Fluid Phase Equilibria 384 (2014) 134142

Contents lists available at ScienceDirect

Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Isothermal vaporliquid equilibrium for binary mixtures containing

furfural and its derivatives
Wen-Ping Tai, Hao-Yeh Lee, Ming-Jer Lee *
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Rd., Sec. 4, Taipei 106-07, Taiwan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 August 2014
Received in revised form 23 October 2014
Accepted 25 October 2014
Available online 29 October 2014

The isothermal vaporliquid equilibrium (VLE) data were measured for the binary systems of
2-methylfuran + furfuryl alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural at 353.2, 373.2,
and 408.2 K over entire composition range, including the vapor pressures of ve constituent compounds.
The experimental results of the investigated binary systems show no azeotrope formation and positive
deviations from Raoults law. The thermodynamic consistency of these new binary VLE data has been
conrmed by point, area, and innite dilution tests. The WilsonHOC, the NRTL-HOC, and the UNIQUACHOC models were used to correlate the VLE data. Comparable results were obtained from these three
models.
2014 Elsevier B.V. All rights reserved.

Keywords:
VLE
2-Methylfuran
Furfuryl alcohol
Furan
Furfural

1. Introduction

2. Experimental section

As fossil fuels are gradually depleted, biomass will inevitably

become an alternative resource to provide a kind of renewable
energy and raw materials for chemical industries in the future.
Furfural is one of the key intermediates to connect the bio-resource
to bio-fuels or chemical products [1]. In this green manufacturing
route, furfural alcohol can be synthesized via hydrogenation of
furfural using isopropyl alcohol as a solvent. Simultaneously,
several by-products, including 2-methylfuran and furan, may also
be generated from this series of chemical reactions [2]. To provide
reliable VLE data for the related process development, we
measured the isothermal VLE for three binary systems:
2-methylfuran + furfuryl alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural at 353.2, 373.2, and 408.2 K over entire
composition range, including the vapor pressures of ve constituent compounds. No VLE data at the comparable conditions are
available in literature for the above mentioned mixtures. All the
new binary VLE data were validated by thermodynamic consistency tests and then correlated with the WilsonHOC [3], the
NRTL-HOC [4], and the UNIQUAC-HOC [5] models. The optimal
values of binary parameters were obtained from the data
correlation.

2.1. Chemicals
2-Methylfuran (purity: 0.99 in mass fraction) was purchased
from ACROS (USA) and furan (purity: 0.99 in mass fraction) from
Alfa Aesar (USA). Furfural (purity: 0.99 in mass fraction), furfural
alcohol (purity: 0.98 in mass fraction), and isopropyl alcohol
(purity: 0.999 in mass fraction) were supplied by SigmaAldrich
(USA). The purity levels of these chemicals were conrmed by
chromatographic analysis. All the chemicals were used without
further purication. The materials description is given in Table 1
for each pure compound. The density of each compound has been
measured with a vibrating-tube densimeter (DMA 4500, Anton
Paar, Austria) to an uncertainty of 0.1% and compared with
literature value in Table 1. The deviations between experimental
and literature values are from 0.01 to 0.19%. It should also be noted
that furfural and furfural alcohol are light-sensitive compounds.
We handled these two substances with care. The degassing process
was operated in dark and the ask was warped with aluminum foil.
The color will become from yellowish, initially, to brownish after
the measurement process, especially at higher temperature
408.2 K. A small impurity peak can be detected from the phase
equilibrium samples by GC, but the amount of the impurity is less
than 0.7% in the worst case.
2.2. Apparatus and procedure

* Corresponding author. Tel.: +886 2 2737 6626; fax: +886 2 2737 6644.
E-mail address: mjlee@mail.ntust.edu.tw (M.-J. Lee).
http://dx.doi.org/10.1016/j.uid.2014.10.037
0378-3812/ 2014 Elsevier B.V. All rights reserved.

A static VLE apparatus was employed in the present study to

measure the VLE data. The equipment is similar to that of Lee and

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

Nomenclature
A
A1A9
Aij
aij
bij
C0C2
D0D3
G
I1 and I2
MW
n
P
q
r
R
Rg
T
Tb
V
x
y
Z

index of area consistency test

parameters of the extended Antoine equation
interaction variables in Wilson model
parameters of the activity coefcient model
parameters of the activity coefcient model (K)
variables used in consistency tests
variables used in consistency tests
molar Gibbs free energy (J mol1)
indices of innite dilution consistency test
molecular weight (g mol1)
number of data points
pressure (kPa)
surface area parameter of UNIQUAC model
volume parameter of UNIQUAC model
gas constant (kPa cm3 mol1 K1 or J mol1 K1)
radius of gyration ()
temperature (K)
normal boiling temperature (K)
molar volume (cm3 mol1)
mole fraction of liquid phase
mole fraction of vapor phase
compressibility factor

