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Fluid Phase Equilibria 227 (2005) 113–124

Vapor–liquid equilibria in the binary system


(−)-beta-pinene + (+)-fenchone
Analysis in terms of group contributions models of
some binary systems containing terpenoids
I. Batiu∗
Department of Chemical Engineering and Material Science, “Babeş-Bolyai” University of Cluj-Napoca,
Arany Janos 11, 400028 Cluj-Napoca, Romania

Received 30 May 2004; accepted 21 October 2004

Abstract

Isobaric vapor–liquid equilibrium measurements are reported for the binary system (−)-beta-pinene + (+)-fenchone at the constant pressure
of 13.33 kPa in the temperature range from 341.60 K to 393.25 K. The boiling temperatures of the mixtures were also measured at seven
constant compositions in the pressure range from 2.56 kPa to 20.80 kPa. The experimental data were found to be thermodynamically consistent.
Reduction of the vapor–liquid equilibrium data was carried out by means of the Wilson, NRTL and UNIQUAC equations. Our data on
vapor–liquid equilibria for mixtures containing terpenoids are examined in terms of the DISQUAC and modified UNIFAC (Dortmund) group
contributions models. Interaction parameters of the DISQUAC model are reported.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Vapor–liquid equilibria; Terpenoids; DISQUAC; Modified UNIFAC (Dortmund); Gibbs energy

1. Introduction (5) (R)-(−)-carvone + n-decane [5];


(6) n-decane + (−)-menthone [(2S,5R)-2-isopropyl-5-meth-
In previous papers we reported vapor–liquid equilibrium ylcyclohexanone] [6];
(VLE) data for following binary systems containing terpenes, (7) n-decane + (+)-fenchone [6].
terpenoids, and n-alkanes:
We selected both saturated and unsaturated, monocyclic
(1) (S)-(+)-carvone [(S)-(+)-4-isopropenyl-1-methylcyclo- and bicyclic terpenoids, containing ketone or ether groups. In
hexen-6-one] + (+)-limonene [(R)-(+)-4-isopropenyl-1- (S)-(+)-, respectively (R)-(−)-carvones, the ketone group is
methylcyclohexene] [1]; in mesomeric position with the double bond in the ring. All
(2) (−)-beta-pinene {(1S,5S)-(−)-6,6-dimethyl-2-methyle- these chemical compounds are found as main components in
nebicyclo [3.1.1]heptane} + eucalyptol [1,3,3-trimethyl- many essential oils.
2-oxabicyclo[2.2.2]octane] [2]; Group contribution methods are of major interest for the
(3) (R)-(−)-carvone [(R)-(−)-4-isopropenyl-1-methylcy- development, design and optimisation of thermal separation
clohexen-6-one] + eucalyptol [3]; processes. Because experimental data are often not available,
(4) n-octane + (+)-limonene [4]; group contribution methods are used to predict the required
phase equilibrium data and the related thermodynamic excess
properties. A survey of the literature [7] shows that experi-
∗ Tel.: +40 264 593833; fax: +40 264 590818. mental vapor–liquid equilibrium data are missing for many
E-mail address: batiu@chem.ubbcluj.ro. mixtures containing terpenoids.

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.10.032
114 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

The purpose of the present work was to measure VLE structures of all the terpenes and terpenoids refered to in this
of binary mixtures of (−)-beta-pinene + (+)-fenchone and to paper are presented in Fig. 1.
check the predictive capability of two group contribution
models, DISQUAC and modified UNIFAC (Dortmund), for
this mixture and for the previous reported mixtures contain- 2. Experimental
ing terpenoids.
No experimental VLE data are available in the literature 2.1. Chemicals
for the binary system (−)-beta-pinene + (+)-fenchone [7].
(−)-Beta-pinene is a bicyclic terpene hydrocarbon while (−)-Beta-pinene, CAS RN 18172-67-3, ACROS OR-
(+)-fenchone is a bicyclic terpenoid ketone. The chemical GANICS (Ney Jersey, USA) material of stated purity

Fig. 1. Chemical structure of some terpenes and terpenoids.


