Journal of Solution Chemistry, Vol. 33, No.

5, May 2004 (

C 2004)

Liquid–Liquid Equilibria of Linalool + Ethanol +

Water, Water + Ethanol + Limonene, and
Limonene + Linalool + Water Systems
Alberto Arce,1,∗ Alicia Marchiaro,2 and Ana Soto1

Received March 12, 2004; revised April 15, 2004

The present work was undertaken to determine liquid–liquid equilibria for ternary
systems involved in the citrus essential oil terpeneless using dilute alcohol. Tie-line data
have been determined for the linalool + ethanol + water, water + ethanol + limonene,
and limonene + linalool + water ternary systems at 298.15 K. The experimental
data were satisfactorily correlated using the UNIQUAC and NRTL equations, and the
obtained binary interaction parameters are reported. The UNIFAC group-contribution
method did not allow adequate predictions of liquid–liquid equilibria involved in this
study.

KEY WORDS: LLE; limonene; linalool; ethanol; essential oil.

1. INTRODUCTION
Essential oils are plant products, usually somewhat volatile, giving the odors
and tastes characteristic of the particular plant, thus possessing the essence.
They are basically a mixture of terpenic hydrocarbons and oxygenated deriva-
tives. Among their components, oxygenated compounds are generally considered
preferable due to odor, and their content has become a definitive parameter in
establishing the price of the oil and representing its quality.
Citrus oil is an essential oil, the two main components are the terpene hy-
drocarbon limonene and the oxygenated terpenoid linalool. The present work was
undertaken to evaluate the aqueous solutions of ethanol as agents for their sep-
aration. With this in mind, we have determined liquid–liquid equilibria (LLE)
for linalool + ethanol + water, water + ethanol + limonene, and limonene +
1 Department of Chemical Engineering, University of Santiago de Compostela, E-15782 Santiago,
Spain; e-mail: eqaaarce@usc.es.
2 Present address: Facultad de Ciencias Naturales, Universidad Nacional de la Patagonia, Provincia del

Chubut Argentina.

561
0095-9782/04/0500-0561/0

C 2004 Springer Science+Business Media, Inc.
562 Arce, Marchiaro, and Soto

Fig. 1. Experimental tie-lines for linalool + ethanol + water, water + ethanol

+ limonene, and limonene + linalool + water ternary systems at 298.15 K.

linalool + water ternary systems at 298.15 K. In the literature(1) we have only

found LLE data for the water + ethanol + limonene system at 293 K.
The experimental data have also been correlated using the UNIQUAC and
NRTL equations, and have been compared with the predictions of the UNIFAC
group contribution method.

2. EXPERIMENTAL
All chemicals used were chromatography-grade products, supplied by Fluka
with nominal purities of 98 mass% for limonene (4-isopropenyl-1-methyl-
cyclohexene) and 97 mass% for linalool (3,7-dimethyl-1,6-octenedien-3-ol), and
by Merk with nominal purity of 99.8 mass% for ethanol. Water was purified us-
ing a Milli-Q plus system. These purities were verified by gas chromatography
and the chemicals were used without further purification. Their densities and re-
fractive indices were measured at 298.15 K and atmospheric pressure, and are
compared with published values(2,3) in Table I. Densities were measured with an
Anton Paar DMA 60/602 densimeter precise to within ±10−5 g-cm−3 . Refractive
indices were measured with an Atago RX-5000 refractometer with an accuracy
of ±4 × 10−5 .
First, solubility curves at 298.15 K were determined by the cloud-point
method.(4) These curves were used to calibrate the gas chromatograph by an
internal standard method. The chromatograph used was an Hewlett-Packard 5890
Series II apparatus equipped with a thermal conductivity detector and an HP-FFAP:
Liquid–Liquid Equilibria for Ternary Solvents 563

Table I. Densities (ρ) and Refractive Indices (n D ) of the Pure Components at

298.15 K and Atmospheric Pressure

ρ (g-cm−3 ) nD
Component Experimental Literature Experimental Literature

Limonene 0.83717 0.8383(2) 1.47027 1.4701(2)

Linalool 0.85774 0.85760(3) 1.45970 Not found
Ethanol 0.78522 0.78493(2) 1.35920 1.35941(2)
Water 0.99704 0.99704(2) 1.33250 1.33250(2)

25 m × 0.2 mm × 0.3 µm capillary column. Helium was used as the mobile phase.
The injection volume was 0.5 µL, and the split ratio was 1:100. Separation was
performed to 403.15 K under isothermal conditions. The greatest errors in the
determination of the mole fraction compositions using the calibration curves were
±0.003.
The tie-line data were determined by analysis of the two layers of heteroge-
neous mixtures. In each case, a mixture with a bulk composition in the immiscibil-
ity region was placed inside an equilibrium cell, where it was stirred for 1 h in order
to ensure intimate contact between the phases and was then left standing for 4 h to
achieve thermodynamic equilibrium (the time necessary to attain equilibrium, no
variation of compositions with time, was established in preliminary experiments).
The whole procedure was carried out at constant temperature using water from a
thermostat (Selecta Ultraterm 6000383) and the water temperature was measured
with a thermometer Heraeus Quat 100 precise to within ±0.01 K. When ther-
modynamic equilibrium had been attained, samples of both liquid phases were
collected and analyzed by gas chromatography.

