Collect. Czech. Chem. Commun. 1984, 49, 2446-2457

Excess volumes and excess enthalpies of the mixtures tetrachloromethane + cycloalkane and trichloromethane + cycloalkane: Calculation in terms of equations of state of the van der Waals type

Ivan Cibulka and Robert Holub

Department of Physical Chemistry, Prague Institute of Chemical Technology, 166 28 Prague 6


The excess volumes and excess enthalpies for equimolar compositions and a temperature of 298.15 K for the binary liquid mixture of tetrachloromethane and trichloromethane with cyclopentane, cyclohexane and cyclooctane were calculated in terms of equations of state of the van der Waals type, the Redlich-Kwong equation of state and an equation following from the Flory theory. The pure-component parameters were evaluated in three different ways. The equations of state with pure-component parameters determined from gas-liquid critical constants yielded poor agreement with experiment. The best agreement with experiment was yielded by the Snider-Herrington equation with the pure-component parameters evaluated from molar volumes and thermal pressure coefficients and by the Flory equation. The Frisch equation extended to mixtures by using the van der Waals one-fluid approximation gave a good agreement with experiment in case of mixtures of molecules of approximately the same size. The excess entropies and the values of temperature derivatives of excess functions were as well calculated and compared with available experimental data.