I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 115

>99.4%, tested by GC using a Carlo Erba chromatograph, Table 1


was used without further purification. Experimental vapor–liquid equilibrium data of the binary system (−)-beta
pinene (1) + (+)-fenchone (2) at P = 13.33 kPa
(+)-Fenchone, CAS RN 4695-62-9, S.C. FARES S.A.
(Orăştie, Romania) material, was purified by batch distilla- T (K) x1 y1 γ1 γ2 GE /RT
tion on a column packed with Dixon rings. The GC purity 396.45 0.0000 0.0000 1.7000 1.0000 0.0000
was 99.9 wt.%, as determined by means of a Carlo Erba gas 393.25 0.0450 0.1485 1.6445 1.0023 0.0246
391.00 0.0850 0.2450 1.5359 1.0032 0.0394
chromatograph. 387.15 0.1770 0.4050 1.3718 1.0082 0.0627
384.65 0.2595 0.5050 1.2624 1.0213 0.0761
382.00 0.3610 0.6000 1.1744 1.0556 0.0926
2.2. Apparatus and procedure
379.75 0.4510 0.6720 1.1340 1.0973 0.1077
377.60 0.5720 0.7555 1.0807 1.1401 0.1005
An all-glass 240 cm3 recirculation still (Sieg and Roeck 375.85 0.6690 0.8125 1.0552 1.2109 0.0993
Type, Normag Labor-und Verfahrenstechnik GmbH & Co., 374.40 0.7730 0.8735 1.0326 1.2620 0.0776
Hofheim am Taunus, Germany) was used. The temperature T 373.15 0.8845 0.9320 1.0063 1.4020 0.0446
372.50 0.9290 0.9570 1.0060 1.4807 0.0342
(K) was measured by means of a Hg thermometer calibrated
371.85 1.0000 1.0000 1.0000 1.5800 0.0000
against IPTS-68 within σ(T) = 0.05. The differences between
Boiling temperature T, liquid xi and vapor yi mole fractions, activity coeffi-
the IPTS-68 and ITS-90 are within the limit of the experi- cients γ i and molar excess Gibbs energy GE /RT.
mental error. A pressure controller maintained the pressure P
within 15 Pa around the desired values. P (Pa) was measured
using a Hg manometer within σ(P) = 30. coefficients γ i were calculated by [9]:
Prior to an experimental run, the equilibrium still was thor-  
yi P (Bii − Vi )(P − Pi0 ) + Pδij yj2
oughly cleaned and evacuated. It was then charged with the ln γi = ln + ,
appropriate amounts of components and pressure was ad- xi Pi0 RT
justed to the required value by means of a vacuum pump. i, j = 1, 2 (1)
Equilibrium was attained under continuous stirring and re-
circulation of the two phases for 1 h. Samples of the liquid where
and condensed vapor were taken after pressurizing the appa-
ratus to atmospheric pressure. δij = 2Bij − Bii − Bjj , i, j = 1, 2 (2)
The standard state for the calculation of activity coeffi-
2.3. Sample analysis cients is the pure component at the pressure and temperature
of the solution. The Rackett equation was used to calculate
The equilibrium compositions were determined with the liquid molar volumes Vi .
a Carlo Erba Strumentatione (Milano, Italy) model 6000 The second virial coefficients Bii and Bij were calculated
VEGA Series 2 gas chromatograph having a 50 m long by the method of Pitzer and Curl [10]. The critical properties
and 0.3 mm diameter column packed with OV-1 chemi- for (−)-beta pinene and (+)-fenchone were estimated by the
cal bounded, coupled with a data acquisition system Type method proposed by Bae et al. [11] and by Joback’s group
Spectra-Physics D.P. 700 (Milano, Italy). A flame ioniza- contribution method [12]. The molar excess Gibbs energies,
tion detector operating under a temperature gradient of GE (J mol−1 ) were calculated from:
10 K min−1 in the range from 353 K to 473 K was used. Injec- 
tor and detector temperatures were 523 K. Hydrogen at a pres- GE = RT xi ln γi (3)
sure of 70 kPa was used as carrier gas. The amount of injected The experimental VLE data of the mixtures were found
product was 0.1 × 10−3 mL. Calibration was performed us- to be thermodynamically consistent as tested by using the
ing gravimetrically prepared solutions. The response factor maximum likelihood multimodel fitting method described by
of the detector was between 1.2330 and 1.2597 for the mix- Panaitescu [13]. The objective function (S) is defined as fol-
ture (−)-beta-pinene + (+)-fenchone. Very good separations lows:
were achieved under these conditions. The precision of the
N

analyses was generally within σ(xi ) = σ(yi ) = 0.002 in mole  (Pie − Pic )2 (Tie − Tic )2 (xie − xic )2
fraction, at any concentration. S= + +
σP2 σT2 σx2
i=1

(yie − yic )2
3. Results + (4)
σy2

The direct experimental boiling temperatures T of the pure where N is the number of experimental points, Pie , Tie , xie
terpenoids were measured previously and published [1–6,8] and yie are the experimental data and Pic , Tic , xic and yic are
A series of isobaric T–x–y measurement was performed the corresponding calculated values for pressure, tempera-
at (13.33 ± 0.030) kPa (Table 1). The experimental activity ture, and the liquid and vapor compositions, respectively. In
116 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

this paper, the standard deviation for pressure, temperature, Table 2


and liquid and vapor compositions were set to σ P = 30 Pa, Experimental vapor–liquid equilibrium data of the binary system (−)-beta
σ T = 0.05 K, σ x = 0.002 mol fr. and σ y = 0.002 mol fr., respec- pinene (1) + (+)-fenchone (2)
tively. According to this test the VLE measurements are con- T (K) x1 P (kPa)
sidered consistent if the values of the statistic criterion of 347.15 0.1770 2.56
selection of the each experimental point (Ro) and of the all 356.95 0.1770 3.99
experimental points (Ro global) is less 2.45. At 13.33 kPa the 368.20 0.1770 6.36
378.80 0.1770 9.53
values of the calculated Ro global criterions were: 0.765 (Wil- 381.80 0.1770 10.70
son), 0.772 (NRTL) and 0.711 (UNIQUAC), respectively. 387.15 0.1770 13.37
The thermodynamic consistency of the isobaric VLE data 342.80 0.3610 2.67
was also checked against the point-to-point test of Van Ness, 353.40 0.3610 4.34
modified by Fredenslund [14] using a second order Legendre 353.50 0.3610 4.36
362.75 0.3610 6.44
polynomial. According to this test, the data are considered 372.35 0.3610 9.32
consistent if the mean absolute deviation in y, MAD (y) is 379.10 0.3610 12.00
less than 0.01. At 13.33 kPa we found MAD (y) = 0.00279 382.00 0.3610 13.33
The experimental VLE data together with the activity co- 349.80 0.5720 4.51
efficients and the molar excess Gibbs energies are reported 350.25 0.5720 4.57
357.05 0.5720 6.15
in Table 1 and Figs. 2 and 3. 357.25 0.5720 6.17
Another series of T–P measurements was performed 367.45 0.5720 9.18
at seven constant liquid-phase compositions. For the mix- 374.45 0.5720 11.88
tures of (−)-beta-pinene (1) + (+)-fenchone (2): x1 = 0.1770 374.60 0.5720 11.91
± 0.001; x1 = 0.3610 ± 0.001; x1 = 0.5720 ± 0.001; x1 = 377.60 0.5720 13.33
341.60 0.6690 3.38
0.6690 ± 0.001, x1 = 0.7730 ± 0.001, x1 = 0.8845 ± 0.001 341.90 0.6690 3.41
and x1 = 0.9290 ± 0.001 (Table 2). 351.75 0.6690 5.23
Reduction of the VLE data was carried out by means of 358.75 0.6690 6.95
the Wilson [15], NRTL [16] and UNIQUAC [17] equations. 366.55 0.6690 9.52
The Wilson, NRTL and UNIQUAC binary parameters were 373.15 0.6690 12.04
375.85 0.6690 13.33
obtained by minimizing the following objective function (S) 380.40 0.6690 15.73
383.55 0.6690 17.53
N
   343.90 0.7730 3.95
 P10 352.75 0.7730 5.76
S= 1− x1 γ1 (A12 , A21 )
P 360.25 0.7730 7.79
i=1 366.15 0.7730 9.92
   366.60 0.7730 9.95
P20
− x2 γ2 (A12 , A21 ) = min . (5) 371.50 0.7730 11.94
P 371.65 0.7730 12.05
i 374.40 0.7730 13.33
379.55 0.7730 15.93
where N is the number of experimental points, P the total pres- 383.00 0.7730 18.00
347.15 0.8845 4.78
sure, P10 and P20 are the vapor pressures of pure components 354.05 0.8845 6.39
1 and 2, A12 and A21 are, respectively, the binary parameters 360.25 0.8845 8.27
of the Wilson, NRTL and UNIQUAC models; γ 1 and γ 2 are 367.25 0.8845 10.86
the activity coefficients; x1 and x2 are the mole fractions of 373.15 0.8845 13.33
components 1 and 2 in the liquid phase. 378.35 0.8845 16.20
381.75 0.8845 18.24
The parameters of each model, the mean deviations in 383.35 0.8845 19.30
vapor composition, MD (y) and in pressure, MD (P) (Pa) are 349.35 0.9290 5.47
reported in Table 3. 353.70 0.9290 6.52
The purport of the calculated binary parameters, A12 and 361.90 0.9290 9.11
A21 is: Λ12 , Λ21 (Wilson); τ 12 , τ 21 (NRTL) and (u12 −u22 ), 367.45 0.9290 11.24
372.30 0.9290 13.33
(u21 −u11 ) (UNIQUAC). 376.85 0.9290 15.70
The vapor phase mole fractions, yi , at the pressure of 381.55 0.9290 18.59
13.33 kPa, calculated using the Wilson, NRTL and UNI- 385.00 0.9290 20.79
QUAC binary parameters obtained from our P–T–xi experi- Boiling temperature T, liquid mole fractions xi and pressure P.
mental data, are in good agreement with our P–T–xi –yi ex-
perimental data (Table 1). The mean deviations in yi MD (y)
are 0.01 (Wilson), 0.009 (NRTL) and 0.009 (UNIQUAC),
respectively.
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 117

