Vous êtes sur la page 1sur 5

Fluid Phase Equilibria 238 (2005) 72–76

Liquid–liquid equlibria of the mixture linalool + ethanol + water


at different temperatures
A. Cháfer ∗ , J. de la Torre, R. Muñoz, M.C. Burguet
Chemical Engineering Department, University of Valencia, 46100 Burjassot, Valencia, Spain
Received 14 June 2005; received in revised form 9 September 2005; accepted 12 September 2005

Abstract
In this work, experimental liquid–liquid equilibria (LLE) data of the linalool + ethanol + water system are presented. The LLE of this system
has been measured at 293.15, 303.15, 313.15 and 323.15 K. The equilibrium data presented are correlated using NRTL and UNIQUAC equations.
Finally, the reliability of these models is tested by comparison with experimental results.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Liquid–liquid equilibria; Linalool; Ethanol; Water; UNIQUAC; NRTL

1. Introduction trate the oxygenated compounds, which are mainly responsible


for the characteristic citrus flavor and fragrance. This procedure
One of the most, if not the most, industrially significant essen- is known as “deterpenation” or “folding” and is carried out to
tial oils, is the citrus peel oil. The citrus oils are used in a wide improve oil stability, increase oil solubility, and to reduce storage
variety of applications in major industries such as flavor, food, and transport costs [2].
cosmetic, pharmaceutical and chemical industries, but the major Deterpenation is currently done by distillation, solvent
consumption by far is in the flavor industry. extraction, or chromatographic separation. The main drawbacks
Citrus oils are obtained from the small balloon-shaped glands of these conventional processes are low yields, formation of
or vesicles located in the flavedo or colored portion of the citrus thermally degraded undesirable by-products, and/or solvent con-
peel. The quality of these oils depend on factors such as soil, tamination of the products [2]. Solvent extraction is probably
climate, extraction method of the oil, weather, maturity and, the most commonly used by industry. The solvents most often
variety of the fruit [1]. employed are hexane and chloroform, because of their intrinsic
Citrus oils are complex mixtures of over 200 chemical com- characteristics of selectivity related to terpenes and oxygenated
pounds, of which more than 100 have been identified [1]. These compounds [3]. In view of a possible future food, cosmetic or
include high-volatile components such as terpenes, sesquiter- pharmaceutical application of the extract, it is necessary to use
penes and oxygenated compounds, and non-volatile compounds, solvents such ethanol or water.
such as pigments and waxes. The terpene fraction can constitute The light components of the essential oil mixtures are com-
from 50% up to more than 95% of the oil. However, this frac- pletely soluble in ethanol but not completely soluble in water.
tion gives little contribution to the flavor and fragrance of the The solution obtained by adding ethanol to water maintains the
oil. Since terpenes are mostly unsaturated compounds, they are polar characteristics of water, but its polarity is lowered by the
easily decomposed by heat, light and oxygen to unpleasant off- presence of the alcohol.
flavors and aromas. Therefore, it is common industrial practice Alcoholic extracts of citrus essential oils are particularly
to remove some of the terpenes and, as a consecuence, to concen- requested by the industry for the following reasons [4,5]: (1)
They are highly soluble in aqueous solutions and can therefore
be used to make drinks and perfumes; (2) They enhance the
∗ Corresponding author. Tel.: +34 963543434; fax: +34 963544898. aromatic strength of the mixture; (3) Oxidation reactions are
E-mail address: amparo.chafer@uv.es (A. Cháfer). reduced in the presence of the alcohol.

0378-3812/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2005.09.009
A. Cháfer et al. / Fluid Phase Equilibria 238 (2005) 72–76 73

