J. Chem.

Thermodynamics 2002, 34, 1431–1437

doi:10.1016/S0021-9614(02)00189-1
Available online at http://www.idealibrary.com on

Isobaric (vapour þ liquid) equilibria

of (linalool þ 1propanol) and
(linalool þ 1butanol)

Dongshun Deng, Haoran Li, and Shijun Hana

Department of Chemistry, Zhejiang University, Hangzhou 310027,
PR China

The isobaric (vapour + liquid) equilibria (VLE) data for (linalool + 1-propanol) and
(linalool + 1-butanol) at the pressures p ¼ (20.00, 30.00, 40.00, 50.00, and 60.00) kPa
were measured using an inclined ebulliometer with a pump-like stirrer. The equilibrium
liquid compositions were corrected by taking account of the effects of evaporation ratio
and vapour-phase holdup. The corrected VLE data have been correlated using the
UNIQUAC equation with the temperature-dependence binary parameters to model the
liquid-phase and the viral equation of state to model the vapour-phase. Experimental
vapour pressures of linalool are also included. Ó 2002 Elsevier Science Ltd. All rights reserved.

KEYWORDS: (vapour + liquid) equilibria; linalool; 1-propanol; 1-butanol; ebulliometer

1. Introduction
Linalool (3,7-dimethyl-3-hydroxy-1,6-octadiene, CAS: [78-70-6]), a leuco transparent
liquid with strong odour, is one of the most important fractions in citrus oil which is
widely used as a raw material of flavour. It is also one of the intermediates for the
synthesis of vitamin. The (vapour + liquid) equilibria (VLE) are important and
necessary to the design of separation processes and to optimize unit operation pro-
cesses in chemical engineering. The present paper reports the measured and corrected
isobaric (vapour + liquid) equilibrium data for (linalool + 1-propanol) and (linal-
ool + 1-butanol) at the pressures p ¼ (20.00, 30.00, 40.00, 50.00, and 60.00) kPa. The
measured isobaric VLE data are analyzed using the UNIQUAC equation with the
temperature-dependence binary parameters. The vapour pressures of linalool were also
determined.
The survey of the literature shows that the experimental isobaric VLE data for the
above binary systems are not available.

a
To whom correspondence to be addressed (E-mail: [email protected], [email protected]).

0021-9614/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
1432 D. Deng et al.

2. Experimental
The 1-propanol and 1-butanol (analytical reagent grade, supplied by Shanghai Chemical,
PR China) were refluxed over freshly activated CaO for at least 4 h and then fractionally
distilled. Linalool (highest commercial grade, Zhejiang NHU) was distilled by using a
150 cm-high column under the reduced pressure. The refined reagents were dried and
stored over type 0.4 nm sieves in the dark at about T ¼ 298:15 K. The storage did not
exceed 10 days. The purities of the materials checked by gas chromatography area
analysis were better than 0.995 mass fraction. The physical properties of the pure ma-
terials are listed in table 1 along with literature values.
An inclined ebulliometer with a pump-like stirrer was used to measure the isobaric
(vapour + liquid) equilibria data as described previously.ð6Þ The temperature inside the
ebulliometer was measured with a standard platinum resistance thermometer connected
to a digital multimeter (Keithley 195A) with final accuracy of 0.01 K. The pressure was
indirectly measured by the boiling temperature of pure water in a separate ebulliometer.
All the mixtures were prepared by directly weighing and the uncertainty on the com-
position measurements was estimated to be 0.0001 in mole fraction.

