Volumetric properties of binary liquid mixtures: Application of the Prigogine–Flory–Patterson theory to excess molar volumes of dichloromethane with benzene or toluene

The values of the density were measured for binary liquid mixtures of benzene and toluene with dichloromethane over entire range of concentration using a vibrating-tube densimeter at T = (288.15, 293.15, 298.15, and 303.15) K and atmospheric pressure. The excess molar volumes, calculated from the density results, are positive for the systems of dichloromethane with benzene over the whole concentration range and present an approximate sigmoid curve for the dichloromethane with toluene. The VmE values have been fitted to the Redlich–Kister polynomial equation, and other volumetric properties such as the partial molar volumes, Vi¯, the apparent molar volume, Vϕi  , and the partial molar excess volumes at infinite dilution, (ViE¯)∞, were calculated over the whole composition range. The Prigogine–Flory–Patterson (PFP) theory and its applicability in predicting VmE at T = 298.15 K are tested. Good agreement was found for the mixtures dichloromethane with benzene. For the mixtures dichloromethane with toluene, which shows an approximate S-shaped VmE behaviour, the correlation fails.