Elsevier

Thermochimica Acta

Volume 479, Issues 1–2, 5 December 2008, Pages 17-27
Thermochimica Acta

Volumetric and transport properties of ternary mixtures containing 1-propanol, triethylamine or tri-n-butylamine and cyclohexane at 303.15 K: Experimental data, correlation and prediction by ERAS model

https://doi.org/10.1016/j.tca.2008.09.006Get rights and content

Abstract

The excess molar volumes (VmE), viscosity deviations (Δη), and excess Gibbs energies of activationG*E) of viscous flow have been investigated from densities and viscosities measurements for two ternary mixtures 1-propanol + triethylamine + cyclohexane and 1-propanol + tri-n-butylamine + cyclohexane and corresponding binaries at 303.15 K and atmospheric pressure over the entire range of composition. The empirical equations due to Redlich–Kister, Kohler, Rastogi et al., Jacob–Fitzner, Tsao–Smith, Lark et al., Heric–Brewer, and Singh et al., have been employed to correlate VmE, Δη, and ΔG*E of ternary mixtures with their corresponding binary parameters. The results are discussed in terms of the molecular interaction between the components of the mixture. Further, the Extended Real Associated Solution (ERAS) model has been applied to VmE for the present binary and ternary mixtures and the results are compared with the experimental data.

Introduction

Excess properties of mixtures provide information about the molecular interactions between the various components and can be used for the development of molecular models describing the thermodynamic behaviour of mixtures. Experimental results of multi-component mixtures are very important for industrial application. Therefore the properties of multi-component mixtures are often estimated from the corresponding data of the constituent binary mixtures but the reliability of such estimation is always questionable and has to be tested.

Mixtures of alkanols with amines have been subject of many investigations [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], as they are highly non-ideal systems with large negative excess thermodynamic properties as a result of strong cross-association through formation of hydrogen bonds. Cyclohexane a non-associating inert molecule acts as an order-breaking molecule when mixed with associating components. Since, the excess properties of ternary mixtures are reflecting differences in molecular size, shape, and interaction of three components; it is of interest and significance to study effect of addition of cyclohexane in the mixture formed from alkanol and amine.

We are engaged in systematic studies of thermodynamic, acoustic, and transport properties of mixtures involving alkanols, alkylamines, and hydrocarbons. Speeds of sound, viscosities and excess molar volumes of their binary mixtures have been reported [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26]. As an extension, in the present work, excess molar volumes (VmE), viscosity deviations (Δη), and excess Gibbs energies of activation (ΔG*E) of viscous flow of two ternary mixtures 1-propanol (A) + triethylamine (B) + cyclohexane (C) and 1-propanol (A) + tri-n-butylamine (B) + cyclohexane (C) and constituent binary mixtures at 303.15 K and atmospheric pressure over the entire range of composition have been reported. The ternary results of VmE, Δη, and ΔG*E have been correlated through empirical or semi theoretical equations due to Redlich–Kister [27], Kohler [28], Rastogi et al. [29], Jacob–Fitzner [30], Tsao–Smith [31], Lark et al. [32], Heric–Brewer [33], and Singh et al. [34]. Further, the Extended Real Associated Solution (ERAS) model [14], [35], [36], [37] has been applied to describe the excess molar volumes of presently investigated binary and ternary mixtures.

Section snippets

Materials

Cyclohexane (cC6H12, Merck GR), 1-propanol (C3H7OH, Merck AR), triethylamine ((C2H5)3N, Fluka AG) and tri-n-butylamine ((C4H9)3N, Fluka AG) were used after further purification and drying by the standard procedures [38]. cC6H12 was dried over molecular sieve type 4 Å (Fluka) and was fractionally distilled over sodium. C3H7OH was purified by refluxing over lime for 5 h and then distilling through 1-m column. (C2H5)3N and (C4H9)3N were kept over sodium and fractionally distilled twice [39]. The

Results

The excess molar volumes of binary and ternary mixtures at each composition have been calculated using the following expressionVmE=i=A,B,CxiMiρi=A,B,CxiMiρiwhere Mi is the molar mass of pure component, ρ and ρi represent densities of mixture and pure components i, respectively. The VmE is estimated to be accurate within 0.005 cm3 mol−1.

The viscosity deviations from linear dependence on mole fraction were calculated byΔη=ηi=A,B,Cxiηiwhere η and ηi represent viscosities of mixture and pure

ERAS model

The ERAS model due to Heintz and co-workers [35], [36] combines the linear chain association model with Flory’s equation of state [60] and is applicable to mixtures consisting of one associating component (A, alkanol) and other weakly associating component (B, alkylamine), which forms cross-association complex (AiB). This model provides a quantitative treatment of HmE, GmE, and VmE and accounts for the competing effects present in the binary mixtures [10], [11], [12], [13], [61], [62], [63],

Discussion

The values of VmE (Fig. 1, Fig. 2, Fig. 3) are positive while Δη (Fig. 6) negative for (C2H5)3N + cC6H12, (C4H9)3N + cC6H12 and C3H7OH + cC6H12 due to disruption of dipolar order in trialkylamine or breaking of hydrogen bonds in 1-propanol [15], [22]. This is in agreement with the positive HmE values of these solutions [56], [57]. Comparing the values of VmE and Δη for 1-alkanol + cyclohexane (Table 3), it is seen that VmE and Δη values decrease with chain length of 1-alkanol from 1-propanol to

Conclusions

The values of VmE are positive while Δη negative for binary mixtures of trialkylamine or 1-propanol with cyclohexane, due to disruption of dipolar order or breaking of hydrogen bonds. Large negative values of VmE result from cross-hydrogen bonding between the molecules of 1-propanol and trialkylamine in their binary mixtures.

Large standard deviations are observed when the VmE, Δη, and ΔG*E of viscous flow were correlated with the empirical equations containing only binary parameters. The

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    Present address: The QUILL Research Centre, School of Chemistry and Chemical Engineering, Queen’s University of Belfast, Belfast BT9 5AG, Northern Ireland, United Kingdom.

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