3. Data reduction
The principle of ebulliometric determination of vapour and liquid equilibrium consists in
measuring the boiling temperature at constant pressure or the equilibrium pressure at
constant temperature as a function of the gravimetrically determined composition of
solutions. But for the systems with components largely differing in boiling points, the
difference between the overall composition x0i and the equilibrium liquid composition xi
is not negligible.ð7Þ The ‘‘real’’ or equilibrium liquid composition correction becomes
critical. While this causes no instability in the data reduction, heavy reliance must be
placed on the estimated values for the vapour space and the liquid holdup.ð8Þ The equi-
librium liquid composition xi is related to the overall composition x0i by the following
non-linear equation set:ð9Þ
x01 ¼ y1 ðnv =nÞ þ x1 ðnl =nÞ þ ðfy1 þ x1 Þð1  nl =n  nv =nÞ=ð1 þ f Þ; ð1Þ

TABLE 1. Physical properties of pure materials: density d, refractive index n,

and normal boiling point

Materials d (298.15 K)/ðg  cm3 Þ n (D, 298.15 K) Tb (101.325 kPa)/K

Exptl. Lit. Exptl. Lit. Exptl. Lit.

ð1Þ ð1Þ
Linalool 0.8720 0.8733 1.4637 1.4673 361.11 362.15ð1Þ
(293.15 K) (293.15 K) (1.867 kPa)
1-Propanol 0.79960 0.79965ð2Þ 1.3830 1.3833ð2Þ 370.24 370.30ð4Þ
1-Butanol 0.80594 0.80589ð3Þ 1.3961 1.3970ð3Þ 390.50 390.43ð5Þ
 Isobaric equilibria (vapour+liquid) 1433

where f is the reflux ratio and n the total number of moles in the ebulliometer. The
vapour-phase holdup, nv , includes the non-condensed vapour in the equilibrium chamber
and, in the main, as well as the condensate in the cooler and the tubing. The liquid-phase
holdup, nl , is caused by the presence of a film of the equilibrium liquid on the ther-
mometer well and on the wall of the equilibrium chamber. Detailed effects of evaporation
ratio, liquid-phase holdup and vapour-phase holdup on the magnitude of the correction
results have been discussed in the literature.ð10Þ According to the design of the ebulli-
ometer used, the liquid-phase holdup and the vapour-phase holdup were set to be 0 and
0.02, respectively. After the calibration through several systems exerting a large boiling
point difference for which reliable and accurate PTx data were available from the liter-
ature, the average value of evaporation ratio was 0.015. Dependence of the above cor-
relation factors, the equilibrium compositions of the determined systems were obtained
and listed in tables 2 and 3.

4. Results and discussion

The isobaric experimental data and calculated vapour compositions for the binary sys-
tems (linalool + 1-propanol) and (linalool + 1-butanol) are presented in tables 2 and 3.
The following fundamental equation can be used to calculate the (vapour + liquid)
equilibrium:

 
pyi /i ¼ pis /si xi ci exp vLi ð p  pis =RT ; ð2Þ
where p is the total pressure, xi and yi are the corrected liquid-phase and calculated
vapour-phase mole fractions of component i, respectively. /i is the vapour-phase fugacity

TABLE 2. Isobaric VLE data and calculated vapour composition for

{linalool (1) + 1-propanol (2)}

x01 x1 20.00 kPa 30.00 kPa 40.00 kPa 50.00 kPa 60.00 kPa
(nominal) (corrected) T/K y1 T/K y1 T/K y1 T/K y1 T/K y1

0.0000 0.0000 332.98 0.0000 341.39 0.0000 347.76 0.0000 352.88 0.0000 357.18 0.0000
0.0499 0.0513 333.49 0.0013 341.65 0.0017 348.60 0.0016 354.33 0.0014 358.83 0.0014
0.0998 0.1033 334.27 0.0029 342.60 0.0033 349.66 0.0033 355.44 0.0033 359.96 0.0034
0.2003 0.2072 336.76 0.0064 345.19 0.0066 352.33 0.0072 358.20 0.0079 362.79 0.0084
0.2997 0.3100 339.86 0.0104 347.75 0.0104 354.69 0.0117 360.66 0.0133 365.67 0.0145
0.4986 0.5156 346.02 0.0220 354.88 0.0232 362.46 0.0264 368.75 0.0299 373.75 0.0324
0.7002 0.7231 356.30 0.0529 366.06 0.0589 374.41 0.0666 381.35 0.0736 386.86 0.0784
0.8077 0.8324 366.75 0.1053 377.48 0.1176 386.55 0.1317 393.96 0.1442 399.72 0.1525
0.9088 0.9219 383.80 0.2558 394.91 0.2720 404.50 0.2984 412.59 0.3238 419.16 0.3417
0.9487 0.9643 398.12 0.4822 408.92 0.4903 418.37 0.5225 426.48 0.5548 433.24 0.5775
1.0000 1.0000 416.80 1.0000 428.78 1.0000 437.86 1.0000 445.26 1.0000 451.55 1.0000
1434 D. Deng et al.

