Examination of the excess thermodynamic properties of n-alkane binary mixtures: a molecular approach.

A modification of the statistical associating fluid theory, the so-called Soft-SAFT equation of state, is proposed to predict the excess thermodynamic properties of binary mixtures of n-alkanes. n-Alkane molecules are modeled as fully flexible Lennard-Jones chains. This molecular model accounts for the most important microscopic features of real chainlike molecules: attractive and repulsive interactions between different chemical groups and the connectivity of the segments that form the molecules. In this work we consider an additional microscopic effect that can profoundly affect certain thermodynamic properties, namely, the conformational changes when two different n-alkane molecules are mixed. We propose, following the work of Vega and co-workers [J. Chem. Phys. 1999, 111, 3192], a simple model to account for the conformational changes in molecules. The resulting free energy is combined with the SAFT free energy to describe the excess thermodynamic properties of binary mixtures of n-alkanes. Predictions from the theory are compared with experimental data taken from the literature. The agreement between the experiments and the theoretical predictions is excellent in all cases. This work shows that although minor microscopic effects, such as the conformational changes in the molecules that form the mixtures, have only a very small effect on the usual thermodynamic properties, such as pressure, chemical potential, phase equilibria, and excess volumes, they can contribute significantly to other thermodynamic properties. In fact, one of the main conclusions of this work is that it is essential that conformational effects be taken into account in molecular-based theories if an accurate description of certain excess properties (excess enthalpy for instance) is desired.