, 1643 (1986);Trans. Metal Chem. 10, 223 (1985);Int. J. Chem. Kin. 18, 215 (1986).Google Scholar
  14. 14.
    K. H. M. Halawani and C. F. Wells,J. Chem. Res. (S), 58 (1988), (M), 0501; D. A. Bush and C. F. Wells,J. Chem. Soc. Faraday Trans. I 86, 941 (1990).Google Scholar
  15. 15.
    K. J. Laidler and P. A. Landskroener,Trans. Faraday Soc. 52, 200 (1956).Google Scholar
  16. 16.
    T. L. Broadwater and R. L. Kay,J. Phys. Chem. 74, 3802 (1970).Google Scholar
  17. 17.
    A. C. Brown and D. J. G. Ives,J. Chem. Soc. 1608 (1962).Google Scholar
  18. 18.
    G. Åkerlöf,J. Am. Chem. Soc. 54, 4125 (1932).Google Scholar
  19. 19.
    C. F. Wells,J. Chem. Soc. Faraday Trans. I. 73, 1851 (1977).Google Scholar
  20. 20.
    E. Grunwald and S. Winstein,J. Am. Chem. Soc. 70, 846 (1948).Google Scholar
  21. 21.
    C. F. Wells,Trans. Faraday Soc. 66, 204 (1970);J. Chem. Soc. Faraday Trans. I 70, 694 (1974).Google Scholar
  22. 22.
    H. S. Frank and M. W. Evans,J. Chem. Phys. 13, 507 (1945); H. S. Frank and W.-Y. Wen,Discussion Faraday Soc. 24, 133 (1957); G. Némethy and H. A. Sheraga,J. Chem. Phys. 36, 3382, 3401 (1962); N. Laiden and G. Némethy,J. Phys. Chem. 74, 3501 (1970).Google Scholar
  23. 23.
    C. F. Wells,J. Chem. Soc. Faraday Trans. I 72, 601 (1976);Austral. J. Chem. 36, 1739 (1983); I. M. Sidahmed and C. F. Wells,J. Chem. Soc. Faraday Trans. I 82, 2577 (1986).Google Scholar
  24. 24.
    I. M. Sidahmed and C. F. Wells,J. Chem. Soc. Dalton Trans. 2034 (1981); G. S. Groves and C. F. Wells,J. Solution Chem. 15, 211 (1986).Google Scholar
  25. 25.
    M. J. Blandamer, B. Briggs, J. Burgess, D. Elvidge, P. Guardado, A. W. Hakin, C. D. Hubbard, and S. Radulovic,J. Chem. Soc. Faraday Trans. I 84, 2703 (1988).Google Scholar
  26. 26.
    C. F. Wells,Thermochim. Acta 132, 141 (1988).Google Scholar
  27. 27.
    M. J. Blandamer, J. Burgess, and E.-E. Abu-Gharib,Trans. Metal Chem. 9, 193 (1984); M. J. Blandamer and J. Burgess,Trans. Metal Chem. 13, 1 (1988).Google Scholar

Copyright information

© Plenum Publishing Corporation 1990

Authors and Affiliations

  • Kamal H. M. Halawani
    • 1
  • Cecil F. Wells
    • 1
  1. 1.School of ChemistryUniversity of BirminghamBirminghamUK

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