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The dissociation constants of the simplest dibasic organic acid, oxalic acid were determined conductometrically and pH metrically in ethanol + water mixtures (0–87 wt% of ethanol). These data were coupled with solubility values of oxalic acid and potassium hydrogen oxalate to calculate the Gibbs energies of transfer of oxalic acid, bioxalate(HOX − ), oxalate(OX 2− ) and potassium(K + ) ions from water to aquo + ethanolic mixtures. The values of Δ G  0  t (H 2 OX), Δ G  0  t (HOX − ), Δ G  0  t (OX 2− ), Δ G  0  t (K + ) represent the quantitative measure of solute or ion solvent interactions. p K  1  and p K  2  values and solubility values of oxalic acid (in general) increase continuously with increase in organic co-solvent though KHOX shows the reverse behaviour. Δ G  0  t (H 2 OX) and Δ G  0  t (H + ) are negative  i.e . favourable for the dissociation process whereas Δ G  0  t (HOX − ), Δ G  0  t (OX 2− ), and Δ G  0  t (K + ) (at above 16 wt% of alcohol) are positive and hence unfavourable. Though the increase in basicity is helpful for the dissociation process, the dielectric constant and H-bonding capability enhance the association process as the organic co-solvent increases.

zeitschrift für physikalische chemie

Studies on the Solubility and Dissociation Constants of Oxalic Acid in Aquo + Ethanolic Mixtures and Determination of Single-Ion Gibbs Energy of Transfer from Aqueous to Aquo + Ethanolic Mixtures