Fluid Phase Equilibria 338 (2013) 128134

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Fluid Phase Equilibria

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Vaporliquid equilibrium of the ethanol + 3-methyl-1-butanol system at 50.66,

101.33 and 151.99 kPa
Jairo A. Duran, Fernando P. Crdoba, Ivn D. Gil, Gerardo Rodrguez, Alvaro Orjuela
Department of Chemical and Environmental Engineering, Grupo de Procesos Qumicos y Bioqumicos, Universidad Nacional de Colombia, 111321, Bogot, Colombia

a r t i c l e

i n f o

Article history:
Received 16 May 2012
Received in revised form
13 September 2012
Accepted 1 November 2012
Available online 9 November 2012
Keywords:
VLE
Fusel oil
Isoamyl alcohol
Thermodynamic consistency

a b s t r a c t
In this work, the isobaric vaporliquid equilibrium (VLE) for the ethanol (1) + 3-methyl-1-butanol (2)
system at three different pressures is reported. Measurements were done in a dynamic equilibrium
cell (Fischer Labodest VLE 602) at 50.66, 101.33 and 151.99 kPa. The experimental data were tested
for thermodynamic consistency with total area, point, Van Ness, and Herington tests. Herington test was
E
slightly modied considering the Hm /Gm
relation. Data were correlated using the NRTL and UNIQUAC
activity models. NTRL showed the lowest deviation with respect to the experimental data at the three
operating pressures. Quality of regressed parameters for this system was tested comparing results with
isothermal equilibrium data reported elsewhere.
2012 Elsevier B.V. All rights reserved.

1. Introduction
In recent years due to the current efforts for making biofuels as
an alternative for fossil fuels, ethanol industry and its by-products
have been growing very fast. Among them, fusel oil obtained during
bioethanol distillation can be considered a valuable raw material
for several by-products of industrial interest. It is mainly composed of isoamyl alcohol, water, isobutanol, ethanol and other
short-chain alcohols (C2 C5). Yields of fusel oil in an industrial
plant may vary between 1 and 11 L/1000 L of ethanol produced
(absolute basis) depending on the substrate, nitrogen-containing
additives and conditions used during fermentation, and also on distillation conditions [1]. Regarding to the composition, Patil et al.
[1] presents a characterization of fusel oil in terms of two main
fractions: a low boiling fraction (LBF) and a high boiling fraction
(HBF). The rst one corresponds to 9598% (v/v) and is mainly
composed by isoamyl alcohol (6080%), ethanol (515%) and water
(820%) [1]. The other fraction is composed by fatty acids and
their esters, some pyrazines and unsaponicable material. Due to
the low yield and the difculties related to the isolation of pure
alcohols from fusel oil, it is traditionally burned in steam boilers
or blended with the fuel ethanol. However, fusel alcohols can be
used as low cost and renewable sources for the production of biosolvents, avoring agents, pharmaceuticals and plasticizers. These
higher added-value products have the potential for improving the

Corresponding author. Tel.: +57 1 3165000x14303; fax: +57 1 3165617.

E-mail address: aorjuelal@unal.edu.co (A. Orjuela).
0378-3812/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2012.11.004