From an industrial point of view, the knowledge of the ther- Table 1


modynamic and transport behaviour of a fluid is essential in Densities d, refractive indices nD , at 298.15 K and atmospheric pressure
the modern methods for the processes design and control. In Component d (kg m−3 ) nD
this way the phase equilibria study (VLE, LLE, . . .) supplies Experimental Literature Experimental Literature
essential information for the separation processes design and
optimization. Linalool (1) 858.08 857.74a 1.4595 1.45970a
Ethanol (2) 785.12 784.91b 1.3593 1.33594b
Unfortunately, the study of the solvent extraction technique Water (3) 997.06 997.05b 1.3325 1.33250b
is limited by the lack of data on the thermodynamic behavior
a Arce et al. [9].
of systems containing terpenes, oxygenated compounds, water b Riddick et al. [12].
and ethanol. Examination of the literature yields data on the
solubility of limonene in water at temperatures from 273.15
to 293.15 K [6,7], liquid–liquid equilibrium (LLE) data of the and (323 ± 0.1) K. Liquid mixtures were prepared in test tubes,
system d-limonene + ethanol + water from 293.15 to 323.15 K which were filled almost completely. At the end of the setting
[7,8], linalool + ethanol + water and limonene + linalool + water period (more than 6 h), samples were taken from both phases and
at 298.15 K [9]. But, no systematic evaluation has yet been per- analyzed by gas chromatography (HP 6890 Series chromato-
formed on the selectivity capacity of aqueous solutions of ethyl graph equipped with a TCD and an HP3395 integrator). Good
alcohol in relation to the percentage of water in the solvent or the separation of the four components (the components of the equi-
mass flow ratio between the solvent and essential oil mixture. librium mixture and 1-propanol) was obtained on a 2 m × 1/8 in.
As part of our research on the citrus essential oil terpeneless column packed with Porapack Q-S 80/100. The relative accuracy
by liquid–liquid extraction, we have undertaken a systematic allowed for the mole fraction measurements was ±0.001.
study of the phase equilibrium established between limonene The results of the concentrations of the three components of
[8], linalool (two main components of citrus essential oil) and both conjugate phases, and the data of the initial composition
water and ethanol acting as solvents. Also we were studied the mixture were used to check the mass balance [13]. The results
influence of the temperature on the LLE of the system. reported correspond to the values obtained using this method.
In this work, liquid–liquid phase equilibrium data have been
measured for the ternary system linalool + ethanol + water at 3. Results and discussion
temperatures ranging from 293.15 to 323.15 K. The results
obtained have been correlated using the UNIQUAC [10] and The liquid–liquid equilibrium (LLE) data of the ternary
NRTL [11] equations, in order to study the effect of the temper- linalool (1) + ethanol (2) + water (3) system at 293.15, 303.15,
ature on the parameters of these equations and consequently on 313.15 and 323.15 K and atmospheric pressure are presented
the goodness of the correlation with or without consideration of in Table 2. All concentrations are expressed in mole fractions.
the variation of temperature. The results are also graphically presented in Figs. 1-4. In these
figures, the experimental tie lines are shown for all tempera-
2. Experimental tures studied as points joined by solid lines. As can be observed,
temperature has little effect on the LLE of this system.
2.1. Chemicals Two-phase regions were observed at all temperatures investi-
gated. The system exhibited type I phase behaviour, having one
Water from NANOpure was used. Ethanol (Panreac), linalool
(Aldrich) and 1-propanol (Scharlau) had the normal purities
>99.9, >97, and >99.9 mass%, respectively. 1-Propanol is used
as solvent in the chromatographic analysis. Prior to the measure-
ments, chemical purities were checked with gas chromatogra-
phy. The refractive indices and densities of pure liquids were
measured at 298.15 K and atmospheric pressure using an Abbe
refractometer Atago and an Anton Paar DMA 58 densimeter,
respectively. Temperature was controlled to ±0.01 K with a
thermostated batch. The accuracy in refractive index and den-
sity measurements are ±0.0002 and ±0.01 kg m−3 , respectively.
The experimental values of these properties are given in Table 1
together with those given in the literature [7,12].

2.2. Equilibrium measurements

Measurements were made at four temperatures. Equilibrium Fig. 1. LLE of system linalool (1) + ethanol (2) + water (3) at 293.15 K: exper-
imental LLE data from this work: () organic phase, () aqueous phase; (—)
data were obtained by preparing mixtures of known overall com- binodal curve calculated using UNIQUAC model; experimental tie lines (solid
position by mass, followed by stirring and setting for at least 24 h lines); UNIQUAC tie lines (dashed lines, calculated with the parameters of
at constant temperature: (293 ± 0.1), (303 ± 0.1), (313 ± 0.1), Table 4).
74 A. Cháfer et al. / Fluid Phase Equilibria 238 (2005) 72–76

Table 2
Liquid–liquid equilibrium data of linalool (1) + ethanol (2) + water (3) system at
293.15, 303.15, 313.15 and 323.15 K
Temperature (K) Organic phase Aqueous phase

