Thermodynamics of Mixtures Containing Organic Carbonates. Part XV. Application of the Kirkwood-Buff Theory to the Study of Interactions in Liquid Mixtures Containing Dialkyl Carbonates and Alkanes,Benzene, CCl4 or 1-Alkanols

Binary liquid mixtures containing a dialkyl carbonate (dimethyl or diethyl carbonate) and organic solvents such as alkanes, benzene, CCl₄, or 1-alkanols were studied within the framework of the Kirkwood-Buff formalism. The Kirkwood-Buff integrals, linear coefficients of preferential solvation and local mole fractions were calculated. Results were interpreted assuming that the mixtures with alkanes or 1-alkanols are not random mixtures, which can be ascribed to the existence of strong dipolar interactions between like molecules. Systems containing benzene or CCl₄ are both random and more ordered because of the charge transfer or dipole/induced dipole interactions between the polar group of the solute (O–CO–O) and the polarizable solvent molecules. The effect of increasing temperature was also examined.