overall economics of the bioethanol plants [2]. According to this,

it is expected that in the future, bioethanol plants will be able to
tune the fermentation process in order to generate the ethanol
by-products prole that maximizes prots depending on market
demands.
In order to develop separation and purication strategies
for isoamyl alcohol from fusel oil, a good representation of
vaporliquid equilibrium in mixtures with water and ethanol is
required. Systems containing ethanol, water and other alcohols
have been widely studied [38]. Specically, the system isoamyl
alcohol + ethanol has been studied by Martinez et al. [9] and Sanz
and Gmehling [10]. Martinez et al. [9] worked on the equilibrium
with 2-methyl-1-butanol + ethanol at 33.6, 66.6 and 101.3 kPa in a
modied Othmer still, while Sanz and Gmehling [10] worked on
isothermal VLE of both isoamyl alcohols, 2-methyl-1-butanol and
3-methyl-1-butanol, determined experimentally by head space gas
chromatography. In this work isobaric VLE for ethanol with isoamyl
alcohol was measured experimentally using a VLE 602 Fischer
Labodest apparatus at 50.66, 101.33 and 151.99 kPa.
In order to validate the quality of data, thermodynamic consistency tests were used. Several consistency tests have been
investigated over the past years [1122]. Samuels [11] and Kojima
et al. [12] have presented area tests while other authors suggested
the use of point tests or tests based on activity coefcients at innity dilution [1519]. Kang et al. [13] presented a wide review of
commonly used consistency tests and introduced a dataquality
criterion in order to summarize different tests results. Taking into
account the above, consistency of experimental data was evaluated using an area test according to the accepted criteria of Kojima,

J.A. Duran et al. / Fluid Phase Equilibria 338 (2013) 128134

129

Table 1
Materials description.
Chemical name

Source

Initial mass fraction purity

Purication method

Final mass fraction purity

Analysis method

Ethanol
3-Methyl-1-butanol
1,4-Dioxane
MEKc

Quisol Ltd.
J.T. Baker
Merck KGaA
Merck KGaA

0.992
0.995
0.998
0.998

Adsorptiona distillation
None
None
None

0.998

GCb
GCb
GCb
GCb

a
b
c

Adsorption over zeolite A (W.R. Grace & Co.) at 50 C.

Gas chromatography as indicated in Section 2.3.
Methyl ethyl ketone.

Wisniak, RedlichKister [12,13,1922], point test [15,16] and Van

Ness test [18].
2. Experimental
2.1. Materials
Ethanol (>99.0% weight, assay GC) was purchased from Quisol
Ltd. 3-Methyl-1-butanol (>99.5% weight, assay GC) was supplied by
J.T. Baker. 1,4-Dioxane (>99.8% weight, assay GC) and methyl ethyl
ketone (>99.8% weight, assay GC) were used as internal standard
and solvent for chromatographic analyses, respectively, and were
provided by Merck KGaA. Ethanol was puried to >99.8% weight by
dehydration with zeolite A (W.R. Grace & Co.) and then by distillation in a batch system. Other reagents were used without further
purication and did not show any signicant impurities after GC
analysis. Materials used in the experiments are listed in Table 1.
Density, refractive index and normal boiling point of ethanol and 3methyl-1-butanol used in experiments were measured and showed
no signicant differences from those reported in literature as presented in Table 2.
2.2. Apparatus and procedure
The equilibrium cell used in the measurements (Labodest VLE
602D) was an all-glass dynamic-recirculating still equipped with
a Cottrell circulation pump, manufactured by Iludest Destillationsanlagen GmbH (Germany). The Cottrell pump ensures that both
liquid and vapor phases are in intimate contact during boiling
and also in contact with the temperature sensing element. The
equilibrium temperature was measured with a digital temperature
logging module DTM5080 and a Pt 100 resistance thermometer
TMG, model WK 93. The accuracy is estimated to be 0.01 K. A
precision pressure transmitter (WIKA, model P-10) was used to
measure and control the pressure in the equilibrium cell. The
pressure accuracy is 0.01 kPa as indicated by the supplier. This
apparatus allows reaching pressures higher than atmospheric pressure by injection of high purity nitrogen (>99.99%, mole) into a 2 L
buffer tank. Similarly, pressures under 101.3 kPa were attained by
coupling a vacuum pump (Vacuubrand , Model RZ 2.5).
In each experiment, a mixture containing isoamyl alcohol + ethanol was prepared gravimetrically and then 75 1 mL of
the mixture was charged in the still. Then, the pressure was xed