x1 x2 x1 x2

293.15 0.118 0.352 0.010 0.223


0.184 0.364 <0.001 0.190
0.303 0.344 <0.001 0.144
0.368 0.302 <0.001 0.113
0.419 0.268 <0.001 0.103
0.480 0.226 <0.001 0.089
0.562 0.165 <0.001 0.057
0.601 0.132 <0.001 0.042
0.666 0.079 <0.001 0.025
0.745 0.000 <0.001 0.000
303.15 0.109 0.328 0.011 0.215 Fig. 3. LLE of system linalool (1) + ethanol (2) + water (3) at 313.15 K: exper-
0.198 0.342 <0.001 0.171 imental LLE data from this work: () organic phase, () aqueous phase; (—)
0.238 0.335 <0.001 0.156 binodal curve calculated using UNIQUAC model; experimental tie lines (solid
0.319 0.321 <0.001 0.143 lines); UNIQUAC tie lines (dashed lines, calculated with the parameters of
0.379 0.299 <0.001 0.133 Table 4).
0.484 0.238 <0.001 0.088
0.578 0.173 <0.001 0.060
0.678 0.084 <0.001 0.025
0.785 0.000 <0.001 0.000
313.15 0.106 0.309 0.013 0.212
0.235 0.328 <0.001 0.168
0.326 0.307 <0.001 0.117
0.462 0.240 <0.001 0.086
0.558 0.177 <0.001 0.058
0.656 0.093 <0.001 0.028
0.756 0.000 <0.001 0.000
323.15 0.126 0.298 0.011 0.198
0.231 0.316 <0.001 0.164
0.340 0.292 <0.001 0.123
0.442 0.249 <0.001 0.084
0.544 0.172 <0.001 0.051
0.621 0.101 <0.001 0.024
0.741 0.000 <0.001 0.000
Fig. 4. LLE of system linalool (1) + ethanol (2) + water (3) at 323.15 K: exper-
imental LLE data from this work: () organic phase, () aqueous phase; (—)
binodal curve calculated using UNIQUAC model; experimental tie lines (solid
lines); UNIQUAC tie lines (dashed lines, calculated with the parameters of
Table 4).

pair of partially miscible components (linalool + water) and two


pairs of completely miscible components (linalool + ethanol and
ethanol + water), in the temperature range investigated.
In Fig. 5, the temperature effect on the distribution of ethanol
between the aqueous phase and the organic phase is visualized: at
higher temperature the solubility of ethanol in the organic phase

Table 3
The pure component relative van der Waals volume (ri ) and van der Waals
surface area (qi ) used in the correlation of experimental data by UNIQUAC
Compound ri qi

Linalool 7.0356a 6.060a


Fig. 2. LLE of system linalool (1) + ethanol (2) + water (3) at 303.15 K: exper-
Ethanol 2.5755b 2.588b
imental LLE data from this work: () organic phase, () aqueous phase; (—)
Water 0.9200b 1.400b
binodal curve calculated using UNIQUAC model; experimental tie lines (solid
lines); UNIQUAC tie lines (dashed lines, calculated with the parameters of a Bondi [14].
Table 4). b Magnussen et al. [15].
A. Cháfer et al. / Fluid Phase Equilibria 238 (2005) 72–76 75

Table 4
UNIQUAC and NRTL binary interaction parameters for linalool (1) + ethanol (2) + water (3) system
T (K) Comp (ij) UNIQUAC parameters rmsd NRTL parameters rmsd

Aij (J/mol) Aji (J/mol) α Aij (J/mol) Aji (J/mol)

293.15 1–2 −771.08 −1159.94 0.027 0.2 −5336.60 −317.28 0.027


1–3 3121.23 295.33 −461.62 16585.57
2–3 6259.91 −3279.28 7921.79 −4356.57
303.15 1–2 −1067.42 −960.62 0.025 0.2 −2072.63 −555.42 0.034
1–3 4041.39 −23.36 −73.65 8745.81
2–3 1407.69 −2092.52 4156.99 −2028.21
313.15 1–2 784.63 −2015.41 0.024 0.2 −4575.83 −903.03 0.029
1–3 3460.37 510.92 −198.55 19218.90
2–3 4533.93 −2755.31 8784.16 −4674.19
323.15 1–2 887.65 −1978.83 0.028 0.2 −4183.31 −1567.85 0.025
1–3 4069.90 −52.38 −335.32 18434.85
2–3 4344.77 −2308.49 8750.49 −4462.67

was set to 0.1, 0.2, and 0.3 and the results given in Tables 4 and 5
are the best of the three sets (αij = 0.2 for all the binary
pairs).
There are two effective binary interaction parameters for a
pair of substances. Therefore, six effective binary interaction
parameters are required for a ternary system. The correspond-
ing sets of binary interaction parameters were determined by
minimizing the differences between the experimental and cal-
culated mole fractions for each of the components over all the
tie lines. The objective function (OF) used is
M 
 2 
3
OF = (xijk − x̂ijk )2 (1)
k=1 j=1 i=1

