Thermodynamics of mixtures containing a fluorinated benzene and a hydrocarbon

TL;DR

This study investigates the thermodynamic behavior of fluorobenzene and hydrocarbon mixtures using models like DISQUAC and UNIFAC, revealing insights into azeotropy, excess enthalpies, and molecular interactions.

Contribution

It applies and compares DISQUAC and UNIFAC models to new fluorobenzene mixtures, providing interaction parameters and analyzing molecular coordination effects.

Findings

Both models predict double azeotropy in C6F6 + C6H6 system.

Excess molar enthalpies are positive and model-independent for fluorobenzene + n-alkanes.

DISQUAC outperforms UNIFAC in predicting heat capacities and enthalpies.

Abstract

Fluorobenzene, or 1,4-difluorobenzene or hexafluorobenzene + alkane mixtures and hexafluorobenzene + benzene, or + toluene, or + 1,4-dimethylbenzene systems have been studied using thermodynamic properties from the literature and through the application of the DISQUAC and UNIFAC (Dortmund) models and the concentration-concentration structure factor ($S_{\text{CC}}(0)$). Interaction parameters for the contacts F/alkane and F/aromatic have been determined for DISQUAC, and they have been taken from the literature for UNIFAC. Both models predict double azeotropy for the C$_6$F$_6$ + C$_6$H$_6$ system, although in different temperature ranges. Excess molar enthalpies ($H_{\text{m}}^{\text{E}}$) of the fluorobenzene, or 1,4-difluorobenzene + n-alkane systems are positive and are accurately described by the models using interaction parameters independent of the n-alkane, discarding Patterson's effect in such mixtures. DISQUAC calculations confirm that conclusion for C$_6$F$_6$ + n-alkane mixtures. DISQUAC provides better results than UNIFAC on excess molar isobaric heat capacities ($C_{p\text{m}}^{\text{E}}$) of solutions involving n-alkanes, or on $H_{\text{m}}^{\text{E}}$ of C$_6$F$_6$ + aromatic hydrocarbon systems. For mixtures with a given n-alkane, the relative variation of excess molar internal energies at constant volume ($U_{V\text{m}}^{\text{E}}$) and $H_{\text{m}}^{\text{E}}$ and with the fluorohydrocarbons is different, due to structural effects. C$_6$F$_6$ + aromatic hydrocarbon mixtures are characterized by interactions between unlike molecules, as seen from their negative $H_{\text{m}}^{\text{E}}$ values. The $S_{\text{CC}}(0)$ formalism reveals that homocoordination is more important in C$_6$F$_6$ + n-alkane mixtures than in the corresponding systems with C$_6$H$_5$F, and that heterocoordination is dominant in the solutions of C$_6$F$_6$ with an aromatic hydrocarbon.