Fig. 4. Variation of the molar excess Gibbs energy, GE with mole fraction xi ,
Fig. 2. Experimental vapor–liquid equilibrium diagram for the binary
for the binary system n-decane (1) + (+)-fenchone (2) at a constant pressure
system. (−)-Beta-pinene (1) + (+)-fenchone (2) at constant pressure
P = 6.67 kPa: (), experimental; ( ), DISQUAC model;(夽), mod.UNIFAC
P = 13.33 kPa, temperature T (K) as a function of the liquid phase, xi (),
(Do) model.
or vapor phase yi (*), mole fraction composition of component 1.

4. Discussion

The binary system (−)-beta-pinene + (+)-fenchone shows


positive deviations from ideality (Fig. 3).
The previously investigated binary systems [1–6] present
also positive deviations from ideality, except the binary sys-
tem (−)-beta-pinene + eucalyptol, which is almost ideal.
The major contribution to the nonideality of the mixtures
comes from the like dipole/dipole CO/CO interactions in ter-
penoid ketones. Linear ketones + alkanes exhibit fairly large
deviations from ideality, e.g., nonan-5-one + hexane has an
equimolar GE of the order of 300 J mol−1 at 340 K [18].
Cyclic ketones, e.g., cyclohexanone + alkanes have larger de-
viations than linear ketones, e.g., equimolar GE of cyclohex-
anone + heptane at 298 K is ca. 830 J mol−1 [19]. Due to ad-
ditional alkyl groups, cyclic terpenoid ketones + alkanes have
a somewhat smaller GE . At ca. 370 K, the equimolar GE of
the n-decane + (+)-fenchone or + (−)-menthone mixtures is
ca. 450 J mol−1 (Figs. 4 and 5). In (R)-(−)-carvone, the pres-
ence of the polar CO group and of the two C C double bonds,
Fig. 3. Variation of the molar excess Gibbs energy, GE with mole fraction
one of them in relation of mesomery with ketone group in
xi , for the binary system (−)-beta pinene (1) + (+)-fenchone (2) at constant
pressure P = 13.33 kPa: (), experimental; ( ), DISQUAC model; (夽), the cycle, increases the like intermolecular interactions due
mod.UNIFAC (Do) model; (*), mod.UNIFAC (Do) revised group interaction to dipole/induced dipole interactions between CO and C C,
parameters [38]. and this results in a relatively higher deviation from ideality.

Table 3
Binaries parameters A12 and A21 of the Wilson and NRTL and UNIQUAC models for the binary system (−)-beta pinene (1) + (+)-fenchone (2)
T–P–x–y MD (y) MD (P) (Pa) T–P–x MD (P) (Pa)

A12 A21 A12 A21


Wilson 0.6219 0.9843 0.0024 84 1.4886 0.3087 128
NRTL (α = 0.3) −0.1144 −0.6060 0.0025 86 0.4152 20.06 149
UNIQUAC −57.89 −114.09 0.0083 226 −112.21 −51.10 220
Mean deviations in vapor composition, MD (y) and in pressure, MD (P), UNIQUAC parameter unit Jmol−1 .
118 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

Fig. 5. Variation of the molar excess Gibbs energy, GE with mole fraction xi , Fig. 7. Variation of the molar excess Gibbs energy, GE with mole fraction
for the binary system n-decane (1) + (−)-menthone (2) at a constant pressure xi , for the binary system (+)-limonene (1) + (S)-(+)-carvone (2) at a con-
P = 6.67 kPa: (), experimental; ( ), DISQUAC model; (夽), mod.UNIFAC stant pressure P = 6.53 kPa: (), experimental; ( ), DISQUAC model; (夽),
(Do) model. mod.UNIFAC (Do) model.