3. RESULTS
The experimental tie-line data for linalool + ethanol + water, water +
ethanol + limonene, and limonene + linalool + water systems at 298.15 K are
listed in Tables II, III, and IV, respectively. Figure 1 shows experimental tie-lines
for these equilibria.

4. DATA TREATMENT
4.1. Correlation
The experimental data were correlated using the widely employed NRTL(5)
and UNIQUAC(6) equations. The value of the NRTL nonrandomness parameter
was set successively to 0.1, 0.2, and 0.3, and the results given below are in each
case the best of these three sets. The UNIQUAC structural parameters r and q
564 Arce, Marchiaro, and Soto

Table II. Experimental Tie-Lines of the System Linalool (1) + Ethanol (2) + Water (3)

[T = 298.15 K]
Aqueous phase Organic phase

x1 x2 x3 x1 x2 x3

0.0002 0.0000 0.9998 0.8099 0.0000 0.1901

0.0003 0.0194 0.9803 0.7228 0.0681 0.2092
0.0003 0.0441 0.9556 0.6230 0.1496 0.2274
0.0004 0.0623 0.9373 0.5491 0.2061 0.2448
0.0005 0.0847 0.9148 0.4360 0.2784 0.2856
0.0006 0.1107 0.8887 0.3614 0.3324 0.3062
0.0009 0.1260 0.8731 0.3041 0.3587 0.3372
0.0017 0.1487 0.8496 0.2287 0.3804 0.3909
0.0035 0.1712 0.8253 0.1704 0.3787 0.4509
0.0083 0.2032 0.7885 0.1205 0.3601 0.5194

Note. Compositions are given as mole fractions.

were taken from literature.(7−9) The computer program used to fit these equations
minimizes the objective function




FO = (xi jk − x̂i jk )2 (1)
k i j

Table III. Experimental Tie-Lines of the System Water (1) + Ethanol (2) + Limonene (3)

[T = 298.15 K]
Aqueous phase Organic phase
x1 x2 x3 x1 x2 x3

0.0000 0.0065 0.9935 0.9924 0.0053 0.0022

0.0000 0.0962 0.9038 0.9826 0.0157 0.0017
0.0001 0.1468 0.8532 0.9696 0.0256 0.0048
0.0003 0.2158 0.7839 0.9798 0.0172 0.0030
0.0008 0.2604 0.7389 0.9659 0.0317 0.0024
0.0016 0.3350 0.6634 0.9520 0.0450 0.0030
0.0043 0.4108 0.5848 0.9342 0.0602 0.0056
0.0066 0.4509 0.5425 0.9326 0.0611 0.0064
0.0121 0.5117 0.4763 0.9199 0.0737 0.0064
0.0204 0.5613 0.4182 0.9197 0.0742 0.0061
0.0498 0.6748 0.2754 0.8097 0.1698 0.0204
0.0726 0.6959 0.2315 0.7669 0.2098 0.0233
0.0996 0.7005 0.2000 0.7164 0.2558 0.0278
0.2624 0.6134 0.1242 0.5263 0.4141 0.0595

Note. Compositions are given as mole fractions.

Liquid–Liquid Equilibria for Ternary Solvents 565

Table IV. Experimental Tie-Lines of the System Limonene (1) + Linalool (2) +
Water (3)

[T = 298.15 K]
Aqueous phase Organic phase
x1 x2 x3 x1 x2 x3

0.0000 0.0000 1.0000 0.9978 0.0000 0.0022

0.0000 0.0000 1.0000 0.9141 0.0824 0.0035
0.0000 0.0001 0.9999 0.8022 0.1848 0.0130
0.0000 0.0001 0.9999 0.7371 0.2431 0.0198
0.0000 0.0001 0.9999 0.6465 0.3263 0.0272
0.0000 0.0001 0.9999 0.5653 0.3912 0.0435
0.0000 0.0001 0.9999 0.4386 0.4989 0.0625
0.0000 0.0001 0.9999 0.3107 0.5914 0.0979
0.0000 0.0001 0.9999 0.2395 0.6491 0.1115
0.0000 0.0001 0.9999 0.1808 0.6849 0.1343
0.0000 0.0001 0.9999 0.0889 0.7477 0.1634
0.0000 0.0002 0.9998 0.0101 0.7935 0.1964

Note. Compositions are given as mole fractions.

where xi jk is the experimental mole fraction component i in phase j on tie-line k,

x̂i jk is the value calculated using the parameters being optimized.
Table V lists the binary interaction parameters obtained for the ternary sys-
tems, and for both UNIQUAC and NRTL equations. The quality of the correlation
is measured by the residual function F
 0.5



(xi jk − x̂i jk )2
F = 100   (2)
k i j
6M

where M is the number of experimental tie-lines.

