(Liquid + liquid) equilibria for (water + 1-propanol or acetone + β-citronellol) at different temperatures

doi:10.1016/j.jct.2015.02.013

The Journal of Chemical Thermodynamics

Volume 86, July 2015, Pages 20-26

https://doi.org/10.1016/j.jct.2015.02.013 Get rights and content

Highlights

•
Ternary (liquid + liquid) equilibria containing β-citronellol are presented.
•
Distribution ratios of 1-propanol and acetone in the mixtures are examined.
•
The effect on the temperature of the systems is evaluated and discussed.

Abstract

On this paper, experimental (liquid + liquid) equilibrium (LLE) results are presented for systems composed of β-citronellol and aqueous 1-propanol or acetone. To evaluate the phase separation properties of β-citronellol in aqueous mixtures, LLE values for the ternary systems (water + 1-propanol + β-citronellol) and (water + acetone + β-citronellol) were determined with a tie-line method at T = (283.15, 298.15, and 313.15 ± 0.02) K and atmospheric pressure. The reliability of the experimental tie-lines was verified by the Hand and Bachman equations. Ternary phase diagrams, distribution ratios of 1-propanol and acetone in the mixtures are shown. The effect of the temperature on the ternary (liquid + liquid) equilibria was examined and discussed. The experimental LLE values were satisfactorily correlated by extended UNIQUAC and modified UNIQUAC models.

Graphical abstract

(Liquid + liquid) equilibrium data for systems composed of β-citronellol and aqueous 1-propanol or acetone are presented. Distribution ratios of 1-propanol and acetone in the mixtures are examined. The effect of the temperature on the ternary (liquid + liquid) equilibria is evaluated and discussed.

Introduction

As environmentally friendly organic solvents, chemical compounds obtained from natural products have been increasing recently in use [1], essential oils have become important in the global economy not only for their medicinal properties but also due to their wide use in the chemical and food industries [2]. Citronellol (C₁₀H₂₀O) is a natural acyclic monoterpenoid and one the of the important fragrance terpenoids. It is abundant in plant essential oils (major constituents are terpenes and oxygenated terpenoids) and commonly used in perfumes, flavours, synthesis, fine chemicals, and biotransformation. Citronellol is present in many plants such as Cymbopogon nardus [3], Cymbopogon citratus, Monarda citriodora, Pelargonium graveolens, and Artemisia scoparia. The residues of Artemisia scoparia could serve as an important bioresource for extraction of monoterpenoid-rich oil (main components: β-citronellol and citronellal) exhibiting antioxidant activity, and thus hold a good potential use in the food and pharmaceutical industry [4]. As part of our research on the Cymbopogon essential oils by (liquid + liquid) extraction with different solvents, this work reports results for (water + 1-propanol or acetone + citronellol) at different temperatures. These solvents have the presence of polar groups as common factor.

Propanol and acetone are important organic synthetic raw materials, and are also good solvents and extraction agents. Extraction of essential oils from plants by extraction agents is popularly used in industry. The solubility of the terpenoids dissolved into several kinds of solvents and the experimental LLEs of the multicomponent terpenoid mixtures are indispensable for the proper design of their separation process or for the study of their use as industrial solvents. On the other hand, the (liquid + liquid) equilibria in (water + propanol or acetone + citronellol) systems provide important information in the design of equipment for the separation of propanol or acetone from aqueous mixtures. A survey of the literature on the (liquid + liquid) equilibrium systems containing monoterpenoid (or monoterpene) and alcohol, ternary (linalool + ethanol + water), and (limonene + ethanol + water) systems from T = (293.15 to 323.15) K were studied by Cháfer et al. [2], [5]. The (water + ethanol + citral) multicomponent system at T = 303.15 K by Gramajo de Doz [6]; ternary LLE systems (limonene + linalool + 1,2-propanediol or 1,3-propanediol) from T = (298.15 to 318.15) K by Arce et al. [7]; (liquid + liquid) equilibrium data for the system (limonene + carvone + ethanol + water) at T = 298.2 K by Oliveira et al. [8]; ternary LLE (water + acetone + α-pinene, or β-pinene, or limonene) mixtures by Li and Tamura [9]; and ternary (α-pinene + Δ₃-carene) polar compound systems [10] by Antosik and Stryjek, are available in the literature. Furthermore, ternary (water + terpene + 1-propanol or 1-buthanol) systems at T = 298.15 K [11]; (liquid + liquid) phase behaviour of geraniol in aqueous alcohol mixtures [12]; and ternary LLE for β-citronellol in aqueous alcohol at different temperatures [13] have been reported previously. In addition, as far as we know, there are few reports on LLE for (propanol or acetone + terpenoid) mixtures in the literature.