In the mixture with n-decane at ca. 372 K, the equimolar GE In the binary system eucalyptol + (R)-(−)-carvone, the like
is ca. 660 J mol−1 (Fig. 6). dipole/dipole CO/CO and O / O interactions compensate
(S)-(+)-Carvone and (+)-limonene having similar molec- the unlike dipole/dipole CO/ O and dipole/induced dipole
ular structures and the same number of double bonds, the like O /C C interactions. Accordingly, at 375 K, the equimolar
and unlike dipole/induced dipole CO/C C interactions com- GE of the mixture is ca. 418 J mol−1 (Fig. 8), much smaller
pensate. At ca. 376 K, the equimolar GE is ca. 510 J mol−1 than for n-decane + (R)-(−)-carvone (Fig. 6).
(Fig. 7), as expected for a cyclic ketone + n-alkane mixtures. The binary system n-octane + (+)-limonene exhibits rela-
The binary system (−)-beta-pinene + (+)-fenchone tively small deviations from ideality. The contribution to the
(Fig. 3) exhibits a relatively smaller deviation from ideality, nonideality of the mixture comes from the like C C/C C in-
compared to n-decane + (+)-fenchone (Fig. 4), due to the teractions. At ca. 372 K the equimolar GE is ca. 191 J mol−1
compensation of the like dipole/dipole CO/CO with the (Fig. 9).
unlike dipole/induced dipole CO/C C interactions in the The binary system (−)-beta-pinene + eucalyptol is almost
mixture. The equimolar GE at ca. 379 K is ca. 340 J mol−1 . ideal with an equimolar GE of ca. 15 J mol−1 (Fig. 10). This

Fig. 6. Variation of the molar excess Gibbs energy, GE with mole frac- Fig. 8. Variation of the molar excess Gibbs energy, GE with mole frac-
tion xi , for the binary system n-decane (1) + (R)-(−)-carvone (2) at a con- tion xi , for the binary system eucalyptol (1) + (R)-(−)-carvone (2) at a con-
stant pressure P = 6.67 kPa: (), experimental; ( ), DISQUAC model; (夽), stant pressure P = 6.67 kPa: (), experimental, ( ), DISQUAC model; (夽),
mod.UNIFAC (Do) model. mod.UNIFAC (Do) model.
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 119

predict the VLE data of the mixture investigated in this pa-


per, as well as others mixtures investigated previously [1–6],
has been examinated using, whenever available, model pa-
rameters estimated on mixtures containing related simple
molecules.

4.1.1. DISQUAC model


The interactional terms in the thermodynamic properties
under consideration are given by the DISQUAC model as the
sum of the dispersive (DIS) and the quasichemical (QUAC)
contributions.
The equations used to calculate VLE and GE (as well as
E
H ) are the same as in others applications, see for example
[20] and need not be repeated here.
The temperature dependence of the interaction parameters
has been expressed in terms of the interchange coefficients,
dis (dispersive) and C quac (quasichemical), where s and t are
Cst,i st,i
Fig. 9. Variation of the molar excess Gibbs energy, GE with mole frac- the types of groups and i = 1, 2.
tion xi , for the binary system n-octane (1) + (+)-limonene (2) at a constant
pressure P = 20.00 kPa: (), experimental; ( ), DISQUAC model; (夽),
mod.UNIFAC (Do) model.
4.1.1.1. Assessment of geometrical parameters. The relative
molecular volumes ri , the surfaces qi , and the molecular sur-
is a consequence of the compensation of the like weak dipole/ face fraction, αsi , of all the molecular species, have been
dipole O / O interactions in eucalyptol with the unlike calculated on the basis of the CH3 , CH2 , CH, C, O and CO
dipole/induced dipole O /C C interactions in the mixture. group volumes and surfaces recommended by Bondi [21],
We note that all the binary systems refered to in this paper taking arbitrarly the volume, VCH4 , and the surface, ACH4 , of
were found to be thermodynamically consistent as tested by methane as unity [22].
the two methods mentioned above. The assessment of geometrical parameters of cyclic
molecules is a more difficult problem. The c-CH2 and c-
CH group parameters of cycloalkanes have been estimated
4.1. Check the predictive capability of group
previously as a function of the number of atoms in the ring
contribution methods theory
[23].
For all the terpenoids refered to in this paper (Fig. 1) the
Terpenoids are rather complicated molecules containing
groups identified by DISQUAC and their geometrical param-
various functional groups. The applicability of group con-
eters are listed in Table 4.
tribution models (DISQUAC and mod. UNIFAC (Do)) to
It should be noted that all these groups and parame-
ters are taken from previous publications (see above), ex-
cept the alkene group defined as >C C<, independent of
the H atoms or other groups attached to it. This reduces
the number of imaginable groups and permits a better com-
parison of the interaction parameters of molecules contain-
ing >C C< groups. The assessment of geometrical param-
eters of the alkene group defined as >C C< and of the H
atoms are taken from [24]. Moreover we attributed the same
geometrical parameters to the group >C C<, whether situ-
ated in a linear or cyclic alkene. Neither of these choices is
strictly justified, and therefore differences between the in-
terchange coefficients of linear and cyclic molecules will
reflect changes in both the effective contact surfaces and
in their interaction force field. The volumes ri , total sur-
faces qi and molecular surface fractions αst of all terpenes
and related compounds refered to in this paper are listed in
Table 5.
Fig. 10. Variation of the molar excess Gibbs energy, GE with mole frac-
tion xi , for the binary system (−)-beta pinene (1) + eucalyptol (2) at a con-
4.1.1.2. Assessment of interaction parameters. It is
stant pressure P = 13.33 kPa: (), experimental; ( ), DISQUAC model; sometimes difficult to assign unambiguously interchange
(夽), mod.UNIFAC (Do) model. coefficients to individual systems. The coefficients can
120 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

