Research Article  Open Access
Sk. Fakruddin, Ch. Srinivasu, B. R. Venkateswara Rao, K. Narendra, "Excess Transport Properties of Binary Mixtures of Quinoline with Xylenes at Different Temperatures", Advances in Physical Chemistry, vol. 2012, Article ID 324098, 9 pages, 2012. https://doi.org/10.1155/2012/324098
Excess Transport Properties of Binary Mixtures of Quinoline with Xylenes at Different Temperatures
Abstract
The ultrasonic velocity and density of binary liquid mixtures of quinoline with oxylene, mxylene, and pxylene have been measured over the entire range of composition at = 303.15, 308.15, 313.15, and 318.15 K. Using these data, various parameters like adiabatic compressibility (β), intermolecular free length (), and acoustic impedance () and some excess parameters like excess adiabatic compressibility (), excess intermolecular free length (), excess acoustic impedance (), and excess ultrasonic velocity () have been calculated for all the three mixtures. The calculated deviations and excess functions have been fitted to RedlichKister polynomial equation. The observed deviations have been explained on the basis of the intermolecular interactions present in these mixtures.
1. Introduction
In studying the molecular interactions and physicochemical behaviour of binary liquid mixtures [1, 2], the knowledge of thermodynamic and acoustical properties is of great importance. The results are frequently used in process design in many chemical and industrial processes. The studies of binary mixtures containing aromatic hydrocarbons are interesting because they find applications in preferential interactions of polymers in mixed solvents and the studies of polymer phase diagrams. Quinoline is widely used in the manufacturing of dyes, pesticides, and solvent for resins and terpenes. Xylenes are used in printing, rubber, and leather industries. Basically, a binary liquid mixture is formed by the replacement of like contacts in pure liquids by unlike contacts in the mixture. The quantitative and qualitative analyses of excess functions provide information about the nature of molecular interactions in the binary mixtures [3–5]. The literature survey reveals that there has been practically no study of the binary mixtures of these systems from the point of view of their ultrasonic behaviour.
In an attempt to explain the nature of interactions occurring between quinoline and xylenes, ultrasonic velocity and density of binary liquid mixtures of quinoline + oxylene/mxylene/pxylene have been determined over the entire range of composition at = 303.15, 308.15, 313.15, and 318.15 K. Using the experimental values of and , adiabatic compressibility (), intermolecular free length (), and acoustic impedance () and some excess parameters like excess adiabatic compressibility (), excess intermolecular free length (), excess acoustic impedance (), and excess ultrasonic velocity () have been calculated. The results were fitted to the RedlichKister polynomial equation. In the light of excess parameters, the intermolecular interactions have been estimated [8].
2. Experimental
2.1. Materials
The mass fraction of the liquids (obtained from Merck) is as follows: oxylene (0.980), mxylene (0.980), pxylene (0.990), and quinoline (0.987). All the liquids used were further purified by standard procedure [9]. The purity of the samples was checked by comparing the experimental values of ultrasonic velocity and density with those available in the literature [6, 7] and these values are compiled in Table 1.
2.2. Procedure
Job’s method of continuous variation was used to prepare the mixtures of required proportions. The prepared mixtures were preserved in wellstoppard conical flasks. After mixing the liquids thoroughly, the flasks were left undisturbed to allow them to attain thermal equilibrium.
The ultrasonic velocities were measured by using single crystal ultrasonic pulse echo interferometer (Mittal enterprises, India; Model: F80X). It consists of a highfrequency generator and a measuring cell. The measurements of ultrasonic velocities were made at a fixed frequency of 3 MHz. The capacity of the measuring cell is 12 mL. The calibration of the equipment was done by measuring the velocity in carbon tetrachloride and benzene. The results are in good agreement with those reported in the literature [10]. The ultrasonic velocity has an accuracy of ±0.5 ms^{−1}. The temperature was controlled by circulating water around the liquid cell from thermostatically controlled constant temperature water bath (accuracy ±0.01 K).
The densities of pure liquids and liquid mixtures were measured by using a specific gravity bottle with an accuracy of ±0.5%. An electronic balance (Shimadzu AUY220, Japan), with a precision of ±0.1 mg, was used for the mass measurements. Averages of 45 measurements were taken for each sample.
3. Theory
From the experimental data of ultrasonic velocity and density various thermodynamic parameters are evaluated using standard equations.
Adiabatic compressibility: where and are density and ultrasonic velocity, respectively.