where M is the number of tie lines, x indicates the experi-


mental mole fraction, x̂ the calculated mole fraction, and sub-
scripts i, j and k denote, respectively, component, phase and tie
Fig. 5. Influence of temperature on the distribution of ethanol between the line.
aqueous phase and the organic phase in the system linalool + ethanol + water: First the correlation of experimental data was carried out sep-
T = 293.15 K (♦); T = 303.15 K (); T = 313.15 K (); T = 323.15 K ().
arately at each temperature. The parameters (Aij ) calculated in
this way are given in Table 4. Also included in this table is the
decreases to a larger extent than the solubility in the aqueous root-mean-square deviation (rmsd) in the phase composition
phase.  1/2
M  2 3
The UNIQUAC [10] and NRTL [11] models were used to (x ijk − x̂ )2
ijk 
rmsd =  (2)
correlate the experimental data for the ternary system discussed 6M
k=1 j=1 i=1
here. In fitting the UNIQUAC equation, the structural param-
eters, (ri and qi ) recommended by Bondi [14] and Magnussen The rmsd is a measure of the agreement between the experi-
et al. [15], were used for the pure components and are listed in mental and calculated data. In Table 4 it can be observed that
Table 3. The non-randomness parameter (αij ) of the NRTL model the UNIQUAC model provides a slightly better correlation of

Table 5
Optimized binary interaction parameters with negligible dependence of temperature for the linalool (1) + ethanol (2) + water (3) system
Comp (ij) UNIQUAC parameters rmsd NRTL parameters rmsd

Aij (J/mol) Aji (J/mol) α Aij (J/mol) Aji (J/mol)

1–2 4621.11 5845.77 0.032 0.2 −4486.20 7734.30 0.029


1–3 1552.05 3023.95 −157.31 19352.60
2–3 −1557.93 −2923.01 −670.56 −4472.65
76 A. Cháfer et al. / Fluid Phase Equilibria 238 (2005) 72–76

the experimental tie lines than NRTL based on rmsd values and Greek letter
although a good fit is obtained for all temperatures, the param- α non-randomness factor
eters determined for each temperature have no relation between
them. Subscripts
Further, a simultaneous correlation of all the experimental i component i
LLE data of this system was carried out in order to obtain a j component j
unique set of parameters valid for the range of temperatures k component k
studied. Table 5 list the optimized UNIQUAC and NRTL inter-
action parameters (Aij ) obtained in a simultaneous correlation Superscript
of all data assuming that their dependence with temperature is ˆ calculated
negligible. The overall magnitude of rmsd values suggests that
the NRTL and UNIQUAC models provide an adequate represen- References
tation of the phase behavior of the ternary linalool (1) + ethanol
(2) + water (3) system at all temperatures. [1] R.W. Wolford, J.W. Kesterson, J.A. Attaway, J. Agric. Food Chem. 19
(1971) 1097–1105.
[2] P. Dugo, L. Mondello, K.D. Bartle, A.A. Clifford, D.G.P.A. Breen, Fla-
4. Conclusions vor Fragrance J. 10 (1995) 51–58.
[3] R.M. Pangborn, G.F. Russel, in: O.R. Fennema (Ed.), Principles of Food
Liquid–liquid equilibrium of the linalool + ethanol + water Science. Part I. Food Chemistry, Marcel Dekker Inc., New York, 1976,
system has been measured at different temperatures. The LLE pp. 427–464.
data were correlated using the NRTL and UNIQUAC activity [4] C. Babdyopadhyay, in: A. Biswas (Ed.), Frontiers of Applied Chemistry,
Springer-Verlag, New York, 1989, pp. 206–221.
coefficient models. The correlation with the UNIQUAC equa- [5] J. Broderick, Manuf. Chem. 25 (1995) 112–114.
tion gives better results than the NRTL equation with a value [6] H.A. Massaldi, C.J. King, J. Chem. Eng. Data 18 (1973) 393–397.
of the non-randomness parameter at 0.2 and fits the experi- [7] F. Gironi, I. Gonzalez Farias, L. Lamberti, J. Chem. Eng. Data 40 (1995)
mental data satisfactorily. The simultaneous correlation of the 578–581.
four isothermal data sets gives a unique set of parameters [8] A. Chafer, R. Muñoz, M.C. Burguet, A. Berna, Fluid Phase Equilibr.
224 (2004) 251–256.
in the range of the temperature considered, increasing their [9] A. Arce, A. Marchiaro, A. Soto, J. Solut. Chem. 33 (2004) 561–569.
application. [10] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144.
[11] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116–128.
List of symbols [12] J.A. Riddick, W.B. Bunger, T.K. Sakano, Organic Solvents. Physical
A interaction parameters Properties and Methods of Purification, 4th ed., Wiley, 1986.
[13] V. Gomis, F. Ruı́z, J.C. Asensi, M.D. Saquete, Fluid Phase Equilibr. 129
M number of tie lines (1997) 15–19.
q area parameter in UNIQUAC equation [14] A. Bondi, Physical properties of Molecular Crystals, Liquids and
r volume parameter in UNIQUAC equation Glasses, Wiley, New York, 1968.
rmsd root-mean-square deviation [15] T. Magnussen, P. Rasmussen, A. Fredenslund, Ind. Eng. Chem. Process
x composition of liquid phase Des. Dev. 20 (1981) 331–339.