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The thermodynamic dissociation constants for the isoelectronic reaction LH +  ↔ L + H +  [Eq. (1)], (where L = 1,10-phenanthroline or 2,2´-bipyridine) have been determined pH-metrically in urea + water mixtures (0-8 M urea). The data have been utilized to calculate the Gibbs energies of transfer of H +  from water to urea + water mixtures. ΔG 0  t (H + ) values have been found to be increasingly negative. The results indicate the increase in basicity of the urea + water mixtures resulting from the breakdown of water structure by urea. The dissociation constants for the reaction UH +  ↔ U + H +  [Eq. (2)] have also been determined. The variation of the dissociation constant UH +  can be properly correlated with the variation of dielectric constants of the urea + water mixtures. A good correlation exists between the variation of basicity of the solvent mixtures and the dissociation constants of uronic acid.

Gibbs Energy of Transfer of H + Ion from Water to Urea-Water Mixtures