Volumetric, acoustic and spectroscopic properties of 3-chloroaniline with substituted ethanols at various temperatures

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Highlights

  • Thermophysical properties of 3-chloroaniline with substituted ethanols were studied at various temperatures.

  • Excess volume, deviation in viscosity and isentropic compressibility data were correlated with Redlich–Kister equation.

  • Intermolecular hydrogen bonding between amine and hydroxyl group were studied by FTIR spectroscopy.

Abstract

Densities (ρ), speeds of sound (u) and viscosities (η) have been measured for the binary mixtures containing 3-chloroaniline with substituted ethanol such as 2-phenylethanol, 2-chloroethanol and 2-aminoethanol at T = (303.15 to 318.15) K. These experimental data have been used to calculate excess volume (VE), excess isentropic compressibility (κsE), deviation in viscosity (Δη) and excess Gibbs energy of activation of viscous flow (GE). The excess partial molar volumes, Vm,1E and Vm,2E, excess partial molar volumes Vm,1E and Vm,2E at infinite dilution have also been calculated. The variations in these properties with composition for all the binary mixtures suggest that loss of dipolar association, difference in size and shape of the component molecules, dipole–dipole interaction and hydrogen bonding between 3-choroaniline with 2-phenylethanol, 2-chloroethanol and 2-aminoethanol were observed. The excess parameters have been fitted to Redlich–Kister equation and the results were analyzed in terms of specific interactions present in the mixtures. Furthermore, the FTIR spectra have been recorded at T = 298.15 K and found to be useful for understanding the presence of hydrogen bonding between nitrogen atom of amino group of 3-chloroaniline and hydrogen atom of the –OH group of substituted ethanol molecules in the liquid mixtures. A good agreement is obtained between excess quantities and spectroscopic data.

Introduction

Densities (ρ) speeds of sound (u) and viscosities (η) of solutions are very important properties especially for the chemical design and for the optimization of chemical processes. The study of these properties plays an important role in many industrially interesting systems such as organic synthesis, ion extraction systems, gas adsorption solvents and mass transfer phenomena. Furthermore, the study of excess thermodynamic and transfer properties for binary mixtures will provide a lot of important information concerning the deeper understanding of the molecular liquid structure and intermolecular interactions. This work is a part of our program to provide data for the characterization of the molecular interactions between solvents in binary systems [1], [2], [3]. The liquids were chosen for the present study on the basis of their industrial importance. 3-Chloroaniline is a polar solvent and self-associated through hydrogen bonding of its amine group. The amino group in 3-chloroaniline is an electron donor and also plays an important role as proton-acceptor center. 3-Chloroaniline is used as an intermediate in the production of a number of products, including agricultural chemicals, azo dyes and pigments, bactericide or biocide and pharmaceuticals. On the other hand, 2-chloroethanol is a polar, bi-functional compound, consisting of both hydroxyl group as a proton donor and halogen atom as a proton acceptor. It is a versatile solvent used in many industrial areas and also a mutagenic chemical. Mono ethanolamine is a widely used agent in carbon dioxide and hydrogen sulfide removal processes. 2-Phenylethanol has found usage in artificial essences and as a base solvent for some flavor compounds.

In the present study, our focus is on the study of liquid mixtures of substituted ethanol with 3-chloroaniline because there have been few studies on these mixtures [4], [5]. It is expected that there will be significant degree of H-bonding in these binary mixtures, because 3-chloroaniline and substituted ethanols both have a proton donor and a proton acceptor group [6]. To understand the possible associations between 3-chloroaniline and substituted ethanols through OH····NH2 and NH2···· OH bonds, we report the densities, speeds of sound and viscosities for three binary systems (3-chloroaniline with 2-aminoethanol, + 2-phenylethanol, + 2-chloroethanol) at T = (303.15 K to 318.15) K and under 0.1 MPa pressure. The experimental data have been used to compute excess volume (VE), excess isentropic compressibility (κsE), deviation in viscosity (Δη) and excess Gibbs energy of activation of viscous flow (GE). The results are used to qualitatively discuss in terms of specific interactions between unlike molecules.

Section snippets

Materials

All the chemicals (A.R. grade) were used in the present work supplied by Sigma–Aldrich, India and S.D. Fine Chem. Ltd., India. The mass fraction purities of all the chemicals are as follows: 3-chloroaniline (0.99), 2-phenylethanol (Sigma Aldrich) (>99%), 2-chloroethanol (>0.995) and 2-aminoethanol (>0.99). All the chemicals were further purified by the methods as described in the literature [7]. Prior to making experimental measurements, all the liquids were double distilled and partially

Results and discussion

The experimental values of density (ρ), viscosity (η) and speed of sound (u) of the binary liquid mixtures of 3-chloroaniline with substituted ethanols at T = (303.15 to 318.15) K are presented in table 3.

Excess volumes (VE) were calculated from the experimental density values, using the following equation:VE=i=12xiMi(ρ-1-ρi-1),where xi, Mi and ρi are mole fraction, molar mass and density of pure components, respectively, ρ is the density of the mixture, the subscripts i and m represent pure

Conclusions

Densities, speeds of sound and viscosities of binary mixtures of 3-chloroaniline with substituted ethanols (2-phenylethanol, 2-chloroethanol and 2-aminoethanol) have been measured at different temperatures and derived parameters along with their excess values Vm,1E, Vm,2E, Vm,1E and Vm,2E were calculated. The results were analyzed in terms of the molecular interactions through the hydrogen bonding between nitrogen atom of –NH2 group of 3-chloroaniline and hydrogen atom of the –OH group of

Acknowledgment

One of the authors [P.VR] expresses his sincere thanks to Prof. P. Venkateswarlu, Department of Chemistry, S.V. University, Tirupati for providing facilities to carry out some part of the present work.

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