In the present paper, to examine the multicomponent phase equilibrium behaviour of β-citronellol in the (water + 1-propanol) or (water + acetone) mixture and the distribution ratios of 1-propanol or acetone between organic and aqueous phases, we determined the LLE tie-lines for (water + 1-propanol or acetone + citronellol) systems at T = (283.15, 298.15, and 313.15) K and atmospheric pressure. The reliability of the experimental LLE tie-lines was verified by the Hand and Bachman equations. The experimental values were correlated using the extended and modified UNIQUAC models. The effect of temperature on (liquid + liquid) phase equilibria was also studied, and its consequences are discussed.

Section snippets

Materials

3,7-Dimethyloct-6-en-1-ol (CAS No. 106-22-9, (±)-β-citronellol), 1-propanol, and acetone were supplied by the Aladdin Company and were used without further purification. Double-distilled water prepared in our laboratory was used throughout the experiment. The purities in mass fraction (by a GC assay) of the chemical reagents used in this work are shown in table 1. Their densities and refractive indices were measured at T = 293.15 K and atmospheric pressure, and are compared with literature values

Experimental tie-line and reliability results

The experimental ternary LLE tie-line results for the {water (1) + 1-propanol (2) + β-citronellol (3)} and {water (1) + acetone (2) + β-citronellol (3)} systems at T = (283.15, 298.15, and 313.15) K whose composition are expressed in mole fraction x are reported in TABLE 2, TABLE 3.

The reliability of the experimental tie-line values at each temperature was evaluated by using the Hand [16] and Bachman [17] linear correlation equations, respectively, as follows $\ln {(\frac{x_{2}}{x_{3}})}^{II} = k_{1} \ln {(\frac{x_{2}}{x_{1}})}^{I} + b_{1}$ $x_{3}^{II} = k_{2} (\frac{x_{3}^{II}}{x_{1}^{I}}) + b_{2}$ where the

Conclusions

(Liquid + liquid) equilibrium tie-line compositions were presented for the ternary mixtures of (water + 1-propanol or acetone + β-citronellol) at T = (283.15, 298.15, and 313.15) K. The systems have a low solubility for β-citronellol in aqueous phase and a high solubility for water in the organic phase at any of the temperatures studied here. It is concluded that the distribution ratios of 1-propanol or acetone for the systems and the miscible regions increase as temperature increases. The (water +

Acknowledgements

The authors thank the financial support from the National Natural Science Foundation of China (No. 21106021).

References (28)

A. Cháfer et al.
Fluid Phase Equilib.
(2005)
H.P. Singh et al.
Food Chem.
(2009)
A. Cháfer et al.
Fluid Phase Equilib.
(2004)
A. Arce et al.
Fluid Phase Equilib.
(2003)
C.M. Oliveira et al.
Fluid Phase Equilib.
(2013)
X. Li et al.
J. Chem. Thermodyn.
(2010)
M. Antosik et al.
Fluid Phase Equilib.
(1992)
H. Li et al.
Fluid Phase Equilb.
(2008)
T. Zhang et al.
J. Chem. Thermodyn.
(2012)
I. Nagata
Fluid Phase Equilib.
(1990)

G. Maurer et al.

Fluid Phase Equilib.

(1978)

K. Tamura et al.

J. Chem. Eng. Data

(2008)

J. Lawless

The Illustrated Encyclopedia of Essential Oils

(1995)

Mónica B. Gramajo de Doz,∗ Alicia M. Cases, Pablo A. Dı́az, and Horacio N. Sólimo, J. Chem. Eng. Data 52 (2007)...

