Abstract
The interactions of the La(III) cations with three anions (X), nitrate, chloride and perchlorate, in aqueous solutions in the pH range 4.0–6.5, were studied by139La NMR spectroscopy. A single model, involving the formation of the contact ion-pair (inner-sphere complex) (LaX)2+ was successfully and quantitatively applied to the chemical shift and the transverse relaxation rate data. Both measurements gave values for the thermodynamic equilibrium constants of formation of (LaX)2+ (K th ) in good agreement (average K th =0.45±0.05; 0.15±0.09; 0.03±0.01, respectively for nitrate, chloride and perchlorate). The complexes are characterized by chemical shifts of −25, 22 and −3.1 ppm and by transverse relaxation rates of 11.2, 5 and 1.65 kHz respectively for nitrate, chloride and perchlorate. The139La quadrupolar relaxation rate is not controlled by the reorientational correlation time. This finding is discussed, and it is suggested that the very fast exchange of water molecules in the first coordination sphere of La(III) is responsible for the time fluctuation of the electric field gradient at the139La nucleus site.
Similar content being viewed by others
References
C. H. Evans,Biochemistry of the Lanthanides (Plenum, New York, 1990).
J. C. G. Bunzli and D. Wessner,Coord. Chem. Rev. 60, 191 (1984).
A. Habenschuss and F. H. Spedding,J. Chem. Phys. 73, 442 (1980).
D. L. Wertz and S. T. Finch,Inorg. Chem. 18, 1590 (1979).
C. Cossy, L. Helm, and A. E. Merbach,Inorg. Chem. 27, 1973 (1988).
C. Cossy and A. E. Merbach,Pure Appl. Chem. 60, 1785 (1988)
C. Cossy, A. C. Barnes, J. E. Enderby, and A. E. Merbach,J. Chem. Phys. 90, 3254 (1989)
L. Helm and A. E. Merbach,Eur. J. Solid State Inorg. Chem. 28, 245 (1991).
H. B. Silber, R. Bakhshandehfar, L. A. Contreras, F. Gaizer, M. Gonsalves, and S. Ismail,Inorg. Chem. 29, 4473 (1990).
P. J. Breen and W. DeW. Horrocks, Jr.,Inorg. Chem. 22, 536 (1983).
H. B. Silber and R. L. Campbell,J. Less-Common Met. 149, 265 (1989).
A. Fratiello, V. Kubo-Anderson, S. Azimi, T. Flores, E. Marinez, D. Matejka, R. Perrigan, and M. Vigil,J. Solution Chem. 19, 811 (1990).
A. Fratiello, V. Kubo-Anderson, T. Bolinger, C. Cordero, B. DeMerit, T. Flores, D. Matejka, and R. Perrigan,J. Magn. Resonance 83, 358 (1989).
A. Fratiello, V. Kubo-Anderson, T. Bolinger, C. Cordero, B. DeMerit, T. Flores, and R. Perrigan,J. Solution Chem. 18, 313 (1989).
C. Detellier, inNMR of Newly Accessible Nuclei, Vol. 2, P. Laszlo, ed., (Academic, New York, 1983) Chap. 5.
D. Rehder, inMultinuclear NMR, J. Mason, ed., (Plenum, New York, 1987) Chap. 19.
K. Nakamura, K. Kawamura,Bull. Chem. Soc. Jpn. 44, 330 (1971).
J. Reuben,J. Phys. Chem. 79, 2154 (1975).
J. Reuben and Z. Luz,J. Phys. Chem. 80, 1357 (1976).
L. S. Smith, Jr., D. C. McCain, and D. L. Wertz,J. Am. Chem. Soc. 98, 5125 (1976).
P. L. Rinaldi, S. A. Khan, G. R. Choppin, and G. C. Levy,J. Am. Chem. Soc. 101, 1350 (1979).
D. C. McCain,J. Inorg. Nucl. Chem. 42, 1185 (1980).
O. Lutz and H. Oehler,J. Magn. Resonance 37, 261 (1980).
D. F. Evans and P. H. Missen,J. Chem. Soc. Dalton Trans. 1929 (1982).
V. P. Tarasov, G. A. Kirakosyan, S. V. Trots, Yu. A. Buslaev, and V. T. Panyushkin,Koord. Khim. 9, 205 (1983).
C. F. G. C. Geraldes and A. D. Sherry,J. Magn. Resonance 66, 274 (1986).
J. C. G. Bunzli, A. E. Merbach, and R. M. Nielson,Inorg. Chim. Acta 139, 151 (1987).
Y. Ducommun, L. Helm, G. Laurenczy, and A. E. Merbach,Magn. Reson. Chem. 26, 1023 (1988).
Z. Chen, H. Dettman, and C. Detellier,Polyhedron 8, 2029 (1989).
S. J. Lyle and M. M. Rahman,Talanta 10, 1177 (1963).
K. M. Brière and C. Detellier,J. Phys. Chem. 91, 6097 (1987).
M. Fréchette, I. R. Butler, R. Hynes, and C. Detellier,Inorg. Chem. 31, 1650 (1992).
L. A. Bromley,J. Chem. Thermodyn. 4, 669 (1972).
J. F. Zemaitis, Jr., D. M. Clark, M. Rafal, and N. C. Scrivner,Handbook of Aqueous Electrolyte Thermodynamics (DIPPR Publications., New York, 1986).
J.-C. G. Bunzli and J.-R. Yersin,Inorg. Chem. 18, 605 (1979).
Z. Kollarik,Coll. Czech. Chem. Comm. 32, 435 (1967).
J. Reuben and D. Fiat,J. Chem. Phys. 51, 4909 (1969).
G. Anagnostopoulos and P. O. Sakellaridis,J. Inorg. Nucl. Chem. 32, 1740 (1970).
G. Kasabov, L. Genov, and I. Dukov,Godishn. Vyssh. Khim.-Tekhnol. Inst., Sofiya 24, 265 (1978);Chem. Abs. 96, 111080c (1982).
R. V. Southwood-Jones, W. L. Earl, K. E. Newman, and A. E. Merbach,J. Chem. Phys. 73, 5909 (1980).
D. P. Fay, D. Litchinsky, and N. Purdie,J. Phys. Chem. 73, 544 (1969).
B.K. Annis, R.L. Hahn, and A.H. Narten,J. Chem. Phys. 82, 2086 (1985).
A. Gierer and K. Wirtz,Z. Naturorsch. Teil A 8, 532 (1953).
J. Reuben,Biochemistry 10, 2834 (1971).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Chen, Z., Detellier, C. Interactions of La(III) with anions in aqueous solutions. A139La NMR study. J Solution Chem 21, 941–952 (1992). https://doi.org/10.1007/BF00650870
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00650870