Protocatechuic acid, a major metabolite of antioxidant polyphenols found in green tea, has been shown to prevent carcinogenesis or antitumor growth in vitro and in vivo studies. The dilution enthalpies Delta H-dil(m), dissociation enthalpies Delta H-dis(m) and thermodynamic dissociation constants K-a for protocatechuic acid in aqueous NaCl or KCl solutions were simultaneously determined by mixing-flow microcalorimetry at T = 298.15 K. In order to verify the reliability of the fitted dissociation parameters, the values of dissociation enthalpies and thermodynamic dissociation constants were also determined by isothermal titration calorimetry and electrical conductivity methods. The K-a values obtained through the proposed method agree well with those reported in literatures and obtained by other techniques. Enthalpic interaction coefficients (h(2), h(3) and h(4)) were computed according to the McMillan-Mayer model. The trends of h(2) and Delta H-dis(m) for protocatechuic acid with increasing salt molality in both the salt solutions were obtained. The different influence of KCl and NaCl on the values of h(2) and Delta H-dis(m) were discussed in terms of (solute + solute) and (solute + solvent) interactions. The results showed that it is possible to perform in a single calorimetric experiment the simultaneous determination of dilution enthalpies, dissociation enthalpies and constants in a given solvent. (C) 2015 Elsevier Ltd. All rights reserved.