Linear relationships between (s)(s)pK(a) values in acetonitrile-water mixtures and (w)(w)pK(a), values in pure water have been established for five families of compounds: aliphatic carboxylic acids, aromatic carboxylic acids, phenols, amines, and pyridines. The parameters (slope and intercept) of the linear correlations have been related with acetonitrile-water composition, The proposed equations allow accurate estimation of the pK(a) values of any member of the studied families at any acetonitrile-water composition up to 60% of acetonitrile in volume (100% for pyridines). Conversely, the same equations can be used to estimate aqueous pK(a) values from chromatographic pK(a) values obtained from any acetonitrile-water mobile phase between the composition range studied. Estimation of pK(a) values have been tested with chromatographic literature data. (C) 2002 Elsevier Science B.V. All rights reserved.