Disquac Characterization of the Carbonyl-Chlorine Interactions in Binary Mixtures of Linear Ketone with Chloroalkane

Abstract

Both the published and our new data on vapour-liquid equilibrium, excess Gibbs energy GE and excess enthalpy HE for the linear ketone-chloroalkane binary mixtures are interpreted in terms of the DISQUAC group contribution model. The components are characterized by three types of contact surfaces: chlorine (Cl), carbonyl (C=O) and alkyl (CH3, CH2, CH, C). The Cl/alkyl and C=O/alkyl contact parameters are known from the literature. The parameters for C=O/Cl are re-evaluated here using extensive data on linear ketone-chloroalkane mixtures. It was found that the best description of ketone mixtures with 1-chloroalkane, trichloromethane, 1,1,1-trichloroethane, tetrachloromethane and 1,1,2,2-tetrachloroethane is obtained using a dispersive contribution of the C=O/Cl contact only. On the other hand the quasichemical term cannot be neglected for the ketone-α,ω-dichloroalkane systems. The newly evaluated interaction parameters for DISQUAC model enable good prediction of phase equilibrium and thermodynamic properties GE and HE as well as the temperature dependence of GE.