Abstract
Electrolytic conductivities of KF and CsF in methanol solution have been determined at 25°C. The single ion molar conductivities of the fluoride ion, obtained from the two salts are in excellent agreement and indicate that the F− ion is highly solvated in methanol (MeOH). Combination of the present and literature data for related salts in both water and MeOH indicate that while the primary solvation of ions may be more extensive in H2O there is considerable enhancement of the secondary solvation sheath in MeOH. Recalculation of high precision literature conductivity data using a consistent mathematical approach indicates that ion pair formation constants for simple 1:1 electrolytes in MeOH are 1 or 2 orders of magnitude greater than in H2O. This is shown to be entirely due to the less favorable solvation of ions in MeOH, as the Gibbs energies of transfer of the neutral ion pairs MX from H2O to MeOH are also unfavorable. Calculations also show that ion association in MeOH is strongly influenced by coulombic interactions whereas in H2O short range interactions are generally more important.
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Hefter, G.T., Salomon, M. Conductivities of KF and CsF in methanol at 25°C. J Solution Chem 25, 541–553 (1996). https://doi.org/10.1007/BF00973084
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DOI: https://doi.org/10.1007/BF00973084