Greek letters
parameter of NRTL model
activity coefcient
index of point consistency test
deviation
association parameter of HOC model
dipole moment (Debye)
objective function
density (g cm3)
standard deviation
interaction variables in NRTL and UNIQUAC models
fugacity coefcient of component i
acentric factor

a
g
d
D
h
m
p
r
s
t ij
^
f
i
v

Subscripts
c
critical property
cal calculated value
i
component i
exp experimental value
ij
i-j pair
P
pressure
T
temperature
x1
liquid composition of component 1
y1 vapor composition of component 1
Superscripts
cal calculated value
E
excess property
exp experimental value
L
liquid phase
sat saturation

Hu [10] and several modications have been made by Hwang et al.

[11]. A stainless steel made equilibrium cell was placed in a
thermostatic bath (Model: B503S, stability =
0.03 K, Firstek,
Taiwan). The bath temperature was measured by a precision

135

thermometer (Model-1560, Hart Scientic, USA) with a platinum

RTD probe to an accuracy of
0.02 K. Two pressure transducers
(Model: PDCR-912, pressure ranges: 0101.325 kPa and 02.0 MPa,
Druck, UK) with digital indicators (Model: DPI-280, Druck, UK)
displayed the equilibrium pressure to an accuracy of
0.1%. While
the vapor sample was taken with a six-way sampling valve (Model
6T, operable up to 573 K and 2067 kPa, sample size 100 ml, VICI AG
International, Switzerland), the liquid sample was taken with a
four-way sampling valve (Model 6CI4UWT1/2, operable up to
603 K and 2067 kPa, sample size 0.5 ml, VICI AG International,
Switzerland). Compositions of both vapor and liquid samples were
analyzed by a gas chromatography (Model: 8700T, China
Chromatography, Taiwan) with a thermal conductivity detector
(TCD). A stainless steel column Porapak QS (80/100 mesh,
1.5 m  1/8  I.D. 2 mm) was used for sample analysis. High purity
helium (99.99% purity, Gu-Fong Gas Company, Taiwan) was used as
carrier gas. Four samples were replicated for individual phase at
each experimental condition. The averaged area fraction of the
replication samples was converted into mole fraction via
calibration equations. The uncertainties of the reported mole
fractions for liquid and vapor phases are within 0.005 and 0.005,
respectively.

3. Results and discussion

The isothermal VLE data are measured in the present study for
the binary systems of 2-methylfuran + furfuryl alcohol, isopropyl
alcohol + furfuryl alcohol, and furan + furfural at 353.2, 373.2, and
408.2 K over entire composition range. Table 2 lists the coefcients
of the extended Antoine equation for each constituent compound
where the equation is dened as
"
#


Psat kPa
A2
ln
A4 T A5 lnT
A1
100
T K A3
A6 T A7 forA8
 T  A9

(1)

The values of A1A9 are available from the Aspen thermodynamic databank, except for 2-methylfuran. The vapor pressures of
all pure compounds are also determined experimentally in this
study. As shown in Table 3, the measured vapor pressures of
furfuryl alcohol, furan, furfural, and isopropyl alcohol agree well
with the smoothed literature values, which are calculated from the
extended Antoine equation using the coefcients listed in Table 2.
Eon et al. [12] reported the vapor pressures of 2-methylfuran at
temperatures from 333.45 to 373.45 K and the Antoine constants
determined from these data have been collected in the NIST
Chemistry WebBook [13]. Kobe et al. [14] measured the vapor
pressures from 336.72 to 527.59 K. In this study, we measured 23
new data points for 2-methylfuran at temperatures from 353 to
409 K as given in Table 4. The coefcients of the extend Antoine
equation for 2-methylfuran are obtained by tting these new data
to Eq. (1) and listed in Table 2. Table 4 and Fig. 1 compare the
experimental values with the correlated results from the extended
Antoine equation and those from of the Antoine equation using the
constants taken from NIST Chemistry WebBook [13] and the data
reported by Kobe et al. [14]. The deviations are all within 1.0% over
the entire temperature range.
The isothermal VLE data are listed in Tables 57 for the binary
systems of 2-methylfuran + furfuryl alcohol, isopropyl alcohol +
furfuryl alcohol, and furan + furfural, respectively. The tabulated
activity coefcients (gi) were calculated from the criteria of phase
equilibria, i.e.,

136

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

Table 1
Description of the materials useda .
Compound

Supplier

Purity in mass fraction

Purication method

rexp (g/cm3)

rlit(g/cm3)

Data source

2-Methylfuran
Furan
Furfural
Furfural alcohol
Isopropyl alcohol

Acros, USA
Alfa Aesar, USA
SigmaAldrich, USA
SigmaAldrich, USA
SigmaAldrich, USA

0.99
0.99
0.99
0.98
0.999

Degas
Degas
Degas
Degas
Degas

0.9132
0.9331
1.1546
1.1320
0.7809

0.91500
0.9340
1.15525
1.13028
0.78082

[6]
[7]
[8]
[8]
[9]

u(r) = 0.1%.

