Ternary equilibrium data of mixtures consisting of 2-butanol, water, and heavy alcohols at T = 298.2 K

doi:10.1016/j.jct.2012.01.003

The Journal of Chemical Thermodynamics

Volume 49, June 2012, Pages 39-45

https://doi.org/10.1016/j.jct.2012.01.003 Get rights and content

Abstract

Experimental solubility curves and tie-line data for the (water + 2-butanol + organic solvents) systems were obtained at T = 298.2 K and atmospheric pressure. The organic solvents were four heavy alcohols, i.e. 1-hexanol, 1-heptanol, 1-octanol, and 1-decanol. The consistency of the experimental tie-line data was determined through the Othmer–Tobias and Bachman equations. Distribution coefficients and separation factors were calculated to evaluate the extracting capability of the solvents. The experimental data were correlated using the NRTL (α = 0.2) and UNIQUAC models, and binary interaction parameters were obtained. The average root mean square deviation values between the experimental and calculated data show the capability of these models, in particular NRTL model, in correlation of the phase behavior of the ternary systems.

Graphical abstract

Highlights

► Phase equilibria of the (water + 2BuOH + alcohols) system were investigated. ► Experimental LLE data were correlated with NRTL and UNIQUAC models. ► Distribution coefficients and separation factors were evaluated.

Introduction

(Liquid + liquid) equilibrium (LLE) investigations for ternary aqueous mixtures of alcohols with organic solvents are important in evaluation of industrial solvent extraction units [1], [2], [3], [4], [5], [6]. Accurate ternary equilibrium data are always needed for efficient separation of alcohols from water.

The alcohol used in the current study was 2-butanol (2BuOH). It has many scientific and industrial applications. It is a flammable colorless liquid, which is completely miscible in polar organic solvents [7]. The 2-BuOH forms a binary azeotrope with water, which is hard to separate by distillation [8]. Therefore, recovery of this alcohol from aqueous solution using liquid–liquid extraction method is industrially and economically important.

As a detailed evaluation of solvents for the extraction of 2BuOH using the liquid–liquid extraction technique is not available in the literature, the extraction of this alcohol from aqueous mixtures is still an important problem. However, few important investigations have been carried out in recent years on the LLE measurements and the extraction of 2BuOH from aqueous solutions by Monton [9] and co-workers, Chafer and co-workers [10], and Chen and Chang [11]. More LLE data for the ternary aqueous mixture of 2BuOH with a heavy primary alcohol at various temperatures have recently been reported in our previous publication [12].

The type of solvent is one of the most important factors, which strongly influence on the equilibrium characteristics and phase behavior. Among the appropriate organic solvents, heavy alcohols can be tested as extractants for the recovery of 2BuOH from water. For this purpose LLE data of ternary systems consist of water, 2BuOH and heavy alcohols were reported at T = 298.2 K. The heavy primary alcohols (1-hexanol, 1-heptanol, 1-octanol, and 1-decanol) were used as organic solvents, which have suitable molecular structure, low cost, high boiling points, and very low solubility in water.

In order to evaluate the extracting ability of the solvents for the separation of 2BuOH from water, distribution coefficients and separation factors were determined from the tie-line data. The experimental tie-line data were correlated to test consistency with the Othmer–Tobias [13] and Bachman [14] equations. The experimental LLE data were correlated with the non-random two-liquid (NRTL) [15] and UNIQUAC [16] models and the values of the interaction parameters were obtained.

Section snippets

Material

The 2-butanol, 1-hexanol, 1-heptanol, 1-octanol, and 1-decanol with stated mass fraction purities higher than 0.99 were purchased from Merck. The organic chemicals were dried over molecular sieves (Merck type 4A). Distilled and deionised water was used throughout all experiments. All materials were used as received without any further purification. Some measured physical properties for the chemicals used in this study along with the literature values are listed in table 1.

Apparatus and procedure

Refractive indices and

Experimental LLE data

The experimental tie-line compositions of the equilibrium phases for the ternary systems {water + 2BuOH + solvents (1-hexanol, 1-heptanol, 1-octanol, and 1-decanol)} are listed in table 4. The LLE diagrams for the ternary systems are plotted in FIGURE 1, FIGURE 2, FIGURE 3, FIGURE 4. Since the (2BuOH + solvent) mixture is the only liquid pair that is completely miscible and two liquid pairs (2BuOH + water) and (water + solvent) are partially miscible, these ternary systems behave as type-2 LLE [22].

Conclusions

Tie-line data for the {water + 2BuOH + organic solvents (1-hexanol, 1-heptanol, 1-octanol, and 1-decanol)} ternary systems were obtained at T = 298.2 K. The ternary systems exhibit type-2 behavior of the LLE. The UNIQUAC and NRTL (α = 0.2) models were used to correlate the experimental data and to calculate the phase compositions of the mixtures studied. The corresponding optimized binary interaction parameters were also calculated. Both the models give relatively good results for the system

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Ternary equilibrium data of mixtures consisting of 2-butanol, water, and heavy alcohols at T = 298.2 K

Abstract

Graphical abstract

Highlights

Introduction

Section snippets

Material

Apparatus and procedure

Experimental LLE data

Conclusions

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Mol. Liq.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

Colloid Surf. A.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Mol. Liq.