Calorimetric study of nitrile-carbonyl group interactions. Comparison with DISQUAC predictions

Abstract

Marras G., Artal M., Otin S. and Marongiu B., 1994. Calorimetric study of nitrile-carbonyl group interactions. Comparison with DISQUAC predictions. Fluid Phase Equilibria, 98: 149-162. Excess enthalpies, HE, at 298.15 K and atmospheric pressure are reported for binary liquid mixtures of alkanenitriles + n-alkanones. These experimental results, along with literature data on liquid-vapor equilibria (excess Gibbs energies), GE, excess enthalpies, HE, and activity coefficients at infinite dilution, γi∞, are interpreted in terms of the DISQUAC group contribution model. The systems are characterized by three types of contact surfaces: nitrile (CN), carbonyl (CO) and alkane. The interchange energies of the alkane/CN and alkane/CO contacts were determined independently from the study of n-alkane + nitrile and n-alkane + ketone systems. The interaction parameters of the CN/CO contacts are reported in this work. The quasi-chemical parameters for alkanenitrile + ketone are zero except for ethanenitrile-containing mixtures. The dispersive parameters depend on the environment of the CN and CO groups. In general, the model provides a fairly consistent description of the excess functions GE and HE as functions of composition of the n -alkanenitrile + n-alkanone mixtures investigated.