Статья
2016

Thermodynamic study of complexation reactions between 1,7,10,16 Tetra oxa 4,13 diaza cyclo octa decane (Kryptofix22) and Ni2+, Cd2+ and Ag+ metal cations in some pure and binary mixed non-aqueous solvents using conductometry


S. Iravani S. Iravani , G. Rounaghi G. Rounaghi , M. Ebrahimi M. Ebrahimi
Российский электрохимический журнал
https://doi.org/10.1134/S1023193516110070
Abstract / Full Text

The complexation reactions between Ni2+, Cd2+ and Ag+ metal cations with the macrocyclic ligand Kryptofix22 (K22), in pure acetonitrile (AN), ethylacetate (EtOAc), methanol (MeOH) and their binary mixtures have been studied at different temperatures using conductometric method. The obtained results show that in most solvent systems, the stoichiometry of the complexes formed between the macrocyclic ligand and the metal cations is 1: 1 [ML], but in some of the solvent systems, a 1: 2 [ML2] complex and also [M2L], [M2L2] and [M2L3] complexes are formed in solutions. The stability constans of the 1: 1 complexes were obtained using a computer program GENPLOT. A non-liner behavior was observed for changes of logK f of the 1: 1 complexes versus the composition of AN–EtOAc binary solutions. The stability order of the 1: 1 complexes at 25°C in the binary solvent solution of AN–EtOAc (mol % AN = 50) was found to be: (K22.Ag)+ > (K22.Ni)2+ > (K22.Cd)2+. The obtained values of thermodynamic quantities (ΔH c 0S c 0) show that in most of the AN–EtOAc binary solvent solutions, the 1:1 complexation reactions are enthropy stabilized, but from the enthalpy view point, depending on the nature and composition of mixed solvents they are exothermic or athermic.

Author information
  • Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran

    S. Iravani, G. Rounaghi & M. Ebrahimi

References
  1. Pedersen, C.J., J. Am. Chem. Soc., 1967, vol. 89, p. 7071.
  2. Rounaghi, G.H., Mohajeri, M., Ahmadzadeh, S., and Tarahomi, S., J. Inclusion Phenom. Macrocyclic Chem., 2009, vol. 63, p. 365.
  3. Izatt, R.M., Lamb, J.D., Izatt, N.E., Rossiter, B.E., Jr., Christensen, J.J., and Haymore, B.L., Am. Chem. Soc., 1979, vol. 101, p. 6273.
  4. Méric, R., Vignoren, J.-P., and Lehn, J.-M., J. Chem. Soc. Chem. Commun., 1993, p. 129.
  5. Gokel, G.W. and Cram, D.J., J. Chem. Soc. Chem. Commun., 1973, vol. 521, p. 481.
  6. Izatt, R.M., Lamb, J.D., Rossiter, B.E., Izatt, N.E., and Christensen, J.J., J. Chem. Soc. Chem. Commun., 1978, p. 386.
  7. Kyba, E.P., Helgeson, R.C., Madan, K. Gokel, G.W., Tarnowski, T.L., Moore, S.S., and Cram, D.J., J. Am. Chem. Soc., 1977, vol. 99, p. 2564.
  8. Lehn, J.M., Vierling, P., and Hayward, R.C., J. Chem. Soc. Chem. Commun., 1979, p. 296.
  9. Uiterwijk, J.W.H.M., Stavern, C.J.Van., Reinhoudt, D.N., Kruise, L., and Harkema, S., J. Org. Chem., 1986, vol. 51, p. 1575.
  10. Stavern, C.J.Van., Hertorg, H.J., Reinhoudt, D.N., Uiterwijk, J.W.H.M., Kruise, L., and Harkema, S., J. Chem. Soc. Chem. Commun., 1984, p. 1409.
  11. Lamsa, M., Suorsa, T., Pursiainen, J., Huuskonen, J., and Rissanen, K., J. Chem. Commun., 1996, p. 1443.
  12. Lamsa, M., Raitamaa, K., and Pursiainen, J., J. Phys. Chem., 1999, vol. 12, p. 557.
  13. Lamsa, M., Huuskonen, J., Rissanen, K., and Pursiainen, J., J. Chem. Commun. Eur., 1998, vol. 4, p. 84.
  14. Hancock, R.D. and Martell, A.E., Chem. Rev., 1989, vol. 89, p. 1875.
  15. Izatt, R.M., Pawlak, K., Bradshaw, J.S., and Bruening, R.L., Chem. Rev., 1995, vol. 95, p. 2529.
  16. Genplot, Computer Graphic Service, USA, 1989.
  17. Gutmann, V., Coordination Chemistry in Non-aqueous Solutions, New York: Springer, 1968.
  18. Rounaghi, G.H., Mohajeri, M., Atashi, Z., and Mohammadzadeh, R., J. Incl. Phenom., Macrocyclic Chem., 2012, vol. 73, p. 435.