and the heating and stirring system for the liquid phase was turned
on. The still was operated at constant pressure until equilibrium
was reached. Equilibrium condition was assumed when constant
temperature and pressure were obtained for 60 min or longer. To
verify the equilibrium conditions vapor composition was analyzed
until the variation of the mole fraction of ethanol in the vapor phase
was less than 0.020. Then, samples of liquid and condensed vapor
were taken for analysis. The sampling was carried out with special
syringes that allowed withdrawal of small volume samples without disruption of the operation. Experiments were carried out at
50.66, 101.33 and 151.99 kPa. Vapor pressure of pure components
was measured using the same apparatus. At least 15 data points
were taken between 5 and 350 kPa for each component.
2.3. Analysis
The composition of liquid and condensed vapor phases was
determined using a Perkin Elmer Clarus 500 apparatus equipped
with an automatic injector, an HP-1 column (50 m320 m IDWCOT 1.05 m), and a ame ionization detector (FID at 280 C). The
initial oven temperature was programmed at 60 C for 3 min, with
a heating ramp of 5 C/min, raising up to 120 C and then kept for
30 s. The injection port temperature was maintained at 280 C using
split injection mode adjusted to 70:1 ratio. In each analysis, 0.5 L
of sample was injected. Helium was used as carrier gas at 52 cm/s.
VLE samples of around 200 L were diluted in methyl-ethyl ketone
in a 5:1 solvent to sample ratio. Around 80 L of 1,4-dioxane was
added in each sample as internal standard. Six calibration standards were prepared gravimetrically and their compositions were
registered. Compositions and area response factors were well correlated with a linear model (R2 > 0.997 for both ethanol and isoamyl
alcohol). After calibration of the GC technique, an average error of
0.015 in mole fraction of each component was found.
3. Results
3.1. Thermodynamic consistency tests
Despite the availability of vapor pressure data for 3-methyl-1butanol reported in the open literature [2327], measurement of
the vapor pressure for this alcohol was done in order to test the performance and reliability of the equilibrium still used in this work.
Experimental results are listed in Table 3. A numerical regression

Table 2
Comparison of measured properties of the compounds with literature reports.
Component

Ethanol
3-Methyl-1-butanol
a
b
c
d

u(T) = 0.1 K.
u() = 0.0002.
u() = 0.004 g cm3 .
Taken from [26].

Density (g cm3 )

Normal boiling point (K)

Refractive index

Exp.a

Lit.d

Exp.b

Lit.d

Exp.c

Lit.d

351.3
404.9

351.6
405.2

1.3608
1.4033

1.3611
1.4053

0.790
0.817

0.789
0.813

130

J.A. Duran et al. / Fluid Phase Equilibria 338 (2013) 128134

Table 4
Vaporliquid equilibrium data of the system ethanol (1) + 3-methyl-1-butanol (2).a

Table 3
Measured vapor pressure data for 3-methyl-1-butanol.a
Pressure (kPa)

Temperature (K)

Pressure (kPa)

Temperature (K)

T (K)

x1

y1

1

2

ln ( 1 / 2 )