Cited by (10)

Measurement and correlation of liquid–liquid equilibrium data for the ternary systems tetrabutylammonium dicyanamide + 1-propanol/2-propanol + water at different temperatures
2020, Fluid Phase Equilibria
Citation Excerpt :
Stoicescu et al. found that macromolecular n-alcohols can be used as solvents for separating NPA from its aqueous solution, and measured the LLE data for n-alcohols + 1-propanol + water [8]. Li and co-workers proposed that linalool, geraniol, and β-citronellol can also be used as proper solvents for the separation of NPA from aqueous solutions [9,10]. Wang and co-workers showed that 2-methyl-1-propanol has good extraction potential as a solvent to separate IPA from aqueous solutions [11].
In this work the ionic liquid tetrabutylammonium dicyanamide ([N_4,4,4,4][dca]) was selected as extraction solvent to separate 1-propanol (NPA) and 2-propanol (IPA) from their aqueous solutions. The experimental liquid-liquid equilibrium data for the ternary systems ([N_4,4,4,4][dca] + NPA/IPA + H₂O) were measured at 303.15, 308.15, 313.15 and 323.15 K and atmospheric pressure. The equilibrium data were correlated by the NRTL model, and the consistency of correlation parameters was checked. Furthermore, the extraction capability of [N_4,4,4,4][dca] was evaluated using distribution coefficients and selectivities. These parameters, for the ternary systems studied, increase with decreasing temperature. This study shows that [N_4,4,4,4][dca] is a promising solvent for the extraction of NPA and IPA from water.
Fundamentals of phase equilibria
2018, Thermodynamics of Phase Equilibria in Food Engineering
The purpose of this chapter is to present the basic principles of thermodynamics on phase equilibria, aiming its application in food systems. In this chapter, the main concepts are reviewed and the formulation of phase equilibrium conditions is established. Initially an appreciation of the main thermodynamic relations is presented. The concepts of thermodynamics of mixtures are also discussed. Subsequently, it is demonstrated how these properties are related to the equilibrium condition in mono and multicomponent systems. The basic elements for the phase equilibria calculations as well as phase diagrams are shown. In the final part, a debate on the concepts of equilibrium and non-equilibrium is activated from the point of view of theory applied to food systems and the reality found in the industry.
Measurement and thermodynamic modelling of ternary liquid-liquid equilibrium for extraction of thioglycolic acid from aqueous solution with different solvents
2017, Journal of Chemical Thermodynamics
Citation Excerpt :
Thermodynamic (liquid -liquid) equilibrium (LLE) data can reflect the distribution of TGA between the aqueous phase and the solvent phase in extraction process, and provide a good understanding of phase behaviour and the thermodynamic properties for ternary systems of (organic solvents + TGA + water) [5]. Therefore, the phase equilibrium behaviour is of importance for the design, operation and optimization of TGA extraction from aqueous solution [6,7]. Until now, there has been no reported LLE data for the extraction of TGA from aqueous solution.
Liquid-liquid equilibrium (LLE) data for the ternary systems {water + thioglycolic acid + (butyl acetate, isobutyl acetate or isopropyl acetate)} were determined at 293.15 K and 101.3 kPa. The solubility values were obtained by using the titration method. Moreover, the Hand and Othmer-Tobias equations were applied to validate the reliability of the obtained LLE values, and the distribution coefficients and separation factors were calculated to evaluate the solvents performances to extract thioglycolic acid from aqueous solution. The results indicate that isobutyl acetate is the best among the organic solvents studied for the separation of thioglycolic acid from aqueous solution. The thermodynamic NRTL and UNIQUAC models were used to correlate the experimental LLE results for the systems studied, and the binary interaction parameter values of the two models were optimized from the LLE correlation.
Influence of the temperature on the (liquid + liquid) phase equilibria of (water + 1-propanl + linalool or geraniol)
2017, Journal of Chemical Thermodynamics
