The ionization of trichloroacetic acid and evidence for an unusual type of ion pairing

Osmotic and activity coefficients are reported for aqueous solutions of the lithium and potassium salts of iodic acid and trichloroacetic acid. The degree of ionization of the parent acids at various concentrations was estimated from ion exchange measurements, and these values were compared with those obtained from Raman measurements. It was concluded that one obtains comparable values of α, the degree of dissociation, of iodic acid whether these are estimated from hydrogen ion concentrations or anion concentrations. Lack of agreement between like measurements of α for trichloroacetic acid leads to the postulation of an unusual ion pair in which the proton is strongly associated with the chlorine end of the anion. A similar type of ion pairing is suggested in solutions of the aromatic sulfonic acids.