Abstract
Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 1∶1 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E a , ΔH‡ and ΔS‡, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters.
Similar content being viewed by others
References
I. M. Kolthoff,Anal. Chem. 51, 1R (1979).
R. M. Izatt, J. S. Bradshaw, S. A. Nielsen, J. D. Lamb, J. J. Christensen, and D. Sen,Chem. Rev. 85, 271 (1985).
R. M. Izatt, K. Pawlak, J. S. Bradshaw, and R. L Bruening,Chem. Rev. 91, 1721 (1991).
R. D. Boss and A. I. Popov,Inorg. Chem. 24, 3660 (1985).
M. Brighli, P. Fux, J. Lagrange, and P. Lagrange,Inorg. Chem. 24, 80 (1985).
H. J. Buschmann,Inorg. Chim. Acta 98, 43 (1985).
H. J. Buschmann,Thermochim. Acta 97, 219 (1986).
R. M. Izatt, G. A. Clark, J. D. Lamb, J. E. King, and J. J. Christensen,Thermochim. Acta 97, 219 (1986).
L. Che, M. Bos, P. D. J. Grootenhuis, A. Christenhusz, E. Hoggendom, D. N. Reinhoudt, and W. E. Van Der Linden,Anal. Chim. Acta 201, 117 (1987).
L. J. Rodriguez, G. W. Liesegang, M. M. Farrow, N. Purdie, and E. M. Eyring,J. Phys. Chem. 82, 647 (1978).
B. O. Strasser, M. Shamsipur, and A. I. Popov,J. Phys. Chem. 89, 4822 (1985).
M. Shamsipur and A. I. Popov,J. Phys. Chem. 90, 5997 (1986).
P. Szczygiel, M. Shamsipur, K. Hallenga, and A. I. Popov,J. Phys. Chem. 91, 1252 (1987).
M. Shamsipur and A. I. Popov,J. Phys. Chem. 91, 447 (1987).
M. Shamsipur and A. I. Popov,J. Phys. Chem. 92, 147 (1988).
M. K. Amini and M. Shamsipur,J. Phys. Chem. 95, 9601 (1991).
G. W. Gokel, D. J. Cram, C. L. Liotta, H. P. Harris, and F. L. Cook,Org. Synth. 56, 30 (1977).
E. T. Roach, P. R. Handy, and A. I. Popov,Inorg. Nucl. Chem. Lett. 9, 359 (1973).
V. A. Nicely and J. L. Dye,J. Chem. Educ. 48, 443, (1971).
J. A. Pople, W. G. Schneider, and H. J. Bernstein,High Resolution Nuclear Magnetic Resonance (McGrow-Hill, New York, 1959), p.218.
Y. M. Cahen, J. L. Dye, and A. I. Popov,J. Phys. Chem. 79, 1292 (1975).
V. Gutmann,The Donor-Acceptor Approach to Molecular Interactions (Plenum, New York, 1978).
M. Shamsipur and A. I. Popov,J. Am. Chem. Soc. 101, 4051 (1979).
M. Shamsipur, G. Rounaghi, and A. I. Popov,J. Solution Chem. 9, 701 (1980).
M. B. Gholivand, S. Kashanian, and M. Shamsipur,Polyhedron 6, 535 (1987).
S. Kashanian and M. Shamsipur,Inorg. Chim. Acta 155, 203 (1989).
M. K. Amini and M. Shamsipur,Inorg. Chim. Acta 183, 65 (1991).
R. H. Erlish and A. I. Popov,J. Am. Chem. Soc. 93, 5620 (1971).
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).
M. B. Gholivand and M. Shamsipur,Inorg. Chim. Acta 121, 53 (1986).
M. Shamsipur, A. Esmaeili, and M. K. Amini,Talanta 36, 1300 (1989).
M. Saeidi and M. Shamsipur,J. Coord. Chem. 22, 131 (1990).
J. M. Cearso, P. B. Smith, S. Landers, and J. L. Dye,J. Phys. Chem. 81, 760 (1977).
E. Shchori, J. Jagur-Grodzinski, Z. Luz, and H. Shporer,J. Am. Chem. Soc. 93, 7133 (1971).
J. M. Lehn, J. P. Sauvage, and B. Dietrich,J. Am. Chem. Soc. 92, 2916 (1970).
S. H. Lin, K. P. Li, and H. Eyring, inPhysical Chemistry, an Advanced Treatise, Vol. VII, H. Eyring, D. Handerson, and W. Yost, eds., (Academic Press, New York, 1977), p. 1.
B. O. Strasser and A. I. Popov,J. Am. Chem. Soc. 107, 7921 (1985).
B. G. Cox, J. Gracia-Rosas, and H. Schneider,J. Am. Chem. Soc. 103, 1054 (1981).
J. A. A. deBoer and D. N. Reinhoudt,J. Am. Chem. Soc. 107, 5347 (1985).
P. A. Mosier-Boss and A. I. Popov,J. Am. Chem. Soc. 107, 6168 (1985).
J. A. A. deBoer, D. N. Reinhoudt, S. Harkema, G. J. van Hummel, and F. de JongJ. Am. Chem. Soc. 104, 4073 (1982).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Rouhollahi, A., Amini, M.K. & Shamsipur, M. NMR study of the stoichiometry, stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures. J Solution Chem 23, 63–74 (1994). https://doi.org/10.1007/BF00972608
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00972608