5.00
10.00
19.99
40.01
49.99
59.99
79.99
100.01
101.31

335.85
348.92
363.33
379.51
385.12
389.82
397.61
404.01
404.36

120.00
139.99
159.99
180.01
199.99
250.00
300.00
350.01

409.46
414.21
418.51
422.43
426.01
433.27
440.12
445.98

50.66 kPa
374.70
360.32
356.55
348.21
340.95
338.27

0.0697
0.2336
0.2951
0.4911
0.7153
0.8182

0.3849
0.7298
0.7901
0.8990
0.9606
0.9772

1.152
1.088
1.074
1.019
1.010
1.007

1.007
1.015
1.025
1.031
1.053
1.104

0.135
0.069
0.047
0.012
0.042
0.092

101.33 kPa
392.88
386.12
371.55
369.21
366.06
362.05
359.81
353.82

0.0740
0.1372
0.3643
0.4133
0.4940
0.6053
0.6730
0.8825

0.3854
0.5558
0.8189
0.8489
0.8860
0.9254
0.9433
0.9836

1.229
1.179
1.060
1.051
1.026
1.012
1.008
1.007

1.001
1.003
1.005
1.006
1.011
1.017
1.036
1.111

0.205
0.162
0.053
0.044
0.015
0.005
0.027
0.098

151.99 kPa
394.42
382.29
379.83
372.50
371.19
369.33
361.72

0.1887
0.3729
0.4265
0.6166
0.6578
0.7068
0.9940

0.6189
0.8074
0.8385
0.9192
0.9311
0.9433
0.9990

1.094
1.054
1.037
1.007
1.000
1.006
1.002

1.007
1.029
1.041
1.057
1.068
1.112
1.349

0.083
0.024
0.004
0.048
0.066
0.100
0.297

u(T) = 0.08 K and u(p) = 0.04 kPa.

was performed to t vapor pressure data with the Antoine equation

and the parameters obtained are presented in Eq. (1). A maximum
error of 1.3 kPa between observed and calculated vapor pressure in
the range of 343.15 K and 473.15 K was found.
ln(PV /kPa) = 15.02

3179.42
(T/K) 98.90

(1)

As observed in Fig. 1, 3-methyl-1-butanol vapor pressure data

agree with literature reports and Eq. (1) ts well in the evaluated
temperature range.
Vaporliquid equilibrium data for the binary system were used
to calculate activity coefcients by using Eq. (2).
i =

i yi P
xi Pisat

(2)

Fugacity coefcient () was tted to unity assuming ideal

behavior in the vapor phase due to the low to moderate pressures
xed in this work. Vapor pressures of pure components were calculated using Antoine equation using Eq. (1) for 3-methyl-1-butanol
and Eq. (3) for ethanol according with literature report [28].
ln(PV /kPa) = 16.47

3557.11
(T/K) 50.87

(3)

Experimental VLE data with the corresponding calculated activity coefcients are listed in Table 4. Thermodynamic consistency
tests were performed in order to estimate the quality of measured
data. Initially, the RedlichKister total area test using the criteria of
Kojima et al. [12] was performed. Additionally, the tool for thermodynamic consistency available in Aspen Plus 7.2 was used [29].
According to the suppliers, the integrated test is quite similar to
RedlichKister area test. As cited by Kang et al. [13], area tests for

Fig. 1. Vapor pressure for 3-methyl-1-butanol. The continuous line denotes the
Antoine equation with regressed parameters. () Experimental data and ()
reported data from [27].

a
u(T) = 0.07 K, u(p) = 0.03 kPa, u(x1 ) = u(y1 ) = 0.015, and the combined expanded
uncertainty Uc is Uc ( 1 ) = Uc ( 2 ) = 0.001.

isobaric data and binary mixtures can be expressed as indicated in

Eq. (4).

A =
0

1
ln
dx1 +
2

HE
RT 2



T
x1

dx

(4)

Because of the absence of experimental data of excess enthalpies

(HE ) for the system under study, a group contribution method (UNIFAC) implemented in the software Aspen Plus 7.2 was used to
estimate values of HE at different pressures. Fig. 2 presents HE vs.
x1 plot at the pressures under study. Estimated values of HE are
in the same order of magnitude of those obtained in similar polar
mixtures such as 1-butanol + acetic acid (maximum value around
of 405.0 J mol1 at 298.15 K) and 1-butanol + methanol + water
(839.7 J mol1 at 298.15 K and 101 kPa) [30,31]. Taking into
account that estimated and that the previously observed values of
HE in similar systems are low and that experiments were done at

Fig. 2. Estimated HE for the studied system. UNIFAC group contribution method was
used. Lines denote () 50.66 kPa, ( ) 101.33 kPa, and () 151.99 kPa.

