FT-IR studies on excess thermodynamic properties of binary liquid mixtures o-chlorotoluene with 1-propanol, 1-butanol, 1-pentanol, 1-hexanol and 1-heptanol at different temperatures
Introduction
The excess thermodynamic properties of binary liquid mixtures have been very useful to obtain information on the intermolecular interactions and geometrical effects in the systems [1], [2]. Further, the knowledge of transport and thermodynamic properties of binary liquid mixtures containing halogenated hydrocarbons are very important due to their practical applications in various fields including detergents, rubber, plastics, and aerosol propellants [3]. The compound o-chlorotoluene is one of the methyl substituted halobenzene that is used as an intermediate in the pesticide, pharmaceutical and dye industries [4]. Alkanols are polar, self-associated liquids and the dipolar association of alkanols decrease when they are mixed with polar compounds containing halogen atoms, due to the existence of specific intermolecular interactions between the hydroxyl group of alkanols and halogenated hydrocarbons [5]. Further, 1-alkanols are versatile solvents used in chemical and technological processes which are inexpensive and easily available at high purity [6].
An extensive survey of the literature has shown that, few studies that were available on measurements of thermophysical properties for binary mixtures of o-chlorotoluene with dimethylformamide [4], 1-decanol [5], chloroalkanes [7], aromatic hydrocarbons [8] and acetophenone [9] were reported. To the best of our knowledge, volumetric and ultrasonic studies on binary mixtures of o-chlorotoluene with a series of 1-alkanol (C3–C7) were not reported in the literature. The present work was undertaken to know the effect of degree of self association of 1-alkanols when mixed with o-chlorotoluene and how they modify the sign and magnitude of excess thermodynamic properties of component molecules. The FT-IR spectroscopy is a successful method to probe the molecular structure of association effects among molecules, since the FT-IR spectroscopy reveals precise information about water sensitive bonds [10], [11]. Generally, FT-IR spectral technique [12], [13] offer the advantages to measure the association properties and hydrogen bonding capability and to assess interaction of alcohol with water and polar by analyzing band shifts and changes of band shape. Furthermore, FT-IR is also advantageous to evaluate the vibrational properties of bonds through very thin solution films which are usually difficult to handle for the floating properties of solution.
Section snippets
Materials
The mass fraction purity of all the liquids from S.D Fine Chemicals, Ltd.,India was as follows: o-chlorotoluene (0.995), 1-propanol (0.995), 1-butanol (0.995), 1-pentanol (0.990), 1-hexanol (0.985) and 1-heptanol (0.995).The source, purity and water content of solvents used in this work are listed in Table 1. Prior to making the experimental measurements, all the liquids were used after double distillation and partially degassed with a vacuum pump under an inert atmosphere. The purity of all
Volumetric behaviour
Values of the experimental density (ρ), excess volume (VE), ultrasonic sound velocity (u), isentropic compressibility (kS) and excess isentropic compressibility for all the binary systems of o-chlorotoluene with 1-alkanol over the temperature range from (298.15 to 308.15) K are given in Table 3. The excess volume data were calculated from the densities of the pure liquids and their mixtures using the following equation:where x, M and ρ are mole fraction, molar
Conclusions
Values of the excess volume and excess isentropic compressibility are determined for the binary mixtures containing o-chlorotoluene with 1-propanol, 1-butanol, 1-pentanol, 1-hexanol and 1-heptanol at T = (298.15, 303.15, and 308.15) K at atmospheric pressure. The values of VE and show an inversion in sign at all the temperatures for all the binary mixtures over the whole composition range. As the chain length of 1-alkanol molecule increases from 1-propanol to 1-heptanol, the negative excess
Acknowledgments
The authors thank to IIT-Madras for providing the instrumentation facility.
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