Studies of the dissociation of 2,4,6-trinitrophenol in aqueous mixtures of methanol and ethanol at 25 °C
Thermodynamic dissociation constants (sK)m of 2,4,6-trinitrophenol have been determined at 25 °C in aqueous mixtures containing 30, 50, 70, and 90% by weight of methanol and 30, 50, 70, 90, and 95% by weight of ethanol by spectrophotometric method. Solvent effect on the dissociation of the acid: δ(ΔG0) = 2.303RT[p(sK)N − p(wK)N] shows an unusual behaviour, the value decreases and passes through a minimum and ultimately becomes positive as the proportion of organic component in the solvent is progressively increased. The results have been compared with those of other uncharged acids like acetic acid, benzoic acid available from literature. The difference of behaviour (minimum characteristic in δ(ΔG0) curve) has been attributed to very strong dispersion interaction of trinitrophenolate anion with the organic component of the solvent. The overall behaviour of this acid indicates that solvent effect is an involved process being guided by electrostatic and dispersion interactions besides relative solvent basicities.