Table 4 All these parameters are the same as in previous publications


Volumes rG and surfaces qG groups increments [24–27], except those of three contacts:
Group rG qG
a1 CH3 0.79848 0.73103 1. >C C</CH3 , CH2 , or CH (e, a), redetermined with the
a2 CH2 0.59755 0.46552 new definition of the >C C< group on the basis of GE
a3 CH< 0.39603 0.19655 and HE data reported respectively by [28,29] and [30,31];
a4 >C< 0.19451 0.00000
2. CO/>C C< (k, e), redetermined on the basis of GE and
c1 c CH2 (c6 ) 0.58645 0.43277
c2 c CH2 (c5 ) 0.58645 0.47127 HE data reported respectively by [32] and [33];
c3 c CH< (c6 ) 0.38493 0.16380 3. O/>C C< (f, e), redetermined on the basis of GE and HE
c4 c CH< (c5 ) 0.38493 0.20230 data reported respectively by [34] and [35].
e >C C< 0.58528 0.42069
h1 H 0.20240 0.16207 It should be noted that the interchange coefficients values,
quac
h2 H 0.20240 0.21552 Cstdis and Cst , (Table 6) redetermined with the new defini-
f O 0.21612 0.20690 tion of the >C C< group, have been used in our application
k CO 0.68341 0.55172 program to calculate excess Gibbs energy and not represent a
generalized interchange coefficients values of the A–F class
h1 >C CH ; h2 >C CH2
of substances. For calculating generalized interchange coef-
n-Octane = 2a1 + 6a2
n-Decane = 2a1 + 8a2 ficients values (A–F class of substances) a detailed study is
Limonene = 2e + 3c1 + c3 + 2a1 + h1 + 2h2 necessary. The study is in progress.
Beta-pinene = e + 3c1 + 2c3 + a4 + 2a1 + 2h2 4.1.1.2.1. Monocyclic terpene hydrocarbons + n-
Menthone = k + 3c1 + 2c3 + 3a1 + a3 alkanes. Limonene is a monocyclic terpene hydrocarbon
Fenchone = k + 2c1 + c2 + c4 + 2a4 + 3a1
with two double bonds. In mixtures with n-octane there are
Carvone = k + 2e + 2c1 + c3 + 2a1 + h1 + 2h2
Eucalyptol = f + 4c1 + c3 + 2a4 + 3a1 three types of surfaces and is characterised by three types
DISQUAC model.
of contacts: (e, a), (c–e, a) and (c–e, e). The dispersive
interchange coefficients, Ce,t dis have been estimated on the
E E
basis of G and H listed in Tables 7 and 8 . We note that
indeed be varied, within certain limits, without affecting these interchange coefficients have been published previous
significantly the agreement with experiment. [24] (the alkene group beeing defined as >C C<).
Table 6 lists the dispersives Cst,i
dis and the quasichemicals
4.1.1.2.2. Terpenoid ketones + n-alkanes. (−)-Menth-
quac
Cst,i interchange coefficients for all the s, t-contacts of the one is a monocyclic ketone while (+)-fenchone is a bi-
terpenoids and related compounds refered to in this paper. cyclic ketone. (R)-(−)-Carvone is a monocyclic ketone with

Table 5
Volumes ri , total surfaces qi , and molecular surface fractions αsi
ri qi αei αai αki /αfi
Alkanes
n-Hexane 3.9871 3.3241 0.0000 1.0000
n-Octane 5.1822 4.2552 0.0000 1.0000
n-Decane 6.3773 5.1862 0.0000 1.0000
Alkenes
1-Hexene 3.7836 3.1414 0.1339 0.8661
Cyclohexene 3.3359 2.4759 0.1699 0.8201
1-Methylcyclohexene 3.9320 3.0448 0.1382 0.8618
Limonene 5.5190 4.3586 0.1930 0.8070
Beta-pinene 5.3107 3.9397 0.1068 0.8932
Ketones
Butan-2-one 2.8779 2.4793 0.0000 0.7775 0.2225a
Menthone 6.0041 4.5673 0.0000 0.8792 0.1208a
Fenchone 5.6121 4.2839 0.0000 0.8712 0.1288a
Carvone 5.6159 4.4776 0.1879 0.6889 0.1232a
Ethers
Eucalyptol 5.7313 4.2949 0.0000 0.9518 0.0482b
Oxane 3.1484 2.3708 0.0000 0.9127 0.0873b
Oxolane 2.5619 2.0920 0.0000 0.9011 0.0989b
DISQUAC model.
a These values are of α .
ki
b These values are of α .
fi
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 121

Table 6
quac
Dispersives Cstdis and the quasichemicals Cst interchange coefficients
Substances Dispersives Quasichemicals References

C1dis C2dis C1dis C2dis


A. Alkenes + Alkanes (1-hexene + hexane) 0.7203 1.70 0.00 0.00 [This work]
0.6700 1.70 0.00 0.00 [24]
B. Cycloalkenes + Alkanes (Cyclohexene + hexane) 2.20 3.25 0.00 0.00 [This work]
C. Ketones + Alkenes 8.005 10.00 0.00 0.00 [This work]
D. Ketones + Cycloalkene (Butan-2-one + cyclohexene) 8.005 10.00 0.00 0.00 [This work]
E. Oxaalkanes + Alkene (Oxane + 1-hexene) 11.76 12.12 0.00 0.00 [This work]
F. Oxaalkanes + Cycloalkene 11.76 12.12 0.00 0.00 [This work]
G. n-Alkanone + Alkanes 3.65 8.03 4.56 4.04 [25,27]
H. Cycloalkanones + Alkanes 3.69 6.51 4.95 5.50 [25]
I. Oxaalkanes + Alkanes 10.60 18.20 3.40 5.60 [26,27]
12.40 20.00 5.40 7.20 [26]
J. Oxaalkanes + Ketones 4.55 5.15 0.50 0.50 [27]
DISQUAC model.

