Thermodynamic and acoustic properties of binary mixtures of oxolane with aniline and substituted anilines at 303.15, 313.15 and 323.15 K

doi:10.1016/j.tca.2010.04.025

Thermochimica Acta

Volumes 507–508, 10 August 2010, Pages 27-34

https://doi.org/10.1016/j.tca.2010.04.025 Get rights and content

Abstract

Speeds of sound u, isentropic compressibilities κ_S, Rao's molar sound functions R, intermolecular free lengths L_f, specific acoustic impedances Z, excess molar volumes $V_{m}^{E}$ , excess isentropic compressibilities $κ_{S}^{E}$ , excess intermolecular free lengths $L_{f}^{E}$ and excess specific acoustic impedances Z^E, of three binary mixtures of oxolane (tetrahydrofuran) with aniline, N-methylaniline and N-ethylaniline have been reported over the entire range of composition at 303.15, 313.15 and 323.15 K. The excess values have been fitted to Redlich–Kister polynomial equation. The results have been analyzed in terms of molecular interactions between oxolane and anilines. The speeds of sound in present binary mixtures have been estimated from various empirical and theoretical models.

Introduction

The thermodynamic, acoustic and transport properties of non-electrolyte liquid–liquid mixtures provide information about type and extent of molecular interactions, and can be used for the development of molecular models for describing the behaviour of solutions [1], [2], [3], [4], [5], [6]. They are also necessary for engineering calculation, research of mass transfer, heat transfer and fluid flow. The increasing use of cyclic ethers and alkyl and aromatic amines in many industrial processes, as well as theoretical interest in the nature of associated solutions have greatly stimulated the need for extensive information on properties of mixtures involving these components. It has been reported that cyclic ethers interact with amines in their mixtures. Different volumetric and thermal effects are observed upon mixing because of the molecular interactions between cyclic ethers + amine [7], [8], [9], [10], [11], [12], [13]. The formation of hydrogen bonds is assumed to occur between a primary or secondary amine group with weak proton donor ability and the unshared electron pairs on the oxygen atom of cyclic ether. Considerable systematic work on cyclic ether + alkylamine has been reported, whereas data on cyclic ether + aromatic amines is scanty [14], [15]. Considering all these aspects we undertook investigations on the thermodynamic, acoustic and transport properties of binary mixtures involving oxolane and aromatic amines. Oxolane is used as a solvent in many chemical industries due to its proton accepting nature. The aniline is predominantly used [16] as parent substance in the manufacture of several chemical products and intermediates. It is also used in manufacture of synthetic dyes, drugs and as an accelerator in vulcanization of rubber. Secondary amines N-methylaniline and N-ethylaniline are used as a latent and coupling solvent. In the present paper, we report densities, speeds of sound, isentropic compressibilities, Rao's molar sound functions, intermolecular free lengths, specific acoustic impedances, and calculated excess functions of three binary mixtures of oxolane with aniline, N-methylaniline, and N-ethylaniline at 303.15, 313.15 and 323.15 K. This study will also provide a test of Nomoto's relation (NR) [17], Van Dael and Vangeel relation (VVR) [18], Junjie's relation (JR) [19], impedance relation (IR) [20], Schhaffs’ collision factor theory (CFT) [21], [22], Jacobson's free length theory (FLT) [23], and Progogine–Flory–Patterson–Oswal theory (PFPOT) [24], [25], [26], [27] to estimate speed of sound in binary mixtures at different temperatures.

Section snippets

Experimental

All chemicals used in this study were of analytical grade and obtained from s.d.fine-chem., Ltd. The claimed mass fraction purity for the chemicals was >0.995. These liquids were dried over 4 Å molecular sieves and partially degassed prior to use. The purity of these experimental liquids was checked by comparing the observed densities and velocities with those reported in the literature. The measured values are included in Table 1 along with the available literature values [28], [29], [30], [31]

Results and discussion

The results for the densities ρ, speeds of sound u, isentropic compressibilities κ_S, Rao's molar sound functions R [41], specific acoustic impedances Z and intermolecular free lengths L_f, excess molar volumes $V_{m}^{E}$ and excess isentropic compressibilities $κ_{S}^{E}$ for binary mixtures of oxolane with aniline, N-methylaniline and N-ethylaniline at 303.15, 313.15, and 323.15 K over the entire range of composition are given in Table 2, Table 3, Table 4.

From the values of densities and speeds of sound, the

Estimation of speed of sound

The speed of sound u from the Nomoto's relation [17], Van Dael and Vangeel [18], Junjie's relation [19], impedance relation [20], collision factor theory [21], [22], intermolecular free length theory [23], and Prigogine–Flory–Patterson–Oswal theory [24], [25], [26], [27] have also been estimated for the present binary mixtures. The pertinent relations in these calculations and their theoretical basis have been outlined several times and will not be repeated here.

The speeds of sound u_est in the

Conclusions

The values of $V_{m}^{E}$ , $κ_{S}^{E}$ and $L_{f}^{E}$ are negative and Z^E are positive for binary mixtures of oxolane with aniline, N-methylaniline and N-ethylaniline at 303.15, 313.15, and 323.15 K. There exist specific interactions between unlike molecules through hydrogen bonding and dipole–dipole interactions between unlike molecules. The estimation ability of speed of sound in the presently investigated mixtures follows the sequence CFT ≅ NR > IR > FLT > PFPOT > JR > VVD.

Acknowledgement

The authors are thankful to Prof. Dr. AN. Kannappan, Head of Department of Physics, Annamalai University, Annamalainagar, for encouragement and providing facilities.

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