Thermodynamics of chlorobenzene, or bromobenzene, or 1-chloronaphthalene or 1,2,4-trichlorobenzene + alkane mixtures

Abstract

The systems C${}_6$H${}_5$Cl, or C${}_6$H${}_5$Br, or 1-chloronaphthalene, or 1,2,4-trichlorobenzene, or 1-methylnaphthalene, or 1,2,4-trimethylbenzene + alkane have been investigated by means of the their excess molar properties, including, when the needed data are available, those at constant volume, internal energies ($U_{V\text{m}}^{\text{E}}$) and heat capacities ($C_{V\text{m}}^{\text{E}}$), and using the DISQUAC, and Flory models, and the concentration-concentration structure factor formalism. The position of the mixtures within the $G_{\text{m}}^{\text{E}}$ (excess molar Gibbs energy) vs. $H_{\text{m}}^{\text{E}}$ (excess molar enthalpy) diagram has been also determined. Interactions between C${}_6$H${}_5$X molecules become stronger in the sequence X = H $\approx$ F $\approx$ Cl < Br. These interactions are weaker than those between 1-chloronaphtahlene or 1,2,4-trichlorobenzene molecules. It is shown that the considered systems have some common features: dispersive interactions are dominant, structural effects for solutions with shorter n-alkanes are large and $U_{V\text{m}}^{\text{E}}$ decreases when the number ($n$) of C atoms of the alkane increases. This variation is held when an n-alkane is replaced by a branched alkane with the same $n$ in systems with C${}_6$H${}_5$Cl or 1-chloronaphthalene. This suggests that larger alkanes are poorer breakers of the interactions between aromatic halogenated compounds. Viscosity and $C_{V\text{m}}^{\text{E}}$ data support this conclusion. The parabolic dependence of $C_{V\text{m}}^{\text{E}}$ with $n$ indicates that the short orientational order of long n-alkanes is destroyed. Aromaticity and proximity effects are discussed.

References in corpus (3)

• Orientational effects in alkanone, alkanal or dialkyl carbonate + alkane mixtures and in alkanone + alkanone or + dialkyl carbonate systems
• Thermodynamics of mixtures containing aromatic nitriles
• Thermodynamics of mixtures containing a fluorinated benzene and a hydrocarbon

Cited by in corpus (3)

• Density and speed of sound of (iodobenzene + n-alkane) liquid mixtures at $T$ = (288.15 to 308.15) K. Application of the Prigogine-Flory-Patterson model
• Viscosities of iodobenzene + n-alkane mixtures at (288.15-308.15) K. Measurements and results from models
• n-alkanoate + n-alkane mixtures: folding of hydrocarbon chains of n-alkanoates