Table 7 Table 10
Molar excess Gibbs energies (GE ) of the alkenes or cycloalkenes with n- Molar excess enthalpies (HE ) of the cycloalkenes with ketones
alkanes (m is the number of C atomes in the n-alkane) Cycloalkene Ketones T (K) E (J mol−1 )
Hexp References
Alkenes/cycloalkenes m T (K) GEexp (x = 0.5) References
Cyclohexene Butan-2-one 298.06 860 (x = 0.532) [33]
(J mol−1 ) 298.15 877 (x = 0.50) [33]
1-Hexene 6 328.15 25 [29] 343.15 910 (x = 0.532) [33]
Cyclohexene 6 278.15 96 [28]
283.15 55
288.15 85 4.1.1.2.3. Terpenoid ketones + monocyclic and bicyclic
293.15 102 terpene hydrocarbons. In the mixture of (S)-(+)-carvone
298.15 102 + (+)-limonene we have considered four types of surfaces
with the following types of contacts: (k, a), (k, e), (k,
Table 8 c–e), (e, c–e), (e, a) and (c–e, a) while the mixture of (+)-
Molar excess enthalpies (HE ) of the alkenes or cycloalkenes with n-alkanes fenchone + (−)-beta-pinene is characterized by three types of
(m is the number of C atomes in the n-alkane) surfaces and the following types of contacts: (k, a), (k, e) and
Alkenes/cycloalkenes m T (K) Hexp
E (x = 0.5) References (e, a).
(J mol−1 ) 4.1.1.2.4. Terpenoid oxaalkanes + bicyclic terpene hy-
1-Hexene 6 298.15 61 [31] drocarbons. The mixture of eucalyptol + (−)-beta-pinene
Cyclohexene 6 298.15 165 [30] is characterized by three types of surfaces and by the fol-
lowing types of contacts: (f, e), (f, a), and (e, a). The dis-
persive parameters Cf,e dis have been estimated on the basis
two double bonds, one of them in relation of mesomery E E
of G and H listed in Tables 11 and 12. For the con-
with the ketone group. In mixtures with n-decane the bi-
nary systems are characterised by the following types of Table 11
contacts: (k, a) in (−)-menthone and (+)-fenchone, respec- Molar excess Gibbs energies (GE ) of the alkenes with oxaalkanes
tively (k, a), (k, e), (k, c–e) (e, a), (c–e, a) in (R)-(−)- Alkenes Oxaalkenes T (K) GEexp (x = 0.5) References
carvone. The dispersive interchange coefficients,Ck,c dis
–e for (J mol−1 )
ketone + cycloalkenes have been estimated on the basis of 1-Hexene Oxane 263.15 170 [34]
GE and HE listed in Tables 9 and 10. For the contact ke- 333.15 163 [34]
tone + alkene we used the same dispersive interchange coef- 1-Hexene Oxolane 263.15 245 [34]
ficients, Ck,c
dis . For the contact (k, a), we used the dispersive
–e
333.15 232 [34]
dis and quasichemical C dis interchange coefficients pub-
Ck,a k,a
lished in the literature [25,27]. Table 12
Molar excess enthalpies (HE ) of the alkenes or cycloalkenes with oxaalkanes
Alkenes/ Oxaalkenes T (K) Hexp
E (x = 0.5) References
Table 9 cycloalkenes (J mol−1 )
Molar excess Gibbs energies (GE ) of the cycloalkenes with ketones
1-Hexene Oxane 333.15 197 [34]
Cycloalkene Ketones T (K) GEexp (x = 0.5) (J mol−1 ) References
Cyclohexene Oxane 298.15 148 [35]
Cyclohexene Butan-2-one 293.15 670 [32] 1-Hexene Oxolane 333.15 290 [34]
313.15 643 [32] Cyclohexene Oxolane 298.15 286 [35]
122 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

Table 13
Rk and Qk parameters and group assignment for mod. UNIFAC (Do) method [36]
Main group Subgroup No. Rk Qk
1 ‘CH3 ’ CH3 1 0.6325 1.0608
CH2 2 0.6325 0.7081
CH 3 0.6325 0.3554
C 4 0.6325 0.0000
9 ‘CH2 CO’ CH3 CO 18 1.7048 1.6700
CH2 CO 19 1.7048 1.5542
42 ‘c-CH2 ’ c-CH2 78 0.7136 0.8635
c-CH 79 0.3479 0.1071
c-C 80 0.3470 0.0000
43 ‘c-CH2 O’ c-CH2 OCH2 27 1.7023 1.8784
c-CH2 O[CH2 ]1/2 83 1.4046 1.4000
c-[CH2 ]1/2 O[CH2 ]1/2 84 1.0413 1.0116

tact (f, a) we used the dispersive Cf,a


dis and quasichemical The mod. UNIFAC (Do) is revised and extended periodi-
quac
Cf,a interchange coefficients published in the literature caly [38–41] to improve the capability of prediction.
[26,27].
4.1.1.2.5. Terpenoid oxaalkanes + terpenoids ketones. 4.1.2.1. Assessment of geometrical parameters. According
For the more complex binary system eucalyptol + (R)-(−)- to the mod. UNIFAC (Do) model majority of the terpenoids
carvone we have considered four types of surfaces and the molecules refered to in this paper have been decomposed
following types of contacts: (k, a), (k, e), (k, f), (f, a), in groups, except (+)-fenchone and eucalyptol. The mod.
(f, e), (a, e). We used the dispersive Ck,f
dis and quasichemi- UNIFAC (Do) model [36] do not define CCO, from (+)-
quac
cal Ck,f interchange coefficients published in the literature fenchone, respectively c-COC, from eucalyptol, subgroups.
[27]. For these subgroups we have considered the existing van
der Waals properties Rk and Qk defined for the CH2 CO
4.1.2. Modified UNIFAC (Do) model (19) subgroup, respectively the c-[CH2 ]1/2 O[CH2 ]1/2 (84)
The equations used in mod. UNIFAC model [36] to cal- subgroup.
culate γ i , VLE or GE are the same as in the original UNI- Table 13 lists the van der Waals values of Rk and Qk for
FAC [14,37]. One of the main differences between original the all groups refered to in this paper.
UNIFAC and mod. UNIFAC (Do) is the introduction of tem-
perature dependent interaction parameters to permit a better 4.1.2.2. Assessment of interaction parameters. We used the
description of the real phase behavior as a function of tem- group interaction parameters published in [36]. For the main
perature: group (42) we used the group interactions parameters pub-
 a  lished in the original mod. UNIFAC (Do) [36] and also
nm
Original UNIFAC : ψnm = exp − (6) the revised group interactions parameters published in [38].
T
Table 14 lists the modified UNIFAC (Do) group interaction
Mod. UNIFAC(Do) : parameters [36] and revised modified UNIFAC (Do) group
 interaction parameters [38] of the main group 42, (‘c-CH2 ’),
anm + bnm T + cnm T 2 with the main groups 1 (‘CH2 ’), 2 (‘C C’) and 9 (‘CH2 CO’),
ψnm = exp − (7)
T respectively. We note that the revised mod. UNIFAC (Do)
group interaction parameters predict better the values of mo-