J.A. Duran et al. / Fluid Phase Equilibria 338 (2013) 128134

131

Table 5
Regressed parameters for the Margules-type correlation.
Parameter

50.66 kPa

101.33 kPa

151.99 kPa

A12
A21

0.166 0.04
0.112 0.01

0.203 0.01
0.119 0.01

0.115 0.02
0.262 0.02

high temperatures, the second term in Eq. (4) is negligible and can
be removed.
Considering the above, Eq. (4) can be rewritten as,

AS =

ln
0

1
dx1
2

(5)

Kang et al. [13] suggested regressing plotted data by means of

a polynomial relation with the form presented in Eq. (6), with n, in
between (4) and (6).
ln

 
1

2

= an x1n + an1 x1n1 + + a1 x1 + a0

(6)

Due to the lack of experimental data at the innite dilution

zones, that a polynomial equation could not t data adequately
near the ends of the binary diagram and that calculated areas
were incorrect, this procedure was rejected. However a continuous representation of experimental data was obtained by using a
Margules-type expression [32]. Data in area test plot could be tted
as following,
ln

 
1

2

= x22 [A12 + 2(A21 A12 )x1 ] x12 [A21 + 2(A12 A21 )x2 ] (7)

Value of the parameters A12 and A21 were obtained by the

minimization of the difference between calculated and predicted
activity coefcients. An adequate tting was observed with the use
of Eq. (7). In Table 5, regressed parameters for the three data sets are
shown. Values of R2 higher than 0.991, were obtained in the data
tting of the area plot for three operating pressures using parameters of Table 5. Hereafter, areas in Eq. (5) were calculated based on
the continuous line obtained from Margules correlation.
Although the simplication in Eq. (4), Kang et al. [13] emphasized that neglecting excess enthalpies is not a recommended
practice because of the large contribution of this term on the calculated area (as high as 4 102 ). However, the lack of experimental
data on HE for many systems may force to neglect that contribution
in the calculations as commented by Herington [19] and Wisniak
[21]. Regarding this problem, Herington [19] proposed an empirical inequity in order to estimate the right-hand side of the integral
in Eq. (4) concerning to HE data. Using the maximum value of HE
and the extreme boiling temperatures of the mixture, it can be
demonstrated that,

ln
0

1
Hm |Tmax Tmin |
dx1 <
2
RT 2

(8)

Considering that,
d(GE /RT )
1
= ln
2
dx1

(9)

The left-side of inequity (8) could be expressed in terms of excess

free energy as,



 Hm   Tmax Tmin 

|AS |

< 50 

E 
Tmin
A
Gm

(10)

Herington [19] and Wisniak [21] obtained an average value of

E based on measured data of 15 sys3.0 for the relation Hm /Gm
tems. Then, Eq. (10) is approximately,
D = 100

 
D  < J

(12)

where D, can be expressed by the areas above (L) and below (W) of
the abscissa axis in ln( 1 / 2 ) vs. x1 (area test plot).



 (L W ) 

(L + W )

D = 100 

|AS |
 Tmax Tmin 
< 150 
=J
A
Tmin

(11)

(13)

According to Heringtons experience, deviation from experimental errors will give an uncertainly of 10 units in D. Hence, if
|D J| > 10, the evaluated data must be considered inconsistent.
E parameNevertheless, Wisniak [21] re-evaluated the Hm /Gm
ter in Eq. (10) based on data available on literature. He found that
E could vary between 0 and 28.6 and the value
values of Hm /Gm
of 3.0 was exceeded in more than 20% of the systems examined.
E from experimental
Wisniak correlated data of Hm against Gm
data with good results using the relationship,
E
(J mol1 )
Hm (J mol1 ) = 237.02 + 1.3863Gm

(14)

In this work, values of GE were calculated from experimental

data with the expression,


GE
xi ln i
=
RT

(15)

E data were plotted against composition and correlated with

Gm
a second order polynomial as shown in Fig. 3. Maximum was
obtained by simple derivation. Values of Hm were calculated with
E are 0.93, 0.60 and 0.14 for
Eq. (14). Calculated values for Hm /Gm
data sets at 50.66, 101.33 and 151.99 kPa, respectively. An average
of 0.56 was used in the modied consistency area test. Then, Eq.
(10) could be rewritten ad hoc as,



 Tmax 
=J
T

D < 28 

min

100

Fig. 3. Calculated excess free energies of mixing. () 50.66 kPa, () 101.33 kPa, ()
151.99 kPa, () polynomial adjustment.

