Physicochemical study of intermolecular interactions in 1,4-dioxane + aromatic hydrocarbons binary mixtures at different temperatures by using ultrasonic and viscometric methods

doi:10.1016/j.jct.2017.01.016

The Journal of Chemical Thermodynamics

Volume 108, May 2017, Pages 145-161

https://doi.org/10.1016/j.jct.2017.01.016 Get rights and content

Highlights

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Reports ultrasonic speed and viscosity of 1,4-dioxane + aromatic hydrocarbon mixtures.
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The study provides estimation of excess properties of these mixtures.
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Provides information on nature and relative strength of interactions in these media.
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Correlates acoustic and transport properties with interactions in these mixtures.
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Viscosity data is correlated with various empirical and semi-empirical models.

Abstract

The speeds of sound, u and viscosities, η of the binary mixtures of 1,4-dioxane with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene over the entire composition, including those of pure liquids, were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and at atmospheric pressure. From the experimental data, the excess isentropic compressibility, $κ_{s}^{E}$ , excess speed of sound, $u^{E}$ , excess molar isentropic compressibility, $K_{s,m}^{E}$ and deviations in viscosity, Δη have been calculated. The partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}$ and ${\overline{K}}_{s,m, 2}$ , and excess partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{E}$ and ${\overline{K}}_{s,m, 2}^{E}$ over the whole composition range, partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{\circ}$ and ${\overline{K}}_{s,m, 2}^{\circ}$ , and excess partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{\circ E}$ and ${\overline{K}}_{s,m, 2}^{\circ E}$ of the components at infinite dilution have also been calculated. The results indicated the presence of weak interactions between 1,4-dioxane and aromatic hydrocarbon molecules, which follows the order: benzene > toluene > o-xylene > m-xylene > p-xylene > mesitylene. It is observed that the interactions depend on the number and position of the methyl groups in these aromatic hydrocarbons. Further, the viscosities of these binary mixtures were correlated theoretically by using various empirical and semi-empirical models and the results were compared with the experimental findings.

Graphical abstract

Excess isentropic compressibilities, $κ_{s}^{E}$ as function of volume fraction, ϕ₁ of 1,4-dioxane + aromatic hydrocarbon binary mixtures.

Introduction

The knowledge of physicochemical properties of non-aqueous binary liquid mixtures has relevance in theoretical and applied areas of research and such results are frequently used in designing process (flow, mass transfer or heat transfer calculations) in many chemical and industrial processes [1], [2]. The speeds of sound, viscosity of binary liquid mixtures and parameters derived from these properties can be used as important tools for investigating intermolecular interactions between component molecules in liquid mixtures [3], [4], [5], [6], [7], [8], [9]. The speed of sound can be considered as a thermodynamic property, provided that a negligible amount of ultrasonic absorption of the acoustic waves of low frequency and of low amplitude is observed; in that case, the ultrasonic absorption of the acoustic waves is negligible [10]. In continuation to our ongoing research on experimental and theoretical studies of physicochemical properties of non-aqueous binary liquid mixtures [11], [12], [13], here we report the results of ultrasonic and viscometric studies on the binary mixtures of 1,4-dioxane with six aromatic hydrocarbons (benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene) over the entire composition range at six different temperatures.

1,4-Dioxane is an excellent aprotic solvent, having zero dipole moment [14], and is commercially used in polymerization and other chemical reactions, in the cleaning of polymer surfaces and electronic materials. On the other hand, the aromatic hydrocarbons possess large quadrupole moments [15], causing an orientational order between molecules of these liquids. The orientational order is due to the partial alignment of neighbouring segments or possibly of whole molecules [15]. Also, the binary mixtures containing aromatic hydrocarbons are interesting because they find applications in the studies of polymer phase diagrams and preferential interaction of polymers in mixed solvents [16], [17]. 1,4-dioxane is cyclic ether, having electron-donor ability [18] towards the aromatic rings which act like electron-acceptors [19]. Therefore, the 1,4-dioxane + aromatic hydrocarbon mixtures will be interesting as these may involve charge-transfer interactions which may be influenced by the presence of alkyl groups on the ring. A survey of literature indicates that there have been some studies [3], [4], [5], [6], [7], [8], [9], [20], [21], [22] on 1,4-dioxane + benzene/toluene/o-xylene mixtures from the point of view of their ultrasonic and viscometric behaviour.

In the present paper, we report speed of sounds, u and viscosities, η of 1,4-dioxane + benzene, +toluene + o-xylene, +m-xylene, +p-xylene, and +mesitylene binary mixtures, including those of pure liquids, at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure, covering the entire composition range, expressed by the mole fraction, x₁ of 1,4-dioxane. The density, ρ data used in the present work have been taken from our earlier study [13]. From the experimental data, the excess isentropic compressibility, $κ_{s}^{E}$ , excess speed of sound, $u^{E}$ , excess molar isentropic compressibility, $K_{s,m}^{E}$ and deviations in viscosity, Δη have been calculated. The partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}$ and ${\overline{K}}_{s,m, 2}$ , and excess partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{E}$ and ${\overline{K}}_{s,m, 2}^{E}$ over the whole composition range, partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{\circ}$ and ${\overline{K}}_{s,m, 2}^{\circ}$ , and excess partial molar isentropic compressibilities, ${\overline{K}}_{s,m, 1}^{\circ E}$ and ${\overline{K}}_{s,m, 2}^{\circ E}$ of the components at infinite dilution have also been calculated. The variation of these parameters with composition and temperature of the mixtures have been discussed in terms of intermolecular interaction in these mixtures.

Section snippets

Experimental

The 1,4-dioxane and the aromatic hydrocarbons (benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene, mass fraction purities >0.99) were products from Spectrochem Pvt. Ltd., India and were purified by using the standard methods described in the literature [14], [23]. The mass fraction purities of the purified chemicals were determined by gas chromatography. The final purities and other specifications of the chemicals used are given in Table 1. Before use, the pure chemicals were stored

Results and discussion

The experimental values of speed of sounds, u and viscosities, η of binary mixtures of 1,4-dioxane with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene, over the whole composition range expressed in mole fraction, x₁ of 1,4-dioxane at the investigated temperatures are listed in Table 3, Table 4, respectively.

The u and η data of pure liquids have been compared with those reported earlier (Table 2). The comparison has been given graphically as Figs. S1 and S2 in the Supplementary

Conclusion

The speed of sounds and viscosities of binary mixtures of 1,4-dioxane + benzene, + toluene, + o-xylene, + m-xylene, + p-xylene, and + mesitylene, including those of pure liquids have been measured at different temperatures. The values of $κ_{s}^{E}$ , $u^{E}$ , $K_{s,m}^{E}$ , Δη, ${\overline{K}}_{s,m, 1}$ , ${\overline{K}}_{s,m, 2}$ , ${\overline{K}}_{s,m, 1}^{E}$ , ${\overline{K}}_{s,m, 2}^{E}$ , ${\overline{K}}_{s,m, 1}^{\circ},$ ${\overline{K}}_{s,m, 2}^{\circ},$ ${\overline{K}}_{s,m, 1}^{\circ E}$ and ${\overline{K}}_{s,m, 2}^{\circ E}$ have been calculated. The variation of these parameters with composition indicated the presence of weak interactions of electron donor-acceptor type between

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