Hard sphere study of condensation entropy

A simple procedure is devised to calculate the Ben-Naim standard condensation entropy by treating neat liquids as hard sphere fluids. The calculated values are close to the experimental ones for nonpolar liquids, but not for polar aprotic ones and for H-bonded liquids. For the latter the calculated entropy values become close to the experimental ones if the molecular van der Waals diameters are used instead of the effective ones. This implies that the magnitude of the orientational entropy loss due to H-bond formation is quantitatively similar to that of the configurational entropy gain for the decrease in excluded volume due to the bunching up effect caused by H-bonds.