Table 14
Modified UNIFAC (Do) group interaction parameters [36] and revised modified UNIFAC (Do) group interaction parameters [38] for the main group 42 (c-CH2 )
with the main groups 1, 2, 9
n m anm (K) bnm (K) cnm (K) amn (K) bmn (K) cmn (K)
1 42 −680.95 4.0194 −0.6878 × 10−2 1020.8 −6.0746 0.1015 × 10−1
a1 42 −117.10 0.5481 −0.00098 170.90 −0.8062 0.00129
2 42 −78.19 0.1327 0.00 182.40 −0.3030 0.00
a2 42 2.4060 −0.1882 0.00 60.20 0.1565 0.00
9 42 156.53 −0.7135 0.00 498.92 −0.4400 × 10−1 0.00
a9 42 168.20 −0.8197 0.00 464.50 0.1542 0.00
a Revised modified UNIFAC (Do) group interaction parameters.
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 123

lar excess Gibbs energy, GE , in all the systems refered to in systems comparative with experimental GE values. A new
this paper, except the binary system (−)-beta-pinene + (+)- c-COC structural group should be defined for eucalyptol.
fenchone (Fig. 3), where the prediction is unsatis-
factory.
5. Conclusions
4.1.3. Comparison with experiment
A detailed comparation between experimental data and Isobaric vapor–liquid equilibrium (VLE) measurements
calculated values of the molar excess Gibbs energy, GE , (T–x–y) are reported for the binary system (−)-beta-
from DISQUAC and mod. UNIFAC (Do) is presented in pinene + (+)-fenchone.
Figs. 3–10. More discussions are necessary for each chemical We have realized a comparative study about the predictive
structure. capability of two group contribution models, DISQUAC and
mod. UNIFAC (Do), in mixtures containing terpenoids. Ter-
4.1.3.1. Terpenes and terpenoids + n-alkanes. The exami- penoids are complicated molecules, saturated or unsaturated,
nation of the terpenes and terpenoids + n-alkane mixtures is acyclic, monocyclic or bicyclic, containing various functional
of importance in order to test the validity of the model param- groups, the ketone group, sometimes being in relation of me-
eters for each individual terpene. As a matter of fact, various somery with the double bonds in the cycle. The literature [7] is
intramolecular effects such as group proximity, steric and very poor in vapor–liquid equlibria experimental data in mix-
cyclization may seriously affect the model parameters. tures containing terpenoids. The mod. UNIFAC (Do) does
The DISQUAC model, using the dispersive and qua- not define some subgroups, like CCO, from (+)-fenchone, re-
sichemcal interchange coefficients, taken from previous pub- spectively c-COC, from eucalyptol. Thus, the GE predictions
lications and redetermined with the new definition of >C C< in the binaries systems containing eucalyptol are unsatisfac-
group, is appropiate for all the investigated terpenes and ter- tory. The GE predictions in the binary systems containing
penoids + n-alkanes mixtures, except the binary system n- (+)-fenchone depend of the other component in mixture and
octane + (+)-limonene (Fig. 9) where the prediction is rather of the group interaction parameters. Thus, in mixture with
poor. an inert component, like n-decane, the GE predictions is very
A very good prediction of the mod. UNIFAC (Do) model good while in mixtures with (−)-beta-pinene the GE predic-
was found for the mixtures of n-decane with (R)-(−)-carvone tions depend of the group interaction parameters.
(Fig. 6) and (+)-fenchone (Fig. 4) while in the systems con- The GE predictions using DISQUAC model are appropiate
taining (−)-menthone (Fig. 5) and (+)-limonene (Fig. 9) the for all the studied binary systems.
agreement is satisfactory. A new CCO structural group should
be defined for (+)-fenchone. List of symbols
A12 , A21 binary parameters of the models Wilson, NRTL,
4.1.3.2. Terpenoids + terpenoids. The examination of the UNIQUAC
GE predictions using the DISQUAC model containing only Bii , Bjj pure component second virial coefficient
terpenoids is appropiate for all the binary systems, ex- Bij cross second virial coefficient
cept binary system (+)-limonene + (S)-(+)-carvone (Fig. 7) GE molar excess Gibbs energy
where calculated GE is smaller than exp. GE values. We HE molar excess enthalpy
note a very good prediction in the binary system (−)-beta- P total vapor pressure
pinene + eucalyptol (Fig. 10) comparative with the mod. Pio saturated vapor pressure of pure component i
UNIFAC (Do), where the calculated GE values are very high. R universal gas constant
The examination of the GE predictions using the mod. S objective functions in Eqs. (4) and (5)
UNIFAC (Do) is appropiate for the binary system (+)- T absolute temperature
limonene + (S)-(+)-carvone (Fig. 7). In this system, the ViL molar volumes of the saturated liquid
original UNIFAC model [37] predicts more accurate the x, y liquid and vapor composition mole fraction, respec-
VLE experimental data than mod. UNIFAC (Do) model tively
[1,36,38]. Cstdis dispersive interchange coefficients (DISQUAC
In the binary system (−)-beta-pinene + (+)-fenchone model)
quac
(Fig. 3) the GE predictions is appropiate using the original Cst quasichemical interchange coefficients (DISQUAC
group interaction parameters mod. UNIFAC (Do) [36] and model)
unsatisfactory using the revised group interaction parameters ri , qi relative molecular volumes or surfaces, respectively
mod. UNIFAC (Do) [38]. (DISQUAC model)
In the others two binary systems of terpenoids: (−)- rG , qG relative volumes or surfaces group increments, re-
beta-pinene + eucalyptol (Fig. 10) and eucalyptol + (R)-(−)- spectivey (DISQUAC model)
carvone (Fig. 8) the GE predictions values are unsatisfac- anm ,amn ,bnm ,bmn ,cnm ,cmn group interaction parameters
tory. The GE calculated values are very high in both binary (mod. UNIFAC (Do) model)
124 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124

