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For the liquid system water + acetic acid, we give the results of new calorimetric measurements regarding the molar excess enthalpy H̅ E  for 25 °C, 30 °C, 35 °C, 40 °C, 55 °C, and 70 °C, covering nearly the entire range of com­ positions. The experimental data show that H̅ E  is positive for all compositions and temperatures except in the region of low acid concentrations at temperatures below 55 °C where the process of mixing the pure liquid components is exothermic (H̅ E &lt;0). Using values of the molar excess Gibbs function G̅ E  (always positive) derived from earlier data on vapour-liquid equilibria, we compute the molar ex­cess entropy S̅ E  which is always negative. The “symmetryrule” concerning the composition dependence of G̅ E  (as compared to that of H̅ E  and S̅ E ) has again been confirmed. The composition dependence of S̅ E  is similar to that of the molar excess volume.

Thermodynamic Excess Functions for the Liquid System W ater + Acetic Acid from Calorimetric Data