(16)

min

Using Herington test reported in Eqs. (11) and (12), all three data
sets were found inconsistent. After recalculation of the parameter
J using Eq. (16), all data sets were found consistent, even when a
conservative criterion of 5 instead of 10 was used. Even though
Herington test has been used successfully in systems containing
alcohols, esters and non-polar compounds [3336], some papers
have shown data sets that passed RedlichKister test but failed Herington test [37,38]. This failure in the Herington test as noticed by
Wisniak [21] could lead to consider some VLE data inconsistent
even when they are not. Resa et al. [39] used the modication recommended by Wisniak [21] in the calculation of particular values
E for the binary mixtures acetone + propyl ether and
of Hm /Gm
isopropyl ether at 101.325 kPa. Those researchers calculated Hm
E from a regression of experimental data.
using Eq. (14) and Gm

132

J.A. Duran et al. / Fluid Phase Equilibria 338 (2013) 128134

Table 6
Results of thermodynamic consistency tests.
Parameter

50.66 kPa

101.33 kPa

151.99 kPa

Total area
Area
Result

0.013
Passed

0.001
Passed

0.001
Passed

Van Ness
T
y
Result

0.066
0.219
Passed

0.039
0.083
Passed

0.058
0.147
Passed

Point

Result

1.888
Passed

1.470
Passed

6.926
Failed

Herington
D
J
|D J|
Result

9.309
22.754
13.444
Failed

0.408
22.643
22.2356
Failed

0.171
22.793
22.622
Failed

Modied Herington
Jcorrected
|D J|corrected
Result

4.222
5.087
Passed

4.202
3.794
Passed

4.229
4.059
Passed

Aspen Plus
Result

Passed

Passed

Failed

Fig. 4. Diagram of ln  i vs x1 at 50.66 kPa. () ln  1 , () ln  2 , () NRTL modeled.

Resa and co-workers found good results in thermodynamic conE = 3 in Eq. (10) and
sistency by leaving out the value of Hm /Gm
using an ad hoc consistency test.
Concerning other consistency testing methods, area test was
also evaluated using Aspen Plus 7.2 which uses total area test by
RedlichKister [1719]. Additionally, Van Ness and point tests were
passed for all three data sets according to the criteria reported by
Kang et al. [13]. A summary of thermodynamic consistency tests
results are shown in Table 6. According to the obtained results,
Herington test modied by Wisniak was applied in data rejection.

Even though only 68 experimental data were found consistent

from around 15 that were measured at each pressure, all of them
seem to follow the VLE tendency in a Txy plot as noticed in Fig. 5.
3.2. Data regressions
Parameters for NRTL and UNIQUAC activity based models
[40,41] were obtained through a numerical regression by using the
Aspen Plus 7.2 calculation tool. Deming algorithm was used as
convergence method. Temperature dependent parameters of NRTL
model were considered in their linear form,
ij = aij +

bij
T/K

(17)

Fig. 5. Phase diagram (Txy ) for the system ethanol (1) + 3-methyl-1-butanol (2) at the three pressures under investigation. Markers denote () 50.66 kPa, () 101.33 kPa, ()
151.99 kPa. () NRTL, (----) UNIQUAC. Filled markers represent rejected data according with ad hoc Wisniak test.