Table 2
Parameters of the extended Antoine equationa .
Compound

A1

2-Methylfuranb
Furanc
Furfuralc
Furfural alcoholc
Isopropyl alcoholc

17.4859
63.2251
83.0571
63.5521
99.2071

a
b
c

A2

A3

A4

A5

248.3232
0.0306
6.8370
0
0
8.0636
0
0
11.1300
0
0
7.2425
0
0
12.6760


Extended Antoine equation: lnPsat kPa=100 A1 A2 = TK A3  A4 T A5 lnT A6 T A7 forA8  T  A9 .
Determined from the vapor pressure data measured in this work.
Taken from thermodynamic databank of Aspen Plus process simulation package.

gi

225.3
5417.0
8372.1
8846.6
9040.0

^ yP
f
i i
sat sat
i P i exp

xi f

(2)

V Li P  Psat
i =RT

where xi, yi, and Psat

i are liquid mole fraction, vapor mole fraction,
and vapor pressure for component i, respectively. The liquid molar
volume, V Li , was estimated from the modied Rackett model [15].
sat
^ are the fugacity coefcients of pure i at
The variables fi and f
i
saturation condition and the fugacity coefcient of component i in
the vapor phase. These two fugacity coefcients were calculated
from two-term virial equation with the second virial coefcient

A6

A7

A8 (K)

A9 (K)

14.7121
7.5E-06
8.8E-03
2.8E-06
5.5E-06

0.0033
2
1
2
2

353.0
187.0
236.0
258.0
185.2

409.2
490.2
670.2
632.2
508.3

estimated from the Hayden and OConnell model [16]. The molar
excess Gibbs free energies, GE, listed in Tables 57 were calculated
from the following denition:
G E RT

2
X
xi lng i

(3)

i1

Figs. 24 are the phase diagrams of 2-methylfuran + furfuryl

alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural,
respectively. All these investigated systems exhibit positive

Table 3
Vapor pressures of furan, furfural, furfuryl alcohol, and isopropyl alcohola .
Psat
exp (kPa)

b
Psat
cal (kPa)

Dev Pc (%)

455.1
735.6
1513.3

455.7
735.1
1513.6

0.13
0.07
0.02

Furfural
353.2
373.4
408.0

5.9
13.6
46.3

5.9
13.7
46.3

0.00
0.74
0.00

Furfuryl alcohol
353.3
373.0
407.9

2.6
7.0
30.1

2.6
7.0
30.2

0.00
0.00
0.33

93.8
200.1
593.8

94.0
200.9
594.3

0.21
0.40
0.08

T (K)
Furan
353.4
373.1
407.9

Isopropyl alcohol
353.3
373.5
408.3
a
b
c

u(T) = 0.1 K; u(P) = 0.1%.

Calculated from theextended Antoine
equation.

sat
sat
DevP% 100%  Psat
cal  P exp =P exp .

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

137

Table 4
Vapor pressures of 2-methylfurana .
T (K)

b
Psat
exp (kPa)

c
Psat
cal (kPa)

Dev Pd (%)

e
(kPa)
Psat
lit

Dev Pf (%)

353.8
353.8
357.5
357.5
358.3
362.4
362.5
363.1
367.2
367.4
367.9
373.4
373.6
373.9
398.2
398.4
398.8
403.0
403.2
403.3
408.4
408.6
409.0

161.8
162.6
181.5
181.7
186.5
210.5
211.1
214.9
242.1
242.7
246.0
285.3
286.4
288.4
527.6
530.3
533.8
587.6
591.7
592.3
667.2
670.2
676.7

162.3
162.5
181.7
181.9
186.4
210.6
210.7
214.5
241.3
242.2
245.5
285.3
286.4
289.3
527.1
530.1
534.6
589.1
592.0
593.5
666.4
669.4
675.5
AARDg (%) = 0.14

0.31
0.06
0.11
0.11
0.05
0.05
0.19
0.19
0.33
0.21
0.20
0.00
0.00
0.31
0.09
0.04
0.15
0.26
0.05
0.20
0.12
0.12
0.18
AARDg (%) = 0.53

163.3
163.6
181.9
182.1
186.4
209.9
209.9
213.6
240.0
240.9
244.1
283.7

0.93
0.62
0.22
0.22
0.05
0.29
0.57
0.60
-0.87
0.74
0.77
0.56

a
b
c
d
e
f
g

u(T) = 0.1 K; u(P) = 0.1 %.

