Nuclear magnetic resonance studies of thallium(I)-205 in aqueous solution
The relaxation (longitudinal and transverse) of thallium(I) ions in aqueous solution is observed to be independent of the resonance frequency, isotopic substitution in the solvent (D/sub 2/O for H/sub 2/O), the resonant spin (/sup 203/Tl for /sup 205/Tl), the salt concentration, and th e nature of the anions. It is, however, very sensitive to dissolved oxygen, and a linear dependence of the relaxation rate on the gas pressure up to 5 atm has been observed. It is concluded that, in oxygen-free solutions, Tl(I) is dominantly relaxed by the transient spin-rotation interaction and, in oxygenated solutions, by the electron- nuclear dipole -- dipole interaction with considerable penetration of the hydration sphere by oxygen. No complex between the thallous ion and oxygen molecules appears to form as there is no appreciable increase in oxygen solubility in aqueous thallous solutions nor is there any appreciable shift in the Tl(I) resonance when the solutions are oxygerated. Solvent isotope shifts of thallium ions in light and heavy water have been determined. They are, contrary to other systems studied, rather dependent on the salt concentration and the nature of the anions. These observations are interpreted as a differential competition of various anions and solvent molecules in their interactions with the thallium ion. (auth)
- Research Organization:
- Univ. of Waterloo, Ont.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-29-018115
- OSTI ID:
- 4346780
- Journal Information:
- J. Amer. Chem. Soc., v. 96, no. 2, pp. 404-410, Journal Name: J. Amer. Chem. Soc., v. 96, no. 2, pp. 404-410; ISSN JACSA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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