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Conductance study of the thermodynamics of some transition and heavy metal cryptates in binary acetonitrile-dimethylsulfoxide mixtures

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Abstract

A conductance study of the interaction between Co2+, Ni2+, Cu2+, Cd2+, Zn2+ and Pb2+ ions with cryptands C211, C221 and C222 in different acetonitrile-dimethylsulfoxide mixtures has been carried out at various temperatures. The formation constants of the resulting metal cryptates were determined from the molar conductance-mole ratio data. It was found that the stability of Co2+, Ni2+, Cu2+ and Zn2+ cryptates vary in the order C211>C221>C222, while for Cd2+ cryptates the stability order is C221>C222>C211. A linear relationship is observed between logK f of different metal cryptates and the mole fraction of acetonitrile in the solvent mixture. The enthalpy and entropy of cryptate formation reactions were determined from the temperature dependence of the formation constants. The enthalpy and entropy changes are quite sensitive to the solvent composition and the resultingTΔS 0−ΔH 0 plot shows a fairly good linear correlation, indicating the existence of an entropy-enthalpy compensation in the cryptate formation reactions.

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References

  1. B. Dietrich, J.M. Lehn and J.P. Sauvage:Tetrahedron Lett. 2885 (1969).

  2. J.M. Lehn:Pure Appl. Chem. 49, 857 (1977).

    Google Scholar 

  3. J.L. Dye:Progress in Macrocyclic Chemistry (Eds. R.M. Izatt and J.J. Christensen) Vol. 1, Ch. 2, Wiley-Interscience, New York (1979).