Figure 2 compares experimental tie-lines for linalool + ethanol + water,
water + ethanol + limonene, and limonene + linalool + water systems with those
calculated using the NRTL (α = 0.1) equation.

4.2. Prediction
Figure 3 compares the experimental data with those predicted by the UNIFAC
method(10) using interaction and structural parameters taken from literature.(11) The
corresponding F values, Eq. (2), at 298.15 K are 5.74, 2.79, and 3.24, for linalool +
ethanol + water, water + ethanol + limonene, and limonene + linalool + water
systems, respectively.
566 Arce, Marchiaro, and Soto

Table V. Binary Interaction Parameters and Residual Functions, Eq. (2), for UNIQUAC and NRTL
Models Fitted to LLE Data for Linalool + Ethanol + Water, Water + Ethanol + Limonene, and
Limonene + Linalool + Water Systems at 298.15 K

Model Pair i– j Parameters (J-mol−1 ) F

Linalool (1) + ethanol (2) + water (3)

NRTL (α = 0.1) 1–2 −124.24 2492.50
1–3 −4715.43 21325.95
2–3 −5358.37 11483.59 0.5192
UNIQUAC 1–2 2394.36 −583.44
1–3 4070.65 44.890
2–3 −605.51 926.57 0.6373
Water (1) + ethanol (2) + limonene (3)
NRTL (α = 0.1) 1–2 25212.54 −13092.41
1–3 26840.47 4268.60
2–3 5677.56 −716.43 0.8517
UNIQUAC 1–2 953.74 −831.33
1–3 3781.88 10441.52
2–3 −615.71 3691.14 2.0005
Limonene (1) + linalool (2) + water (3)
NRTL (α = 0.1) 1–2 −7312.14 146.41
1–3 7772.34 8645.72
2–3 −4888.77 20891.34 0.1599
UNIQUAC 1–2 1460.48 −1515.00
1–3 9258.17 3831.24
2–3 3246.14 569.75 0.1143

Structural parameters for the UNIQUAC equation

Limonene(6) Linalool(6) Ethanol(7) Water(8)

r 6.2783 7.0356 2.1055 0.92

q 5.2080 6.0600 1.972 1.40

5. CONCLUSIONS
With the aim to evaluate the possibility of using aqueous solutions of ethanol
as agents for limonene–linalool mixtures separation, we have determined liquid–
liquid equilibrium (LLE) for linalool + ethanol + water, water + ethanol +
limonene, and limonene + linalool + water ternary systems at 298.15 K.
Limonene and linalool are completely soluble in ethanol but not quite com-
pletely soluble in water. Ternary equilibria established between ethanol and
water with limonene and linalool, have opposite tie-lines slopes. The next step
of our work is to determine quaternary liquid–liquid equilibria. This
will allow us to evaluate the influence of limonene–linalool ratio in essential
oil, and the percentage of water the solvent, on the effectiveness of
extraction.
Liquid–Liquid Equilibria for Ternary Solvents 567

Fig. 2. Experimental tie-lines for linalool + ethanol + water, water + ethanol + limonene, and
limonene + linalool + water systems at 298.15 K (——o), and those obtained optimizing a NRTL
(α = 0.1) model (- - -∇).

These ternary liquid–liquid equilibria were satisfactorily fitted by both the

UNIQUAC and the NRTL equations in most of the cases, only in the UNIQUAC
correlation of water + ethanol + limonene did we find high deviations between the
experimental and correlated data. The corresponding optimized binary interaction
parameters are reported in Table V.
The experimental data were not satisfactorily predicted by the UNIFAC
method. This method was able to predict tie-lines slopes but deviations found
between experimental and predicted compositions were very high. Prediction
methods frequently provide rough approximations, therefore, it will be always
necessary to obtain at least a few reliable experimental results.
568 Arce, Marchiaro, and Soto

Fig. 3. Experimental tie-lines for linalool + ethanol + water, water + ethanol + limonene, and
limonene + linalool + water systems at 298.15 K (——o), and those predicted using the UNIFAC
method (- - - 䊐).

ACKNOWLEDGMENTS
The authors are grateful to the Ministerio of Ciencia y Tecnologı́a (Spain) for
financial support under project PPQ2003-01236. A.M. is grateful to the European
Union for financial support (Project ALFA-PROQUIFAR).

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