Abstract
The dielectric constant and conductivity of dilute solutions of tetraisoamylammonium nitrate in chlorobenzene are measured between −34.6° and 99.0°C to give association constants for the formation of ion pairs (K A) and triple ions, and electric dipole moments. The quantityK A as a function of temperature is reproduced by the Denison-Ramsey-Fuoss treatment for unolarized ion pairs [Eq. (2)] with a distance of closest approach of 4.90 Å. The dielectric data are reproduced by Onsager's equation with an inherent (gas-phase) dipole moment of the ion pairs of 14.2±0.3 D. Other methods of calculation lead to consistent dipole moments, confirming that the mutual polarization of the ions is important. The energetics of ionic association is considered on the basis that the ion pair may be treated as a polarizable dipole in a spherical cavity.
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Grunwald, E., Effio, A. Electric dipole moments in polar solvents. II. Tetraisoamylammonium nitrate ion pairs in chlorobenzene. Effect of mutual polarization of the ions. J Solution Chem 2, 393–404 (1973). https://doi.org/10.1007/BF00713252
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DOI: https://doi.org/10.1007/BF00713252