Liquid-liquid equilibrium (LLE) data of the solubility curves and tie-line end compositions are presented for mixtures of [water (1) + acetic acid, or pyruvic acid, or valeric acid (2) + chloroform (3)] at T = 293.15 K and atmospheric pressure. Among the studied ternary systems, the largest separation factors give valeric acid. A solvation energy relation (SERLAS) has been used to estimate the liquid-liquid equilibria of associated systems containing a protic solvent. The tie-lines were also predicted through the UNIFAC-original model. The reliability of both models has been analyzed against the LLE data with respect to the distribution ratio and separation factor. SERLAS matches LLE data relatively accurately, yielding a mean error of 18.5% for all the systems considered. (c) 2006 Elsevier B.V. All rights reserved.