Experimental data obtained from this work.
Correlated results from
Antoine equation.
 the extended

sat
sat
DevP% 100%  Psat
cal  P exp =Pexp .
Calculated from the Antoine equation
by using parameters reported in NIST Chemistry WebBook [13] (original data source: Eon et al. [12]).

sat
sat
DevP% 100%  Psat

lit P exp =Pexp .
n
sat
sat
AARD% 100%=nSi1 jPX  Pexp j=Psat
exp , where subscript X represents cal or lit, and n is the number of data points.
i

deviations from Raoults law. In each binary system, no azeotrope

is formed and the light component is dominant in the vapor phase.
According to the experimental results, the compounds in the
related mixtures can be separated efciently by using distillation
technique.
Thermodynamic consistency tests were made for all the new
VLE data. The testing method has been detailed in Kojima et al. [17]
and Lee and Hu [10]. Table 8 gives the results of the
thermodynamic consistency test. All the binary VLE data passed
the thermodynamic consistency evaluation, including the point,
the area, and the innite dilution tests.

[(Fig._1)TD$IG]

P/kPa

1000

4. Vaporliquid equilibrium data correlation

100
340

The gw method was employed to correlate the new binary VLE

data. Three activity coefcient models, including the Wilson, the
NRTL, and the UNIQUAC, were selected to represent the nonideality of liquid mixtures, while the fugacity coefcient in the
vapor phase were estimated from the two-term virial equation
accompanying with the HaydenOConnell (HOC) model for
calculating the second virial coefcient. The optimal values of
the binary parameters were determined by the minimization of the
following objective function p:
360

380

400

420

T/K

8"
#
exp 2
n <
X
Pcal
k P
k1

Fig. 1. Comparison of experimental vapor pressures with literature values for 2methylfuran (open circle: experimental point; open square: literature value [13];
open triangle: literature value [14]; solid line: correlation with extended Antoine
equation).

sp

" cal
#2
T k  T exp
k

sT

" cal
#2
x1;k  xexp
1;k

s x1

" cal
#2 9
=
y1;k  yexp
1;k

sy1

(4)

138

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

Table 5
VLE data of 2-methylfuran (1) + furfural alcohol (2)a .
T(K)

P(kPa)

x1

y1

353.2

2.6b
19.3a
32.0a
53.8a
62.2a
83.8a
97.3a
111.1a
127.8a
146.4a
150.0a
159.1b
7.1b
25.7a
54.2a
86.4a
112.5a
159.0a
179.2a
198.1a
224.9a
254.7a
270.6a
283.3b
30.4b
62.5a
148.9a
241.6a
297.9a
380.5a
424.7a
467.1a
515.2a
581.2a
626.6a
662.3b

0.0
0.058
0.112
0.207
0.259
0.397
0.482
0.572
0.712
0.865
0.929
1.0
0.0
0.032
0.111
0.208
0.290
0.399
0.475
0.571
0.709
0.854
0.929
1.0
0.0
0.028
0.112
0.210
0.300
0.402
0.468
0.571
0.704
0.841
0.925
1.0

0.0
0.869
0.925
0.959
0.966
0.978
0.983
0.987
0.991
0.995
0.996
1.0
0.0
0.729
0.878
0.929
0.949
0.968
0.974
0.979
0.985
0.991
0.995
1.0
0.0
0.522
0.809
0.891
0.916
0.942
0.951
0.960
0.969
0.980
0.989
1.0

373.2

408.2

a
b

g1

g2

ln(g 1/g 2)

(GE/RT)/x1x2

1.832
1.673
1.576
1.466
1.303
1.252
1.208
1.120
1.059
1.011

1.015
1.021
1.049
1.076
1.150
1.200
1.267
1.497
2.029
3.162

0.590
0.494
0.407
0.310
0.125
0.042
0.047
0.290
0.650
1.140

0.903
0.767
0.805
0.798
0.792
0.812
0.855
0.960
1.245
1.399

2.218
1.611
1.437
1.362
1.409
1.334
1.227
1.121
1.051
1.026

1.007
1.023
1.046
1.074
1.095
1.134
1.225
1.442
1.919
2.308

0.790
0.454
0.318
0.237
0.252
0.163
0.001
0.252
0.602
0.810

1.042
0.746
0.673
0.681
0.797
0.814
0.833
0.907
1.106
1.268

1.994
1.807
1.689
1.481
1.427
1.369
1.235
1.104
1.040
1.019

0.996
1.002
1.005
1.054
1.053
1.097
1.201
1.460
1.929
2.383

0.694
0.589
0.519
0.340
0.304
0.221
0.027
0.28
0.618
0.849

0.572
0.685
0.688
0.737
0.724
0.788
0.812
0.872
1.027
1.190

g1

g2

ln (g 1/g 2)