Inter molecular free length: where is the temperature dependent constant [11].
Acoustic impedance: The strength of interaction between the component molecules of binary mixtures is well reflected in the deviation of the excess functions from ideality [12]. The excess properties such as , , , and have been calculated using where is , , , or and represents mole fraction of the component and subscript 1 and 2 for the components 1 and 2, respectively.
The excess values of above parameters for each mixture have been fitted to RedlichKister polynomial equation [13]: The values of the coefficients were calculated by a method of least squares along with the standard deviation (). The coefficient is adjustable to the parameters for a better fit of the excess functions. The standard deviation values were obtained from where is the number of experimental points, is the number of parameters, and and are the experimental and calculated parameters, respectively.
4. Results and Discussion
The structures of the components taken up for study are given in Scheme 1.
The experimental values of ultrasonic velocity () and density () for the three binary mixtures over the entire composition range and at temperatures = 303.15, 308.15, 313.15, and 318.15 K are given in Table 2. The values of the RedlichKister polynomial coefficients evaluated by the method of least squares along with standard deviation are given in Table 3. Plots of , , , and against mole fraction of quinoline for all the three mixtures are given in Figures 1–4.


(a)
(b)
(c)
(a)
(b)
(c)
(a)
(b)
(c)
(a) .
(b)
(c)
The excess transport properties of the mixtures are influenced by three main types of contributions, namely, (i) due to non specific Van der Waals type forces, (ii) due to hydrogen bonding, dipoledipole, and donoracceptor interaction between unlike molecules, and (iii) due to the fitting of smaller molecules into the voids created by the bigger molecules. The first effect leads to contraction in volume hence leads to negative contribution towards and positive contribution towards . However, the second effect leads to negative contribution towards and positive contribution towards .
For all the three mixtures, the results of the excess adiabatic compressibility plotted in Figures 1(a)–1(c) are negative at all the temperatures studied. The negative values of suggest that the mixtures are less compressible than the corresponding ideal mixture. According to Fort and Moore [14], the liquids of different molecular size usually mix with decrease in volume yielding negative values. The strength of the interactions between component molecules increases when excess values tend to become increasingly negative. As the temperature increases, the values also increase in all the three systems, suggesting that the thermal energy activates the molecules towards complex formation between unlike molecules [15]. It is also observed that the molecular interactions are stronger in quinoline + oxylene mixture.
From Figures 2(a)–2(c) it is observed that values are negative for the entire mole fraction range, for all the four temperatures in case of all the three mixtures. The values are increasingly negative as the strength of interaction between component molecules increases [16].
The excess values of which are plotted in Figures 3(a)–3(c) are all positive in all the three liquid systems over the entire composition range and for all the four temperatures studied. The positive excess values of clearly suggest that there exist strong molecular interactions between the molecules of all the three mixtures [17].
The results for the excess ultrasonic velocity plotted in Figures 4(a)–4(c) are positive for all the three mixtures at all the temperatures studied. The positive values of increase with the increase in temperature which indicates the increase in strength of interaction with temperature in all the three mixtures. The higher positive values of are observed in case of quinoline + oxylene mixture, because the –OH group attached to the benzene ring in case of oxylene is stabilized to a great extent through resonance as compared to other mixtures [18].
5. Conclusions
From the data of ultrasonic velocity and density, some thermoacoustical parameters and their excess parameters for the three binary liquid mixtures of quinoline with oxylene, mxylene, and pxylene at = 303.15, 308.15, 313.15, and 318.15 K are calculated for the entire composition range. From the results of these excess parameters, it is observed that there exists a strong molecular interaction between the unlike molecules in all the three mixtures. The interaction is stronger in case of quinoline + oxylene mixture as compared to quinoline + mxylene/pxylene mixtures. These data will be useful in pharma and perfume industries for handling and mixing processes.