    Google Scholar 

  4. R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, J.J. Christensen and D. Sen:Chem. Rev. 85, 271 (1985).

    Google Scholar 

  5. R.M. Izatt, J.S. Bradshaw, K. Pawlak, R.L. Bruening and B.J. Tarbet:Chem. Rev. 91, 1721 (1991).

    Google Scholar 

  6. J.M. Lehn and J.P. Sauvage:J. Am. Chem. Soc. 97, 6700 (1975).

    Google Scholar 

  7. E. Kauffmann, J.M. Lehn and J.P. Sauvage:Helv. Chim. Acta 59, 1099 (1976).

    Google Scholar 

  8. E. Mei, A.I. Popov and J.L. Dye:J. Am. Chem. Soc. 99, 6532 (1977).

    Google Scholar 

  9. M.K. Chantooni and I.M. Kolthoff:J. Solution Chem. 14, 1 (1985).

    Google Scholar 

  10. H.J. Buschmann:Inorg. Chim. Acta 125, 31 (1986).

    Google Scholar 

  11. H.J. Buschmann:Polyhedron 7, 721 (1988).

    Google Scholar 

  12. J. Gutknecht, H. Schneider and J. Stroka:Inorg. Chem. 17, 3326 (1978).

    Google Scholar 

  13. H.J. Buschmann:Inorg. Chim. Acta 98, 43 (1985).

    Google Scholar 

  14. H.J. Buschmann:Inorg. Chim. Acta 108, 241 (1985).

    Google Scholar 

  15. A.K. Convington and K.E. Newman:Pure Appl. Chem. 15, 2041 (1979).

    Google Scholar 

  16. Y. Marcus:J. Chem. Soc., Faraday Trans. 1 84, 1465 (1988).

    Google Scholar 

  17. M. Saeidi and M. Shamsipur:J. Coord. Chem. 22, 131 (1990).

    Google Scholar 

  18. H. Parham and M. Shamsipur:J. Electroanal. Chem. 314, 71 (1991).

    Google Scholar 

  19. P. Chatterjee, A.K. Laha and S. Bagchi:J. Chem. Soc., Farady Trans. 88, 1675 (1992).

    Google Scholar 

  20. M.R. Fat'hi and M. Shamsipur:Spectrosc. Lett. 26, 1797 (1993).

    Google Scholar 

  21. M. Shamsipur, J. Ghasemi, F. Tammaddon and H. Sharghi:Talanta 40, 697 (1993).

    Google Scholar 

  22. A. Rouhollahi, M.K. Amini and M. Shamsipur:J. Solution Chem. 63 (1994).

  23. V. Gutmann:The Donor-Acceptor Approach to Molecular Interactions Plenum, New York (1978).

    Google Scholar 

  24. H. Parham and M. Shamsipur:Polyhedron 11, 987 (1992).

    Google Scholar 

  25. M.S. Greenberg and A.I. Popov:Spectrochim. Acta. 31A, 697 (1975).

    Google Scholar 

  26. Y.C. Wu and W.F. Koch:J. Solution Chem. 20, 391 (1991).

    Google Scholar 

  27. M.K. Amini and M. Shamispur:J. Solution Chem. 21, 275 (1991).

    Google Scholar 

  28. V.A. Nicely and J.L. Dye:J. Chem. Educ. 48, 443 (1971).

    Google Scholar 

  29. M.K. Amini and M. Shamsipur:Inorg. Chim. Acta 183, 65 (1991).

    Google Scholar 

  30. A. Jabbari, M. Hasani and M. Shamsipur:J. Incl. Phenom. 15, 329 (1993).

    Google Scholar 

  31. M. Hasani and M. Shamsipur:J. Incl. Phenom. 16, 123 (1993).

    Google Scholar 

  32. G.J. Janz and R.P.T. Tomkins:Nonaqueous Electrolytes Handbook, Vol. 1, Academic Press, New York (1972).

    Google Scholar 

  33. A.J. Smetana and A.I. Popov:J. Chem. Thermodyn. 11, 1145 (1979).

    Google Scholar 

  34. M. Shamsipur, G. Rounaghi and A.I. Popov:J. Solution Chem. 9, 701 (1980).

    Google Scholar 

  35. P. Henderson:Inorganic Geochemistry, Pergamon, New York (1982).

    Google Scholar 

  36. R.D. Shannon:Acta Crystallogr 32A, 751 (1976).

    Google Scholar 

  37. J.M. Lehn and J.P. Sauvage:Chem. Commun. 440 (1971).

  38. F. Arnaud-Neu, B. Spiess and M.J. Schwing-Weill:J. Am. Chem. Soc. 104, 5641 (1982).

    Google Scholar 

  39. L.L. Soong, G.E. Leroi and A.I. Popov:Inorg. Chem. 29, 1366 (1990).

    Google Scholar 

  40. J. Ghasemi and M. Shamsipur:J. Coord. Chem. 26, 337 (1992).

    Google Scholar 

  41. R.M. Izatt, R.E. Terry, D.P. Nelson, Y. Chan, D.J. Eatough, J.S. Bradshaw, L.D. Hansen and J.J. Christensen:J. Am. Chem. Soc. 98, 7626 (1976).

    Google Scholar 

  42. B.G. Cox, C. Guminki and H. Schneider:J. Am. Chem. Soc. 104, 3789 (1982).

    Google Scholar 

  43. B.G. Cox, P. Firman, D. Gudin and H. Schneider:J. Phys. Chem. 86, 4986 (1982).

    Google Scholar 

  44. M.B. Gholivand and M. Shamsipur:Inorg. Chim. Acta 121, 53 (1986).

    Google Scholar 

  45. M. Shamsipur, A. Esmaeili and M.K. Amini:Talanta 38, 1300 (1989).

    Google Scholar 

  46. M. Shamsipur and A.I. Popov:J. Am. Chem. Soc. 101, 4051 (1979).

    Google Scholar 

  47. R.M. Izatt, J.S. Bradshaw, K. Pawlak, R.L. Bruening and B.J. Tarbet:Chem. Rev. 92, 1261 (1992).

    Google Scholar 

  48. Y. Inoue and T. Hakushi:J. Chem. Soc., Perkin Trans. 2, 935 (1985).

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Razi University, Kermanshah, Iran

    Mojtaba Shamsipur

  2. Department of Chemistry, Shiraz University, Shiraz, Iran

    Jahanbakhsh Ghasemi

Authors
  1. Mojtaba Shamsipur
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  2. Jahanbakhsh Ghasemi
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Additional information

Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82181 (30 pages).

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Shamsipur, M., Ghasemi, J. Conductance study of the thermodynamics of some transition and heavy metal cryptates in binary acetonitrile-dimethylsulfoxide mixtures. J Incl Phenom Macrocycl Chem 20, 157–171 (1994). https://doi.org/10.1007/BF00709340

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  • DOI: https://doi.org/10.1007/BF00709340

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