(GE/RT)/x1x2

1.247
1.213
1.201
1.182
1.147
1.112
1.096
1.085
1.039
1.004

1.004
1.005
1.007
1.016
1.039
1.071
1.105
1.134
1.187
1.218

0.217
0.188
0.176
0.152
0.098
0.037
0.008
0.044
0.133
0.193

0.293
0.260
0.263
0.291
0.327
0.350
0.387
0.431
0.383
0.260

1.287
1.240
1.178
1.144
1.105
1.084
1.077
1.057
1.042
1.003

1.007
1.006
1.014
1.024
1.036
1.048
1.081
1.116
1.152
1.202

0.245
0.208
0.150
0.111
0.064
0.033
0.004
0.055
0.101
0.181

0.354
0.297
0.276
0.272
0.254
0.252
0.305
0.332
0.350
0.234

1.206
1.205
1.179
1.143
1.127
1.112

1.005
1.005
1.008
1.027
1.027
1.035

0.182
0.181
0.157
0.108
0.093
0.071

0.259
0.257
0.247
0.280
0.263
0.272

u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.

Calculated from the extended Antoine equation.

Table 6
VLE data of isopropyl alcohol (1) + furfuryl alcohol (2)a .
T(K)

P(kPa)

x1

y1

353.2

2.6b
9.5a
18.6a
23.6a
33.9a
45.0a
52.5a
58.0a
67.1a
73.5a
84.5a
93.3b
7.1b
27.0a
35.2a
46.5a
60.1a
87.9a
100.4a
116.6a
140.8a
153.3a
179.8a
198.4b
30.4b
92.0a
108.3a
157.1a
242.4a
262.1a
304.8a

0.0
0.062
0.148
0.196
0.296
0.412
0.499
0.561
0.658
0.755
0.901
1.0
0.0
0.084
0.123
0.181
0.250
0.392
0.460
0.541
0.669
0.740
0.904
1.0
0.0
0.099
0.125
0.206
0.350
0.387
0.461

0.0
0.737
0.877
0.908
0.943
0.963
0.972
0.977
0.984
0.989
0.996
1.0
0.0
0.756
0.820
0.871
0.907
0.947
0.958
0.968
0.980
0.985
0.995
1.0
0.0
0.693
0.745
0.837
0.909
0.920
0.938

373.2

408.2

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

139

Table 6 (Continued)
T(K)

a
b

P(kPa)

x1

y1

g1

g2

ln (g 1/g 2)

(GE/RT)/x1x2

346.1a
402.4a
433.5a
512.3a
591.4b

0.536
0.651
0.715
0.857
1.0

0.951
0.967
0.974
0.987
1.0

1.092
1.050
1.031
1.014

1.062
1.083
1.112
1.271

0.027
0.030
0.075
0.226

0.302
0.263
0.256
0.375

u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.

Calculated from the extended Antoine equation.

Table 7
VLE data of furan (1) + furfural (2)a .
T(K)

P(kPa)
b

353.2

5.9
44.7a
85.4a
135.4a
194.8a
214.4a
248.0a
291.3a
315.7a
360.0a
410.4a
452.4b
13.5b
84.7a
148.9a
212.2a
319.2a
348.7a
408.5a
471.1a
514.1a
591.3a
668.1a
735.8b
46.4b
185.8a
273.7a
432.5a
648.6a
709.4a
823.3a
963.1a
1058.6a
1220.8a
1402.8a
1521.0b

373.2

408.2

a
b

x1

y1

0.0
0.08
0.164
0.271
0.401
0.459
0.541
0.642
0.703
0.802
0.918
1.0
0.0
0.073
0.155
0.248
0.405
0.459
0.548
0.656
0.721
0.820
0.920
1.0
0.0
0.080
0.140
0.257
0.411
0.457
0.547
0.653
0.719
0.821
0.931
1.0

0.0
0.875
0.939
0.965
0.979
0.982
0.986
0.990
0.992
0.995
0.998
1.0
0.0
0.845
0.915
0.944
0.968
0.972
0.979
0.985
0.988
0.993
0.997
1.0
0.0
0.754
0.835
0.900
0.942
0.950
0.961
0.972
0.978
0.987
0.995
1.0

g1

g2

ln(g 1/g 2)