Linalool and geraniol are the primary components of rose oil, palmarosa oil, and citronella oil and many other essential oils, and two important compounds used in the flavour and fragrance, cosmetic or pharmaceutical industries. Phase equilibria (LLE, VLE, solubility, etc.) and related thermodynamic properties of a mixture are essential in the processes design and control of mass transfer process. In this work, experimental (liquid + liquid) equilibria data of the systems (water + 1-propanl + linalool) and (water + 1-propanl + geraniol) are presented. The (liquid + liquid) equilibria of both systems were determined with a tie-line method at T = (283.15, 298.15 and 313.15) K under atmospheric pressure. The well-known Hand, Bachman and Othmer–Tobias equations were used to test the reliability of the experimental values. The influence of the temperature on the (liquid + liquid) phase equilibria of the mixtures, the binodal curves and distribution ratios of 1-propanl are shown and discussed. Moreover, the NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. Furthermore, the ternary systems could be represented using the binary parameters of the thermodynamic model with a function of temperature.
Measurement and thermodynamic modeling of ternary (liquid + liquid) equilibrium for extraction of o-cresol, m-cresol or p-cresol from aqueous solution with 2-pentanone
2017, Journal of Chemical Thermodynamics
Citation Excerpt :
And it should be noted that, after the extraction process, a solvent stripping process is usually used to recover the solvent from the aqueous phase to avoid significant solvent loss, and the extraction solvent’s concentration in the aqueous phase could be reduced to below 0.001% (mass percent) [8] after the stripping process. Thermodynamic (liquid + liquid) equilibrium (LLE) data reflect the distribution of cresols between the aqueous phase and the solvent phase in extraction process, provide a good understanding of phase behavior and the thermodynamic properties for ternary systems of {organic solvent + cresols + water} [9], and thus are important thermodynamic properties for the design, operation and optimization of cresols extraction from wastewaters [10,11]. However, only a few studies have been reported for the LLE data in cresols extraction from aqueous solution till now [12–16], searching for a new and more suitable solvent for the removal of cresols is still the primary consideration.
The (liquid + liquid) equilibrium (LLE) data are vital for the liquid extraction of cresols from aqueous solution with 2-pentanone as an extraction agent. Therefore, the ternary LLE data for {2-pentanone + o-cresol, m-cresol or p-cresol + water} were determined at T = (298.15 and 323.15) K and p = 101.3 kPa. And the reliability of the LLE data was ascertained by using the Othmer-Tobias and Hand equations. The distribution coefficients and separation factors were calculated to evaluate the effectiveness of extracting cresols from water. The thermodynamic NRTL and UNIQUAC models were used to correlate the experimental LLE data of the studied systems, and the binary interaction parameter values were obtained from the data correlation.
Determination and modeling of liquid-liquid equilibrium for ternary mixtures of methyl isopropyl ketone, cresol isomers and water
2016, Fluid Phase Equilibria
Citation Excerpt :
In this work, a new extraction solvent, methyl isopropyl ketone (MIPK), was considered for extracting cresols from aqueous solution. Precise liquid-liquid equilibrium (LLE) data are necessary for experimental studying and designing or optimizing solvent extraction process involved in wastewater treatment [23–27]. Consequently, in this work, the LLE data for the ternary systems, (MIPK + o-cresol, m-cresol, or p-cresol + water), were measured at 298.2 K and 313.2 K and 101.3 kPa, which haven't been found in any previous references to data.
Ternary liquid-liquid phase equilibria data for three systems, (methyl isopropyl ketone + o-cresol + water), (methyl isopropyl ketone + m-cresol + water) and (methyl isopropyl ketone + p-cresol + water), were determined at 298.2 and 313.2 K and 101.3 kPa. The ternary phase diagrams composed of liquid-liquid equilibrium (LLE) data were presented graphically. The performance of methyl isopropyl ketone (MIPK) in extracting cresols was evaluated by distribution coefficients and separation factors. It could be concluded from the high distribution coefficients of cresols and separation factors that MIPK is an adequate extractant to extract cresols from its dilute aqueous solutions. The experimental data were correlated by the NRTL and UNIQUAC activity coefficient models. And the deviations between the experimental data and the calculated data from the NRTL and UNIQUAC models are very small, thus the two models both could represent the studied systems well.

View all citing articles on Scopus

View full text

(Liquid + liquid) equilibria for (water + 1-propanol or acetone + β-citronellol) at different temperatures

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Experimental tie-line and reliability results

Conclusions

Acknowledgements

Fluid Phase Equilib.

Food Chem.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

Fluid Phase Equilib.

Fluid Phase Equilb.

J. Chem. Thermodyn.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Eng. Data

The Illustrated Encyclopedia of Essential Oils