Abstract
A thermodynamic study of the association of Na+, K+, Rb+, and Cs+ with dicyclohexano-18-crown-6 in acetonitrile has been carried out at 308, 303, 298, 293, and 288 K using a conductometric technique. The observed molar conductivities, A, were found to decrease significantly for mole ratios less than unity. A model involving 1∶1 stoichiometry has been used to analyze the conductivity data. The stability constant,K, and the limiting molar conductivity, A c , for each 1∶1 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of logK at 298 K, as derived from this study is K+>Na+>Rb+>Cs+. Values of ΔH o and ΔS o are reported and their significance is discussed.
Similar content being viewed by others
References
I. J. Burden, A. C. Coxon, J. F. Stoddart, and C. M. Wheatley:J. Chem. Soc. Perkin Trans. I 220 (1977).
R. M. Izatt, J. S. Bradshaw, S. A. Nielsen, J. D. Lamb, and J. J. Christensen:Chem. Rev. 85, 271 (1985).
H. K. Frensdorff:J. Am. Chem. Soc. 93, 600 (1971).
R. M. Izatt, R. E. Terry, B. L. Haymore, L. D. Hansen, N. K. Dalley, A. G. Avondet, and J. J. Christensen:J. Am. Chem. Soc. 98, 7620 (1976).
R. M. Izatt, D. P. Nelson, J. H. Rytting, B. L. Haymore, and J. J. Christensen:J. Am. Chem. Soc. 93, 1619 (1971).
D. F. Evans, S. L. Wellington, J. A. Nadis, and E. L. Cussler:J. Solution Chem. 1, 499 (1972).
A. Hofmanova, J. Koryta, M. Brezina, and M. L. Mittal:Inorg. Chim. Acta 28, 73 (1978).
Y. Takeda, Y. Kudo, and S. Fujiwara:Bull. Chem. Soc. Jpn. 58, 1315 (1985).
Y. Takeda and H. Yano:Bull. Chem. Soc. Jpn. 53, 1720 (1980).
H. P. Hopkins and A. B. Norman:J. Phys. Chem. 84, 309 (1980).
J. A. Nedler and R. Mead:Comput. J. 7, 308 (1965).
E. Mei, A. I. Popov, and J. L. Dye:J. Phys. Chem. 81, 1677 (1977).
E. Mei, A. I. Popov, and J. L. Dye:J. Am. Chem. Soc. 99, 6532 (1977).
S. Kulstad and L. A. Malmsten:J. Inorg. Nucl. Chem. 43, 1299 (1981).
R. L. Kay, B. J. Hales, and G. P. Cunningham:J. Phys. Chem. 71, 3925 (1967).
G. S. Kell, and A. R. Gordon:J. Am. Chem. Soc. 81, 3207 (1959).
H. J. Buschmann:J. Solution Chem. 16, 181 (1987).
I. M. Kolthoff and M. K. Chantooni:Anal. Chem. 52, 1039 (1980).
C. J. Pedersen:J. Am. Chem. Soc. 92, 386 (1970).
Y. Takeda, H. Yano, M. Ishibashi, and H. Isozumi:Bull. Chem. Soc. Jpn. 53, 72 (1980).
A. J. Smetana, and A. I. Popov:J. Chem. Thermodynamics 11, 1145 (1979).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tawarah, K.M., Mizyed, S.A. A thermodynamic study of the association of alkali metal cations with dicyclohexano-18-crown-6. Journal of Inclusion Phenomena 6, 555–564 (1988). https://doi.org/10.1007/BF00656336
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00656336