(GE/RT)/x1x2

1.180
1.169
1.141
1.111
1.067
1.044
1.028
1.014
1.007
0.995

1.012
1.016
1.031
1.049
1.085
1.130
1.187
1.225
1.279
1.371

0.153
0.141
0.101
0.057
0.016
0.079
0.144
0.189
0.239
0.320

0.327
0.282
0.295
0.296
0.297
0.319
0.344
0.335
0.342
0.285

1.501
1.330
1.208
1.119
1.077
1.053
1.009
0.997
0.999
0.996

1.014
1.043
1.070
1.110
1.152
1.181
1.244
1.315
1.323
1.395

0.392
0.243
0.121
0.008
0.068
-0.115
0.210
0.277
0.281
0.337

0.631
0.608
0.525
0.447
0.446
0.418
0.359
0.369
0.337
0.314

1.392
1.281
1.162
1.106
1.087
1.050
1.020
1.011
1.007
1.002

1.020
1.048
1.105
1.133
1.138
1.192
1.251
1.296
1.319
1.430

0.311
0.201
0.050
0.025
0.045
0.127
0.204
0.248
0.270
0.355

0.605
0.624
0.590
0.475
0.437
0.427
0.400
0.398
0.374
0.417

u(T) = 0.1 K; u(P) = 0.1%; u(x1) = 0.005; u(y1) = 0.005.

Calculated from the extended Antoine equation.

Table 8
Results of thermodynamics consistency tests.
Consistency test indexa
T (K)

2-Methylfuran (1) + furfuryl

353.2
4.92 (+)
373.2
4.08 (+)
408.2
4.22 (+)

A
alcohol (2)
0.55 (+)
0.73 (+)
2.10 (+)

Isopropyl alcohol (1) + furfuryl alcohol (2)

353.2
4.90 (+)
2.61 (+)
373.2
2.24 (+)
2.34 (+)
408.2
2.20 (+)
1.37 (+)
Furan (1) + furfural (2)
353.2
1.92 (+)
373.2
2.47 (+)
408.2
1.52 (+)

1.24 (+)
0.40 (+)
1.35 (+)

GE/RT coefcientb
I1

I2

C0

C1

5.8 (+)
17.1 (+)
11.2 (+)

7.4 (+)
18.5 (+)
7.7 (+)

0.710
0.759
0.787

0.336
0.227
0.293

8.9 (+)
7.5 (+)
9.5 (+)

16.0 (+)
11.8 (+)
8.5 (+)

0.358
0.280
0.257

18.2 (+)
3.2 (+)
21.2 (+)

11.3 (+)
25.3 (+)
5.4 (+)

0.226
0.327
0.338

ln(g 1/g 2) coefcientc

D0

D1

0.394
0.423
0.137

0.005
0.007
0.021

0.791
0.727
0.853

0.269
0.180
0.231

0.287
0.275
0.068

0.037
0.007
0.059

0.127
0.011
0.060

0.026
0.023
0.014

0.259
0.237
0.271

0.035
0.010
0.102

0.037
0.052
0.053

0.028
0.152
0.109

0.027
0.033
0.066

0.012
0.004
0.013

0.264
0.369
0.316

0.044
0.105
0.070

0.063
0.019
0.051

(+): passes the consistency test.

a
Criteria for passing
the thermodynamic consistency
tests: d < 5, A < 3, I1 < 30, I2 < 30.
h
i
b
GE/RT = .x1 x2 C 0 C 1 x1  x2 C 2 x1  x2 2
c
ln g 1 =g 2 D0 D1 x2  x1 D2 6x1 x2  1 D3 x2  x1 1  8x1 x1 .

C2

D2

D3

140

[(Fig._2)TD$IG]

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

800
353.15 K
373.15 K
408.15 K
NRTL-HOC
Wilson-HOC
UNIQUAC-HOC

P/kPa

600

400

200

0
0

0.2

0.4

0.6

0.8

x1 , y1
Fig. 2. VLE of 2-methylfuran (1) + furfural alcohol (2) at 353.2, 373.2, and 408.2 K (solid symbols: experimental liquid phase; open symbols: experimental vapor phase; circle:
353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTL-HOC; short dashed line: WilsonHOC; solid line: UNIQUAC-HOC).

where n is the number of data points and si is the standard

deviation of the measured variable i. In the correlations, the
values of s were set to s P = 0.1%, s T = 0.1 K, s x1 = 0.1%, and
s y1 = 1%. The optimization has been made with the aid of
Aspen Properties software. Table 9 lists the physical properties
of each constituent compound which are needed in the
data correlation. Tables 1012 report the correlated results

from the WilsonHOC, the NRTL-HOC, and the UNIQUAC-HOC

models, respectively. The smoothed curves in Figs. 24
represent the calculated results. As can been seen from the
tabulated values and the graphs, the data correlations are
satisfactory and the average absolute relative deviations
(AARD) obtained from these three thermodynamic models
are comparable.

