An NMR study of thallium nitrate ion association in liquid ammonia
Tóm tắt
205Tl and1H magnetic resonance frequencies have been determined for liquid ammonia solutions of TlClO4 and TlNO3 as a function of electrolyte concentration (5×10−4 to 9.8 M) and temperature. The dependence of the resonance frequency on concentration suggests the presence of free, fully solvated thallium ions, ion pairs, and higher-order ion aggregates. Analysis of lowconcentration205Tl data between 0 and 30°C allowed the determination of TlNO3 ion-pair association constants and thermodynamic parameters (ΔHA=+6.5 kcal-mole−1, ΔSA=+36 e.u.). A preciptous decrease in205Tl resonance frequency was observed for NH3 to TlNO3 mole ratios below 3:1, suggesting the formula (NH3)3Tl+ NO
3
−
for the fully solvated, contact ion pair.
Tài liệu tham khảo
J. F. Hinton and R. W. Briggs,J. Magn. Reson. 19, 393 (1975).
J. F. Hinton and R. W. Briggs,J. Magn. Reson. 22, 447 (1976).
J. F. Hinton and R. W. Briggs,J. Magn. Reson. 25, 555 (1977).
J. F. Hinton and R. W. Briggs,J. Solution Chem. 6, 65 (1977).
J. F. Hinton and R. W. Briggs,J. Solution Chem. 7, 1 (1978).
J. F. Hinton and R. W. Briggs,J. Magn. Reson. 25, 379 (1977).
S. Hafner and H. H. Nachtrieb,J. Chem. Phys. 40, 2891 (1964).
J. Corset, P. V. Huong, and J. Lascombe,Spectrochim. Acta. Part A 24, 1385 (1968).
D. J. Gardiner, R. E. Hester, and W. E. L. Grossman,J. Chem. Phys. 59, 1975 (1973).
D. J. Gardiner, A. H. Haji, and B. P. Straughan,J. Chem. Soc. Faraday Trans. 1 72 93 (1976).
P. Gans and J. B. Gill,J. Chem. Soc. Chem. Commun., 914 (1973).
A. L. Allred and R. N. Wendricks,J. Chem. Soc. A, 778 (1966).
J. H. Roberts, A. T. Lemley, and J. J. Lagowski,Spectrosc. Lett. 5, 271 (1972).
G. Ritzhaupt and J. P. Devlin,J. Phys. Chem. 81, 67 (1977).
R. W. Briggs, K. R. Metz, and J. F. Hinton,J. Solution Chem. 8, 479 (1979).
C. A. Kraus and W. C. Brey,J. Am. Chem. Soc. 35, 1315 (1913).
G. H. Nancollas,Q. Rev. Chem. Soc. 14, 402 (1960).
A. T. Lemley and J. J. Lagowski,J. Phys. Chem. 78, 708 (1974).