References
 K. Narendra, Ch. Srinivasu, Sk. Fakruddin, and P. N. Murthy, “Excess parameters of binary mixtures of anisaldehyde with ocresol, mcresol and pcresol at T = (303.15, 308.15, 313.15, and 318.15) K,” The Journal of Chemical Thermodynamics, vol. 43, no. 11, pp. 1604–1611, 2011. View at: Publisher Site  Google Scholar
 A. Ali, A. Yasmin, and A. K. Nain, “Study of intermolecular interactions in binary liquid mixtures through ultrasonic speed measurement,” Indian Journal of Pure and Applied Physics, vol. 40, no. 5, pp. 315–322, 2002. View at: Google Scholar
 S. I. Oswal and N. B. Patel, “Speed of sound, isentropic compressibility, viscosity, and excess volume of binary mixtures. 2. Alkanenitriles + dimethylformamide, + dimethylacetamide, and + dimethyl sulfoxide,” Journal of Chemical and Engineering Data, vol. 40, no. 4, pp. 845–849, 1995. View at: Publisher Site  Google Scholar
 R. Mehra and R. Israni, “Effect of temperature on excess molar volumes of binary mixtures of hexadecane and butanol,” Indian Journal of Pure and Applied Physics, vol. 38, no. 2, pp. 81–83, 2000. View at: Google Scholar
 A. Ali and A. K. Nain, “Study of intermolecular interaction in binary mixtures of formamide with 2propanol, 1,2propanediol and 1,2,3propanetriol through ultrasonic speed measurements,” Indian Journal of Pure and Applied Physics, vol. 39, pp. 421–427, 2001. View at: Google Scholar
 J. Nath, “Ultrasonic velocities, relative permittivities and refractive indices for binary liquid mixtures of trichloroethene with pyridine and quinoline,” Fluid Phase Equilibria, vol. 109, no. 1, pp. 39–51, 1995. View at: Google Scholar
 J. A. AlKandary, A. S. AlJimaz, and A. H. M. AbdulLatif, “Viscosities, densities, and speeds of sound of binary mixtures of benzene, toluene, oxylene, mxylene, pxylene, and mesitylene with anisole at (288.15, 293.15, 298.15, and 303.15) K,” Journal of Chemical and Engineering Data, vol. 51, no. 6, pp. 2074–2082, 2006. View at: Publisher Site  Google Scholar
 S. Parveen, S. Singh, D. Shukla, K. P. Singh, M. Gupta, and J. P. Shukla, “Molecular interaction study of binary mixtures of THF with methanol and ocresol—an optical and ultrasonic study,” Acta Physica Polonica A, vol. 116, no. 6, pp. 1011–1017, 2009. View at: Google Scholar
 D. D. Perrin and W. L. F. Armarego, Purification of Laboratory Chemicals, Pergamon Press, Oxford, UK, 3rd edition, 1980.
 D. Das and D. K. Hazra, “Molecular interaction study in binary mixtures of N,Ndimethyl acetamide with 2ethoxyethanol at different temperatures,” Indian Journal of Physics B, vol. 77, pp. 519–523, 2003. View at: Google Scholar
 B. Jacobson, “Ultrasonic velocity in liquids and liquid mixtures,” Journal of Chemical Physics, vol. 6, no. 5, pp. 927–928, 1952. View at: Publisher Site  Google Scholar
 D. R. Lide, Ed., CRC Handbook of Chemistry and Physics, CRC Press, Boca Raton, Fla, USA, 76th edition, 1995.
 O. Redlich and A. T. Kister, “Algebraic representation of thermodynamic properties and the classification of solutions,” Indian and Engineering Chemistry, vol. 40, no. 2, pp. 345–348, 1948. View at: Publisher Site  Google Scholar
 R. J. Fort and W. R. Moore, “Adiabatic compressibilities of binary liquid mixtures,” Transactions of the Faraday Society, vol. 61, pp. 2102–2111, 1965. View at: Google Scholar
 S. N. Gour, J. S. Tomar, and R. P. Varma, “Study of molecular interactions in binary mixtures using excess thermodynamic parameters,” Indian Journal of Pure and Applied Physics, vol. 24, p. 602, 1986. View at: Google Scholar
 A. Ali and A. K. Nain, “Ultrasonic and volumetric study of binary mixtures of benzyl alcohol with amides,” Bulletin of the Chemical Society of Japan, vol. 75, pp. 681–687, 2002. View at: Google Scholar
 S. Thirumaran and D. George, “Ultrasonic study of intermolecular association through hydrogen bonding in ternary liquid mixtures,” Journal of Engineering and Applied Sciences, vol. 4, no. 4, pp. 1–11, 2009. View at: Google Scholar
 K. Tiwari, C. Patra, and V. Chakravortty, “Molecular interactions study on binary liquid mixtures of dimethylsulphoxide with benzene, carbontetrachloride and toluene from the excess properties of ultrasonic velocity, density and viscosity,” Acoustics Letters, vol. 19, pp. 53–59, 1995. View at: Google Scholar
Copyright
Copyright © 2012 Sk. Fakruddin et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.