[(Fig._4)TD$IG]
[(Fig._3)TD$IG]

600

1600

400

P/kPa

1200

P/kPa

353.15 K
373.15 K
408.15 K
NRTL-HOC
Wilson-HOC
UNIQUAC-HOC

353.15 K
373.15 K
408.15 K
NRTL-HOC
Wilson-HOC
UNIQUAC-HOC

800

200
400

0
0

0.2

0.4

0.6

0.8

x1 , y1
Fig. 3. VLE of isopropyl alcohol (1) + furfuryl alcohol (2) at 353.2, 373.2, and 408.2 K
(solid symbols: experimental liquid phase; open symbols: experimental vapor
phase; circle: 353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTLHOC; short dashed line: WilsonHOC; solid line: UNIQUAC-HOC).

0.2

0.4

0.6

0.8

x1 , y1
Fig. 4. VLE of furan (1) + furfural (2) at 353.2, 373.2, and 408.2 K (solid symbols:
experimental liquid phase; open symbols: experimental vapor phase; circle:
353.2 K; square: 373.2 K; triangle: 408.2 K; long dashed line: NRTL-HOC; short
dashed line: WilsonHOC; solid line: UNIQUAC-HOC).

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

141

Table 9
Properties of the constituent compounds.
Compound

MWa (g mol1)

Tbb (K)

Tcb (K)

102 Pcb (kPa)

Vc

2-Methylfuran
Furan
Furfural
Furfuryl alcohol
Isopropyl alcohol

82.10
68.07
96.08
98.10
60.10

337.0
304.5
434.9
443.2
355.3

528.0
490.2
670.2
632.0
508.3

47.20
55.00
56.60
53.50
47.65

247
218
252
263
222

a
b
c
d
e
f

(m3 mol1)

Zcc

hd

Rgd ()

qd

rd

vd

md (Debye)

0.266
0.294
0.256
0.268
0.250

0.00e
0.00
0.58
0.00
1.32

2.983e
2.559
3.350
3.422
2.760

2.6280e
1.7400
2.5000
2.6760
2.5276

3.1338e
2.4021
3.1721
3.3784
2.9137

0.249e
0.202
0.368
0.734
0.663

0.650f
0.660
3.598
1.919
1.661

Taken from National Institute of Standards and Technology (NIST) Chemistry WebBook [13].
Taken from thermodynamic databank of Aspen Plus process simulation package.
Estimated from Zc = (PcVc)/(RTc).
Taken from thermodynamic databank of Aspen Plus process simulation package, except for 2-methylfuran.
Obtained from Aspen Plus property estimation by entering MW, Tb,Tc, Pc, Vc and molecular structure.
Taken from McClellan [18].

Table 10
Correlated results from the WilsonHOC model.
Mixture (1) + (2)

T (K)

a12a

a21a

2-Methylfuran + furfuryl alcohol

353.2
373.2
408.2
353.2
373.2
408.2
353.2
373.2
408.2

0.5190

1.2203

205.5

34.3

0.2879

0.6752

27.4

19.5

7.2661

4.2939

2537.5

1582.1

Isopropyl alcohol + furfuryl alcohol

Furan + furfural

b12a (K)

b21a (K)

DP/P AARDb (%)

DT/T AARDb (%)

Dx1/x1 AARDb (%)

Dy1/y1 AARDb (%)

0.21
0.52
0.20
0.07
0.11
0.07
0.20
0.34
0.30

0.17
0.38
0.11
0.08
0.10
0.05
0.10
0.15
0.15

0.15
0.40
0.12
0.04
0.11
0.04
0.18
0.26
0.23

0.20
1.03
0.29
0.09
0.27
0.37
0.22
0.32
0.71

Binary parameters in the Wilson model: lnAij = aij + bij/T.





P
n
AARD: average absolute relative deviation, dened as DP =P AARD% 100% =n nk1 jPcal  Pexp j =Pexp , DT=T AARD% 100%=n Sk1 jT cal  T exp j=T exp ,


k
k

n 
n
jx1 cal x1 exp j
Dy1 =y1 AARD% 100%=n Sk1 jy1 cal  y1 exp j=y1 exp k , Dx1 =x1 AARD% 100%
, where n is the number of data points.
n Sk1
xexp
b

Table 11
Correlated results from the NRTL-HOC model.
Mixture (1) + (2)

T (K)

2-Methylfuran + furfuryl alcohol

353.2
373.2
408.2
353.2
373.2
408.2
353.2
373.2
408.2

Isopropyl alcohol + furfuryl alcohol

Furan + furfural

a12a

a21a

b12a (K)

b21a (K)