TABLE 3. Isobaric VLE data and calculated vapour composition for

{linalool (1) + 1-butanol (2)}

x01 x1 20.00 kPa 30.00 kPa 40.00 kPa 50.00 kPa 60.00 kPa
(nominal) (corrected)
T/K y1 T/K y1 T/K y1 T/K y1 T/K y1

0.0000 0.0000 351.12 0.0000 360.01 0.0000 366.77 0.0000 372.15 0.0000 376.73 0.0000
0.0496 0.0513 351.64 0.0035 360.30 0.0045 367.68 0.0040 373.78 0.0038 377.53 0.0048
0.0998 0.1031 352.60 0.0068 361.18 0.0081 368.48 0.0077 374.49 0.0089 379.73 0.0108
0.1998 0.2064 355.28 0.0142 364.01 0.0158 371.46 0.0161 377.62 0.0210 381.87 0.0236
0.3000 0.3099 357.22 0.0236 365.97 0.0254 373.63 0.0269 380.21 0.0349 384.43 0.0372
0.5000 0.5155 364.63 0.0562 373.58 0.0588 381.41 0.0640 388.12 0.0738 391.35 0.0731
0.6999 0.7197 374.99 0.1341 384.73 0.1398 393.26 0.1521 400.59 0.1630 404.15 0.1579
0.7999 0.8195 383.00 0.2238 393.72 0.2334 402.88 0.2512 410.48 0.2700 415.10 0.2652
0.9055 0.9176 396.37 0.4317 407.40 0.4465 417.05 0.4687 425.34 0.5116 431.26 0.5138
0.9472 0.9571 405.14 0.6129 416.56 0.6283 425.34 0.6466 434.48 0.6980 439.80 0.7012
1.0000 1.0000 416.80 1.0000 428.78 1.0000 437.86 1.0000 445.26 1.0000 451.55 1.0000

coefficient of component i, ci is the liquid-phase activity coefficient. The vLi is the pure
liquid molar volume calculated from the modified Rackett equation.ð11Þ psi , the saturated
vapour pressure, is calculated with the Antoine equation
 
log pis =kPa ¼ A  B=fC þ T ðKÞg: ð3Þ
For 1-propanol and 1-butanol, the Antoine constants given in Kemme et al.ð12Þ were
used. The experimental vapour pressure data of pure linalool are listed in table 4. The
constants in equation (3) were fitted by a non-linear optimization method to minimize the
mean relative deviation in psi . The /i and /si were calculated from virial equation:
!
X XX
ln /i ¼ 2 yj Bij  yi yj Bij p=RT ; ð4Þ
j i j

TABLE 4. Experimental vapour pressures of linalool

T/K pis /kPa T/K pis /kPa T/K pis /kPa T/K pis /kPa
409.38 15.23 429.04 30.24 446.68 52.03 465.81 88.73
414.26 18.30 433.19 34.95 450.53 58.09
418.60 21.34 438.39 40.51 454.99 65.79
424.21 25.90 442.66 46.04 459.77 75.17
A B C
Linalool 5.81618 1329.37 )122.37
 Isobaric equilibria (vapour+liquid) 1435

