Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Electrostatic Gibbs Free Energy and Solvation Number of Tetraalkylammonium Ions in Pyridine at 25${^{\circ}C}$ Obtained Using Conductance of Corresponding Ion

  • Published : 1998.12.20
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Abstract

The equivalent conductances for tetraethylammonium perchlorate (TEAP), tetrabutylammonium perchlorate (TBAP), tetrahexylammonium perchlorate (THAP), and tetradodecylammonium perchlorate (TDDAP) were measured in pyridine (Py) at 25 ℃. The measured data have been analyzed by Onsager conductance theory. From Kohirausch's law of independent migration of ion, the limiting ionic conductances of tetraalkylammonium ions were determined using the limiting ionic conductance of perchlorate cited from reference. Using those and viscosity of pyridine, the Stokes and hydrodynamic radii of tetraethylammonium, tetrabutylammonium, tetrahexylammonium, and tetradodechylammonium ions were calculated. And, the salvation numbers of corresponding ions were also calculated using the hydrodynamic and crystallographic radii and the volume of one pyridine molecule. From those results, the model of salvation for those ions was extracted by comparison with the model for ion salvation. And the electrostatic Gibbs free energy (ΔGel) fitted for our salvation model was calculated. Those of corresponding ions in pyridine at 25 ℃ also increased with increasing radii of tetraalkylammonium ions. This trend of ΔGel was explained by the different ion-solvent interaction between tetraalkylammonium ion and pyridine.

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References

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