Comparison of the free energy of transfer of electrolytes, measured with cells without transference, with the sum of the free energies of the corresponding cations and anions with the Owen-cell on standard conditions

Abstract

The comparison of S2ΔS1G°tr(E1) with the sum of the values for the corresponding cation and anion S2ΔS1G°tr(Ct+)~S2ΔS1G°tr(X-) (measured) with Owen cells, gained by double extrapolation and by the assumption that the liquid junction potential at 1→0 may be neglected) gives values which differ by not more than ±5%. Most of the investigated acids allow the conclusion that the pH values, measured in cells with transference, and having the same electrodes, give good information on the acidity of the organic solvent and its water mixtures, referred to the standard state in water. That means that the pH, changed to the same H+ concentration in the solvent compared with that in water, is essentially an effect of the free energy of transfer of the hydrogen ion and not of very high liquid junction potentials.