VCH4 , ACH4 volumes or surfaces of methane, respectively [12] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and
(DISQUAC model) Liquids, fourth ed., Mc Graw-Hill, Book Company USA, New York,
1987 (ISBN: 0-07-051799-1).
Rk , Qk van der Waals volumes or surfaces, respectively
[13] G.M. Panaitescu, Int. Chem. Eng. 25 (1985) 68–71.
(mod. UNIFAC (Do) model) [14] Aa. Fredenslund, J. Gmehling, P. Rasmussen, Vapor–Liquid Equilib-
ria using UNIFAC, Elsevier, Amsterdam, 1977 (ISBN: 0-444-41621-
Greek letters 8).
γ 1 , γ 2 activity coefficients [15] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127–130.
δij mixture parameter in Eq. (2) [16] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144.
[17] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116–128.
σ standard deviation in Eq. (4) [18] H. Renon, Int. DATA Ser., Sel. Data Mixtures, Ser. A 1 (1973)
ψnm group interaction parameters in Eqs. (6) and (7) 59–67.
(mod. UNIFAC (Do) model) [19] E. Matteoli, L. Lepori, J. Chem. Eng. Data 33 (1988) 247–250.
[20] H.V. Kehiaian, B. Marongiu, Fluid Phase Equilib. 40 (1988) 23–78.
[21] A. Bondi, Physical Properties of Molecular Crystals, Liquids and
Gases, Wiley, New York, 1968.
Acknowledgments [22] H.V. Kehiaian, J.-P.E. Grolier, G.C. Benson, J. Chim. Phys. 75 (1978)
1031–1048.
The author gratefully aknowledges Dr. H.V. Kehiaian [23] M.R. Tine, H.V. Kehiaian, Fluid Phase Equilib. 32 (1987) 211–248.
(ITODYS, University VII Paris, France) for his interest in [24] M.A. Villamañan, H.V. Kehiaian, Fluid Phase Equilib. 42 (1988)
this work and for helpful discussions. Thanks are also due to 165–172.
[25] H.V. Kehiaian, S. Porceda, B. Marongiu, L. Lepori, E. Matteoli,
Dr. G. M. Panaitescu (Petroleum-Gas University of Ploieşti, Fluid Phase Equilib. 63 (1991) 231–257.
Romania) and Dr. Gabriela Bârzan (NACHEMA Comp. S.A. [26] H.V. Kehiaian, M.R. Tine, L. Lepori, E. Matteoli, B. Marongiu, Fluid
Făgăraş, Romania) for their helpful assistance in the compu- Phase Equilib. 46 (1989) 131–177.
tation and analytical work, respectively. Financial support [27] J.A. Gonzales, J.M. Fernandez Martinez, I. Garcia de la Fuente, J.C.
from Romanian CNCSIS, Project 76/2001, 39/2002, 7/2003. Cobos, Can. J. Chem. 74 (1996) 1815–1823.
[28] H.J. Gumpert, H. Köhler, W. Schill, H.J. Bittrich, Wiss. Z. Tech.
Hochsch. Chem. Carl Schorlemmer Leuna-Merseburg 15 (1973)
179–187.
References [29] H. Kirss, L. Kudryavsteva, O. Eisen, Eesti NSV Tead. Akad. Toim.
Keem. Geol. 24 (1975) 15–22.
[1] I. Batiu, L.E. Jimenez, ELDATA: Int. Electron. J. Phys. -Chem. Data [30] K. Günzel, H.J. Bittrich, Z. Phys. Chem. Leipzig 258 (1977)
2 (1996) 59–66. 1073–1080.
[2] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 2 (1996) [31] W. Woycicki, J. Chem. Thermodyn. 7 (1975) 77–81.
231–238. [32] H.C. Van Ness, F. Kohler, Int. DATA Ser., Sel. Data Mixtures, Ser.
[3] I. Batiu, J. Jose, L. Mokbel, L.E. Jimenez, A.P. Bonsfills, ELDATA: A (1990) 254.
Int. Electron. J. Phys. -Chem. Data 4 (1998) 67–74. [33] J. Gmehling, B. Meents, Int. DATA Ser., Sel. Data Mixtures, Ser. A
[4] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 5 (1999) 1–4. (1992) 165.
[5] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 5 (1999) [34] R. Hani, G. Ghanem, A. Ait-Kaci, J. Jose, ELDATA: Int. Electron.
191–195. Phys. -Chem. Data 5 (1999) 149–156.
[6] I. Batiu, Fluid Phase Equilb. 198 (2002) 111–121. [35] J.-P.E. Grolier, A. Inglese, E. Wilhelm, J. Chem. Eng. Data 27 (1982)
[7] I. Wichterle, J. Linek, Z. Wagner, H.V. Kehiaian, Vapor–Liquid 333–335.
Equilibrium in Mixtures and Solutions. Bibliographic Database. [36] J. Gmehling, J. Li, M. Schiller, Ind. Eng. Chem. Res. 32 (1993)
EVLM’2002, ELDATA, Paris, France, 2002, CD-ROM ISBN 2- 178–193.
9507664-9-8 (2002). [37] Aa. Fredenslund, R.L. Jones, J.M. Prausnitz, AIChE J. 21 (6) (1975)
[8] T. Guetachew, I. Mokbel, I. Batiu, Z. Cisse, J. Jose, ELDATA: Int. 1086–1099.
Electron. J. Phys. -Chem. Data (1999) 43–53. [38] J. Gmehling, J. Lohmann, A. Jakob, J. Li, R. Joh, Ind. Eng. Chem.
[9] H.C. Van Ness, M.M. Abbott, Classical Thermodynamics of Res. 37 (1998) 4876–4882.
Non-electrolyte Solutions, Mc Graw-Hill Book Co., New York, [39] J. Lohmann, R. Joh, J. Gmehling, Ind. Eng. Chem. Res. 40 (2001)
1982. 957–964.
[10] K.S. Pitzer, R.F. Curl, J. Am. Chem. Soc. 79 (1957) 2369–2370. [40] J. Lohmann, J. Gmehling, J. Chem. Eng. Jpn. 34 (2001) 43–54.
[11] H.K. Bae, S.Y. Lee, A.S. Teja, Fluid Phase Equilib. 66 (1991) [41] J. Gmehling, R. Wittig, J. Lohmann, R. Joh, Ind. Eng. Chem. Res.
225–232. 41 (2002) 1678–1688.