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An NMR study of thallium nitrate ion association in liquid ammonia

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Abstract

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.

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Hinton, J.F., Metz, K.R. An NMR study of thallium nitrate ion association in liquid ammonia. J Solution Chem 9, 197–207 (1980). https://doi.org/10.1007/BF00648326

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Key words

  • 205Tl NMR chemical shifts
  • liquid ammonia
  • ion-pair association
  • thermodynamic parameters
  • association constant
  • solvated ion pair
  • thallium nitrate
  • thallium perchlorate
  • temperature dependence