J.A. Duran et al. / Fluid Phase Equilibria 338 (2013) 128134

Table 7
Regressed NRTL and UNIQUAC parameters.
NRTL

UNIQUAC

Parameter

Value

Parameter

Value

a1,2
a2,1
b1,2
b2,1
1,2 = 2,1
ymax
Tmax (K)

2.61 0.31
3.71 0.17
857.56 19.64
1171.20 24.41
0.30
0.011
0.550

a12 (K)
a21 (K)
Deviation
ymax
Tmax (K)

113.75 20.77
190.97 11.56
0.014
0.701

133

vapor pressure data for 3-methyl-1-butanol were measured and

well correlated with Antoine equation. Agreement between the
experimental and calculated VLE at three different pressures, was
found. Equilibrium data were tested for thermodynamic consistency using RedlichKister area test, Van Ness test and point test.
Measured data were found to be thermodynamically consistent
according to the adopted ad hoc test of Wisniak, which was modE for the
ied with an adequate value for the relation Hm /Gm
studied system. Data were well tted to NRTL and UNIQUAC activity
models. NRTL model gives a better representation of experimental
data and obtained parameters can be used for the design of separation operations for ethanol and 3-methyl-1-butanol from fusel
oil.
List of symbols

Fig. 6. Diagram (xy) for the ethanol (1) + 3-methyl-1-butanol (2) system at
332.95 K. () Reported data by Sanz and Gmehling [10]. Simulated equilibrium using
NRTL () and UNIQUAC (---------) parameters obtained in this work.

Volume and area parameters (qi , ri ) for the UNIQUAC model

were taken from literature [42]. In both cases, the objective function is the minimization of differences in activity coefcients as
presented in Eq. (18). Table 7 presents the obtained parameters
for NRTL and UNIQUAC activity models. Total sum of squares are
also presented for each data set. Quality of regression could be
veried in Fig. 4, where experimental activity coefcients were
compared with NRTL modeling for data at 50.66 kPa. In this gure,
the calculated uncertainty bars are shown. As observed in Fig. 4, the
condence intervals are broader near the pure components. This is
caused by high uncertainties in the GC characterization of samples at concentrations higher than 0.95 and lower than 0.05 (mole
fraction).
OFmin =

(1 1calc ) +

(2 2calc )

(18)

Fig. 5 presents the phase equilibrium diagram for three

pressures under investigation, where the modeling with NRTL and
UNIQUAC is shown. NRTL and UNIQUAC models were compared
with existing literature data for the system under study [10]. As
shown in Fig. 6, NRTL parameters obtained in this work agree with
isothermal data reported by Sanz and Gmehling [10] at 332.95 K
and can be used for separation process design. In comparison UNIQUAC modeling presents higher deviations from experimental data
(Fig. 5) and reported data in literature for the system (Fig. 6) [10].
Hence, obtained parameters for NRTL activity model should be preferred for design purposes.

A*
A12 , A21
a, b
D, J
G
H
L
n
OF
P
q
r
R
T
W
x
y

total area of RedlichKister test (Eq. (4))

parameters of Margules model (Eq. (7))
parameters of NRTL activity model
parameters of Wisniak test
Gibbs free energy (J mol1 )
enthalpy (J mol1 )
area upon abscissa in area test plot
polynomial order (Eq. (6))
objective function
pressure (kPa)
surface parameter of the UNIQUAC model
size parameter of the UNIQUAC model
universal gas constant (J mol1 K1 )
temperature (K)
area below abscissa in area test plot
mole fraction in liquid
mole fraction in vapor

Greek letters

coefcient of activity

property difference

parameter of point test of thermodynamic consistency


refractive index

temperature dependent parameter of NRTL model
coefcient of fugacity

Subscripts
component
i, j
m
maximum
min
minimum
v
vapor phase
simplied expression
S
Superscripts
calc
calculated value
E
property of excess
sat
saturation
Acknowledgements
This work has been supported by Colciencias, Ecopetrol S.A. and
Universidad Nacional de Colombia (Project No. 1101-490-26038).
J. Duran acknowledges to Rotary Club Intl. Bogota Chapinero for
nancial support received during his postgraduate studies.

4. Conclusions
Isobaric vaporliquid equilibrium of ethanol + 3-methyl-1butanol at three different pressures has been investigated. Also,

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