The identification of racemic species of enantiomeric 3-chloromandelic acid (3-CIMA) as well as ternary solubility measurement in a mixture of water and isopropanol (IPA) was studied in this paper. Thermal analyses were carried out for mixtures of the two enantiomers with different compositions. The binary fusion diagram suggested the presence of a racemic compound for racemate 3-CIMA. It was verified with the ternary solubility phase diagram by dissolving various mixtures into the H2O/IPA solution. Ternary phase diagram revealed a strong temperature dependency of solubility for the 3-CIMA system. In order to shorten the experimental time in the solubility measurement. a semi-empirical thermodynamic model (UNIQUAC) was used to predict the solubility of various compositions of enantiomers at different temperatures. Results indicate that UNIQUAC model can provide good predictions in the solubility-of racemate, eutectic and (R)-3-CIMA in both pure water and H2O/IPA (9/1 weight ratio) system. In addition, structures of racemate and pure (R)-3-CIMA were also studied using a powder X-ray diffractometer. Thermodynamic prediction, thermal analysis. and structural study are in excellent agreement for identifying the enantiomeric 3-CIMA system as a racemic compound forming system. (C) 2008 Published by Elsevier Ltd.