Effect of temperature and composition on the surface tension and surface properties of binary mixtures containing DMSO and short chain alcohols
Introduction
Among the various experimental methods, surface tension is one of the most powerful techniques that provide information about surfaces and intermolecular interaction. The study of the surface properties in liquid mixtures is of great interest from both scientific and industrial points of view [1], [2], [3].
Dimethyl sulfoxide (DMSO) is a non-aqueous dipolar aprotic solvent used in pharmaceuticals, surface cleaners, extraction, electrochemistry and as a solvent for polymers. As pure solvent, DMSO has a large dipole moment and high dielectric constant (the relative dielectric constant ε = 46.50 and dipole moment μ = 4.06 D at 298.15 K) [4], [5], [6].
Also, alcohols are considered to be a water-like solvent in terms of hydrogen-bonding ability and are an important solvent due to their use in the chemical, pharmaceutical, fuel cell, cosmetic industries and others [7], [8], [9], [10].
This study is a continuation of our systematic experimental research on surface properties of binary liquid mixtures that contain polar or polar aprotic solvents [1], [2], [3], [11], [12]. The experimental values of surface tension of the binary systems consisting of DMSO with methanol, ethanol and isopropanol were determined over the whole range of composition at (298.15, 308.15, 318.15 and 328.15) K.
After surveying the literature, a number of research studies have been located on the surface tensions of DMSO with alkanols binary mixtures at various temperatures. However, no surface tension values were previously reported for DMSO with isopropanol at different temperatures and DMSO with methanol and ethanol at (308.15, 318.15 and 328.15) K [1], [2], [13], [14], [15].
After experimental measurements, the data obtained were analysed using various methods. In the first section, the concentration dependence of the surface tension of binary DMSO-alcohol mixtures at various temperatures are correlated using Fu et al. (FLW) [16], the Myers-Scott (MS) [17] and Redlich-Kister (RK) [18] and Li et al. (LWW) equations, and then in a new approach, the effect of alcohol structure on the interaction energy values (between alcohols and DMSO) is discussed in the binary systems [19], [20].
In the second section of this work, by employing the measured surface tensions at various temperatures, the thermodynamic properties of the surface (Hs and Ss) have been obtained. Finally, a Langmuir type isotherm model (or the extended Langmuir (EL)) is employed to determine the surface concentrations from the knowledge of the bulk mole fractions. The results provide information on the molecular interactions between the unlike molecules that exist at the surface and the bulk at various temperatures [20], [21].
Section snippets
Materials
All compounds were purchased from Merck and used without any further purification. Purity of each compound was ascertained by gas chromatography (GC type Agilent 7820A Agilent Technologies). The water mass fraction of the all components was determined by Karl Fisher (K.F.) titration, and it was found to be less than 0.0008 for DMSO and less than 0.004 for alcohols. Chemicals were kept in dark bottles. The detailed information of the materials used in the experiment is listed in Table 1.
The
Correlation of surface tension and concentration in binary mixtures
The concentration dependence of the surface tension of mixtures can be represented in terms of the surface tension deviation, Δσ, defined as:where σ is the surface tension of the mixture, and is the surface tension of the pure component I at the same temperature and pressure of the mixture, xi is the mole fraction of the component I and n is the number of components.
A few empirical and thermodynamic-based equations are available to correlate the surface tension; some of them
Conclusion
In this paper, surface tension values for binary mixtures of alcohol (methanol, ethanol and isopropanol) with DMSO, are reported over ranges of composition at various temperatures. In all systems, the surface tension of mixtures decreases with increasing temperature. The results of the present study show that by adding alcohol to DMSO the surface tension decreases non-linearly and most surface tension changes occur at a low concentration of alcohol. The surface tension deviation, Δσ, is
Acknowledgments
The authors are grateful to Dr. S. Maryam Sajjadi who kindly read the manuscript and made many helpful suggestions. Also, we gratefully acknowledge the financial support received for this research work from the Research Council of Semnan University.
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2020, Journal of Chemical ThermodynamicsCitation Excerpt :The non-ideal behavior of the mixed system also understands by the other parameters such as surface mole fraction of components. Extended Langmuir model (EL) is a new applied model to explain the relationship between the surface tension and the bulk composition of binary liquid mixtures [28–30,40–42]. In this equations, x1 and x2 refers to the number of mole fraction of components 1 and 2 in binary mixtures, and v1 and v2 are molar volume of the components 1 and 2.