TABLE 5. The physical property parameters of pure materials

Materials Pc /kPa Tc /K Vc /(cm3  mol3 ) RD/A DM/D r q

1-Propanol 51.70 536.71 218.20 2.74 1.68 2.78 2.51
1-Butanol 44.13 562.93 274.60 3.23 1.66 3.45 3.05
Linalool 24.28 631.80 545.00 4.10 1.58 6.82 5.84

where the second virial coefficient of pure materials Bii and mixtures Bij were calculated
according to the method of Hayden and OÕConnell.ð13Þ For 1-propanol and 1-butanol, the
physical properties were obtained from the literature.ð14Þ The critical properties of linalool
were estimated by the method of Lydersen and Edmister,ð15Þ which is a group contri-
bution method. The mean rotation radius RD was estimated using the method provided by
Fredenslund et al.ð16Þ The dipole moment DM was calculated according to the method of
Smyth et al.ð17Þ Pure-component parameters r and q are calculated according to the
method given in the literature.ð18Þ The parameters of the physical properties for the pure
materials are listed in table 5.
The liquid-phase activity coefficient ci was calculated from the UNIQUAC equa-
tion.ð19Þ The parameters of the UNIQUAC equation as a function of temperature are given
by the following equation:
ð0Þ ð1Þ ð2Þ
aij ¼ aij þ aij Tr þ aij Tr2 ; ð5Þ
with Tr ¼ T=T0 , where T0 is an arbitrarily chosen reference temperature, in this case
T0 ¼ 315:00 K.

TABLE 6. The correlation results for binary systems: dT is the RMSD of temperature

p/kPa a12 a21 dT /K

ðx1 Linalool þ x2 1-propanolÞ
20.00 0.44
30.00 0.42
40.00 775:93  82:83Tr  76:34Tr2 175:45  32:43Tr  31:99Tr2 0.23
50.00 0.26
60.00 0.35

ðx1 Linalool þ x2 1-butanolÞ

20.00 0.45
30.00 0.40
40.00 705:88  56:99Tr  70:82Tr2 179:84  36:05Tr  32:29Tr2 0.37
50.00 0.31
60.00 0.35
aij is the optimum binary temperature-dependence parameter.
1436 D. Deng et al.

The optimum temperature-dependence parameters were obtained by minimizing the

objective function J, using modified Powell optimization technique.ð20Þ The objective
function is defined as follows:
X
J¼ fðp  pexp Þ=pexp g2j : ð6Þ
j

The optimum binary temperature-dependence parameters aij and the root-mean square
deviation (RMSD) of the temperatures between the experimental and the most probable

FIGURE. 1. T–x1 for linalool (1) + 1-propanol (2) at constant pressure. d, 20.00 kPa; r,
30.00 kPa; r, 40.00 kPa; M, 50.00 kPa; j, 60.00 kPa; - - -, UNIQUAC correlation.

FIGURE. 2. T–x1 for linalool (1) + 1-butanol (2) at constant pressure. d, 20.00 kPa; ,
30.00 kPa; N, 40.00 kPa; }, 50.00 kPa; j, 60.00 kPa; - - -, UNIQUAC correlation.
 Isobaric equilibria (vapour+liquid) 1437

calculated values of the measured variables are listed in table 6. The RMSD of tem-
peratures for binary systems are all less than 0.45 K. Figures 1 and 2 show the temper-
atures for the systems (linalool + 1-propanol) and (linalool + 1-butanol) at various
pressures. The experimental and fitted values are in good agreement. The results indicate
that the isobaric binary VLE data of (linalool + 1-propanol) and (linalool + 1-butanol)
can be satisfactorily correlated by using UNIQUAC equation with binary temperature-
dependence parameters.
We appreciate the financial support provided for this work by the National Natural
Science Foundation of PR China (No. 29976035) and Zhejiang Provincial Natural Sci-
ence Foundation of PR China (No. RC01051).

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(Received 13 March 2002; in final form 13 May 2002)

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