Surface and bulk behavior of (dialkylsulfoxides + carbon tetrachloride) mixtures

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Abstract

Surface tensions, surface tension deviations, densities, and excess molar volumes of binary mixtures of carbon tetrachloride (CCl4) with dimethylsulfoxide (DMSO), diethylsulfoxide (DESO), dipropylsulfoxide (DPSO), and dibutylsulfoxide (DBSO) have been determined over the entire composition range at (298.15 and 313.15) K. The results were fitted by the Redlich–Kister polynomial equation and the corresponding binary coefficients have been derived.

The obtained excess quantities show that both charge-transfer complex formation between CCl4 and dialkylsulfoxides (DASO) molecules and on the other hand sulfoxides’ chain length are crucial factors conditioning the excess thermodynamic properties of (CCl4 + DASO) binary mixtures.

Introduction

It is well-known that surface and bulk properties are closely connected. In general, for the binary mixtures the component with lower surface tension is expected to be displaced to the surface while the other component tends to stay in the bulk [1], [2], [3], [4], [5], [6], [7], [8]. On the other hand, during the mixing processes intermolecular interactions between the molecules of components can affect the surface behavior. Moreover, the occurring of specific intermolecular interactions, such as hydrogen bond formation or charge-transfer complex formation could change a distribution of mixing components on the surface and in the bulk. As a result, for instance, more surface active component remains in the bulk leading to positive values of surface tension deviations.

In the present work, the surface tensions and volumetric properties of (dialkylsulfoxides, DASO + carbon tetrachloride) have been studied. There are several reasons to investigate this system. At the present time it is well recognized that not only dimethylsulfoxide (DMSO) but also its nearest homologues reveal interesting physicochemical features and have biomedical significance as well [9]. Furthermore, the changes in toxicity of the carbon tetrachloride induced by DMSO recently described by Kim et al. [10]. In addition, it should be noted that from the fundamental and structural points of view it is important to reveal how an assuming intermolecular interactions between sulfoxides’ and carbon tetrachloride’s molecules will change surface and bulk behavior in these binary mixtures.

In our relatively recent work on the basis of dielectric relaxation study a complex formation between DMSO (diethylsulfoxide, DESO) and carbon tetrachloride has been suggested [11].

In [12] to explain the mechanism of the laser flash photolysis of (DMSO + carbon tetrachloride) mixtures a ground state complex formation was suggested.

The possibility of complex formation between these molecules was considered in the early works [13], [14], [15] where negative excess molar volume [13], [14] and positive values of molar excess enthalpy [13], [15] were detected for (DMSO + carbon tetrachloride) over the entire composition range.

Recently, surface tensions of (DASO + water) binary mixtures have been determined [9]. The results obtained shown that the character of concentration dependence of surface tension is explained on the basis of changing intermolecular interactions involving both components.

In this work excess molar volumes, surface tension deviations of (DMSO + carbon tetrachloride), {diethylsulfoxide (DESO) + carbon tetrachloride}, {dipropylsulfoxide (DPSO) + carbon tetrachloride}, and {dibutylsulfoxide (DBSO) + carbon tetrachloride} binary mixtures at the temperatures of (298.15 to 313.15) K have been determined. The results of excess molar volumes obtained for (DMSO + carbon tetrachloride) were compared with those known from the literature [13].

Section snippets

Experimental

DMSO commercially available, SIGMA-ALDRICH. Other dialkylsulfoxides were synthesized and purified according to the literature [16].

All the samples were obtained by direct mixing the appropriate amounts of both components (all solutions were prepared by weigh). A possible error in the mole fractions is estimated to be less than 10−4.

The densities of the (DASO + CCl4), as well as pure compounds, were measured over the temperature range from (298.15 to 313.15) K (±0.01 K) using a vibrating tube

Results and discussion

The surface tensions (γ) and surface tension deviations (δγ) for all binary mixtures (CCl4 + DASO) are listed in table 2. Figure 1a and b shows the surface tensions of (CCl4 + DASO) at two different temperatures (298.15 and 313.15) K, respectively against mol fraction of CCl4. The behavior is standard, γ is observed to decrease with increasing temperature. In addition, for each temperature the surface tension decreases with the length of the alkyl chain.

The surface tension deviation (δγ) is defined

Acknowledgements

This work was partially supported by Armenian National Science and Educational Fund (ANSEF), project # 1534. The authors acknowledge the assistance of A. Ghukasyan and A. Avetisyan for obtaining some experimental data.

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