Application of the Cell Method to the Statistical Thermodynamics of Solutions. II. Experimental

Abstract

In connection with the theory of solutions proposed by Prigogine and Mathot [J. Chem. Phys. 20, 49 (1952)], total vapor pressures and volume changes on mixing have been measured for the systems: CCl4–C(Me)4 IC6H12–C(Me)4 IIC6H6–C(Me)4 III.Volume changes only for the systems: CCl(Me)3–CCl4 IVCCl2(Me)2–CCl4 VCCl3(Me)–CCl4 VIC(Me)3OH–CCl4 VII. For the first three systems I, II, and III, one observes a positive excess free energy (positive deviations to the Raoult law) together with a negative excess volume (contraction on mixing), whereas for the last four IV, V, VI, and VII there is a gradual passage from negative (IV) to positive (VII) excess volume. These results are discussed in terms of the molecular interactions AA, BB, and AB. Reasonable agreement is observed between Prigogine and Mathot's theory and experiment.

Boiling Points and Surface Tensions of Mixtures of Benzyl Acetate with Dioxane, Aniline, and meta-Cresol.

“…The accuracy obtained for surface tension was within 0.2%. Density measurements of the pure components as well as the mixtures were made by using a pyknometer described by Mathot and Desmyter (7) and agreed with those quoted by Moore and Styan (9).…”

Excess thermodynamic functions

“…CC1 4 4-cyclopentane has values of the equimolar Gibbs function, enthalpy and volume of +34.1 Jmol" 1 , +77.1 Jmol" 1 and -0.0351 cm 3 mol" 1 , respectively 154 . The principal excess functions of CCl 4 + both TKEBS and OMCTS are all considerably more negative compared to the functions for the same two large molecules when mixed with benzene 121,156 . Mixtures of CC1 4 + neopentane are interesting in that g E ~ h E ~ 320Jmol -1 at 273K with an excess volume of -0.5cm 3 mol" 1 .…”

General and physical chemistry

“…Reasonable agreement with experiment has been obtained. 51 The effect of non-random mixing has been studied by Sarolea,52 but is considered not to affect the conclusions of the previous Nasielski 53 has calculated the partial molar quantities corresponding to this model. Pople 54 has employed a 6 : 12 interaction in the cell theory of regular solutions and has taken account of non-random mixing.…”