Elsevier

Thermochimica Acta

Volume 516, Issues 1–2, 20 March 2011, Pages 64-73
Thermochimica Acta

Thermodynamic and acoustic properties of binary mixtures of ethers. III. Diisopropyl ether or oxolane with o- or m-toluidines at 303.15, 313.15 and 323.15 K

https://doi.org/10.1016/j.tca.2011.01.019Get rights and content

Abstract

Densities ρ and speeds of sound u, of binary mixtures formed by o-toluidine or m-toluidine with diisopropyl ether (DIPE) or oxolane have been measured over the entire range of composition at a temperature of (303.15, 313.15 and 323.15) K and atmospheric pressure. The ρ and u values were used to calculate isentropic compressibilities κS, Rao's molar sound functions R, intermolecular free lengths Lf, specific acoustic impedances Z, excess molar volumes VmE, excess isentropic compressibilities κSE, excess intermolecular free lengths LfE and excess specific acoustic impedances ZE. The results have been used to investigate molecular interactions and structural effects in these mixtures. The speed of sound in present mixtures has been estimated using several empirical and theoretical models to determine their relative predicting ability in terms of pure component properties.

Research highlights

► We report excess properties of molar volumes, isentropic compressibilities, free lengths. ► Four binary mixtures of diisopropylether or oxolane with o- and m- toluidines are studied. ► Molecular interactions estimated qualitatively from magnitude of deviations in the properties. ► The free volume and P* effects has significant contributions in excess properties. ► The speeds of sound in mixtures were estimated with seven 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]. They are also necessary for engineering calculation, research of mass transfer, heat transfer and fluid flow.

Amines are a very interesting class of compounds. Mixtures containing arylamines show very interesting features [6]. Systems with 1-alkanols are characterized by quite large positive deviations from Raoult's law [7], [8], while linear amines + alkanol mixtures behave quite differently [9], [10], [11]. It has been reported that ether interacts with amine in their mixtures [12], [13], [14]. 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 ether molecule. The arylamines are predominantly used as parent substances in the production of antioxidants, agricultural, pharmaceutical and rubber chemicals [15]. They are also used in manufacture of intermediate for synthetic dyes, and organic pigments especially for red color. It is well known that oxolane is an excellent solvent of polymers while diisopropyl ether is used as an oxygenate gasoline additive [16], [17]. All this makes the study of ether-aromatic amine very interesting both industrially and theoretically. Therefore, we have undertaken systematic investigations of thermodynamic and acoustic properties of binary liquid mixtures involving aromatic amines with ethers at different temperatures.

In the previous papers [18], [19] we have reported speeds of sound, isentropic compressibilities, Rao's molar sound functions, intermolecular free lengths, specific acoustic impedances, and various calculated excess properties of binary mixtures of oxolane or DIPE with aniline, N-methylaniline and N-ethylaniline at 303.15, 313.15 and 323.15 K. In this paper, we extend the work on mixtures of diisopropyl ether or oxolane with o-toluidine or m-toluidine. Nomoto model (NM) [20], Van Dael model (VM) [21], Ernst et al. model (EM) [22], impedance model (IM) [23], Schaaffs’ collision factor theory (CFT) [24], Jacobson's free length theory (FLT) [25], and Prigogine–Flory–Patterson–Oswal theory (PFPOT) [26], [27], [28], [29] have also been examined to estimate speeds of sound at different temperatures in the investigated binary mixtures.

Section snippets

Experimental

All chemicals used in this study were of analytical grade 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 speeds of sound with those reported in the literature. The measured values are presented in Table 1 along with the available literature data.

The densities of pure

Results and discussion

The results for the densities, speeds of sound, isentropic compressibilities, Rao's molar sound functions [46], [47], specific acoustic impedances, intermolecular free lengths, excess molar volumes, and excess isentropic compressibilities for four binary mixtures of DIPE or oxolane with o-toluidine or m-toluidine at 303.15, 313.15, and 323.15 K are given in Table 2, Table 3, Table 4, Table 5.

From the values of densities and speeds of sound u, the isentropic compressibilities κS, Rao's molar

Estimation of speeds of sound

Recently, Gayol et al. [55] and Khammer and Shaw [56] described and tested several predictive methods for speed of sound in alkanol + n-alkanes mixtures and discussed the combing rules used in the different models. Glinski [57] discussed the additivity of sound velocity in twenty four randomly selected binary mixtures and found Nomoto model [20] based on Rao's hypothesis [47] provides results similar to those of Ernst et al. model [22] while the Van Dael model [21] often fails. For all three

Conclusions

The magnitude of large negative values of VmE,κSE,andLfE and positive values of ZE for binary mixtures of DIPE with o-toluidine or m-toluidine is much larger than that observed for oxolane mixtures at investigated temperatures 303.15, 313.15, and 323.15 K. This difference is attributed to the effect due to the difference in free volume and internal pressure of involved components. The specific interactions between unlike molecules through hydrogen bonding and dipole–dipole interactions

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