1.6859

0.1097

154.3

126.8

0.9864

0.5469

63.0

57.4

6.1195

8.9728

2243.6

3158.3

DP/P AARDb (%)

DT/T AARDb (%)

Dx1/x1 AARDb (%)

Dy1/y1 AARDb (%)

0.23
0.55
0.19
0.07
0.11
0.06
0.20
0.37
0.28

0.18
0.40
0.11
0.09
0.10
0.05
0.10
0.18
0.14

0.15
0.42
0.12
0.04
0.11
0.04
0.18
0.28
0.22

0.20
1.05
0.32
0.09
0.27
0.36
0.22
0.34
0.70

Binary parameters in the NRTL model: t ij = aij + bij/T and a = 0.3 for all binary systems.




P
n
AARD: average absolute relative deviation, dened as DP=P AARD% 100%=n Sk1 jPcal  Pexp j=Pexp , DT=T AARD% 100%=n nk1 jT cal  T exp j=T exp ,


k
k
n 
n
jxcal
xexp
j
exp
exp 
1
1
Dy1 =y1 AARD% 100%=n Sk1 jycal
, Dx1 =x1 AARD% 100%
k, where n is the number of data points.
1  y1 j=y1
n Sk1
k
xexp
b

Table 12
Correlated results from the UNIQUAC-HOC model.
Mixture (1) + (2)

T (K)

a12a

2-Methylfuran + furfuryl alcohol

353.2
373.2
408.2
353.2
373.2
408.2
353.2
373.2
408.2

0.6592

0.0385

8.5

82.0

0.4936

0.3252

18.6

18.4

2.7895

5.2360

912.8

1717.0

Isopropyl alcohol + furfuryl alcohol

Furan + furfural

a21a

b12a (K)

b21a (K)

DP/P AARDb (%)

DT/T AARDb (%)

Dx1/x1 AARDb (%)

Dy1/y1 AARDb (%)

0.22
0.53
0.19
0.07
0.11
0.07
0.21
0.37
0.31

0.18
0.39
0.11
0.08
0.10
0.05
0.11
0.17
0.16

0.15
0.41
0.12
0.04
0.11
0.04
0.19
0.28
0.24

0.21
1.05
0.31
0.09
0.27
0.37
0.23
0.35
0.74

Binary parameters in the UNIQUAC model: t ij = exp (aij + bij/T).

 cal exp 
n
jP P j
AAD:
average
absolute
relative
deviation,
dened
as
DP=P AARD% 100%
k,
n Sk1
Pexp




exp
exp
cal
cal
n
n
jy1 y1 j
jx1 x1 j
100%
Dy1 =y1 AARD% 100%
S
D
x
=x
AARD%

S
k,
k,
where
n
is
the
number
of
data
points.
1
1
k1
k1
n
n
yexp
xexp
b

DT=T AARD% 100%

n Sk1

jT cal T exp j
T exp

k,

142

W.-P. Tai et al. / Fluid Phase Equilibria 384 (2014) 134142

5. Conclusion

References

Twenty three new vapor pressure data of 2-methylfuran are

measured in at temperatures ranging from 353 to 409 K and
correlated with the extended Antoine equation. Isothermal VLE
data are also determined experimentally with a static apparatus
for the binary systems of 2-methylfuran + furfuryl alcohol, isopropyl alcohol + furfuryl alcohol, and furan + furfural at temperatures
at 353.2, 373.2, and 408.2 K. No azeotropes are found in these three
investigated systems. The experimental results revealed that all
these three systems are positive deviation from Raoults law. The
WilsonHOC, the NRTL-HOC, and the UNIQUAC-HOC models can
accurately correlate the new VLE data obtained from this study.
The parameters determined from this study are useful for the
process simulation and design for the systems containing furfural
and its derivatives.

[1] S.G. Wettstein, D.M. Alonso, E.I. Grbz, J.A. Dumesic, Curr. Opin. Chem. Eng. 1
(2012) 218224.
[2] A.B. Merlo, V. Vetere, J.F. Rugerra, M.L. Casella, Catal. Commum. 10 (2009)
16651669.
[3] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127130.
[4] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135144.
[5] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116128.
[6] A.S. Smith, J.F. La Bonte, Ind. Eng. Chem. 44 (1952) 27402743.
[7] M. Nala, E. Auger, I. Gedik, N. Ferrando, M. Dicko, P. Paricaud, F. Volle, P.J.
Passarello, J.C.D. Hemptinne, P. Tobaly, P. Stringari, C. Coquelet, D. Ramjugernath, P. Naidoo, R. Lugoc, Fluid Phase Equilib. 337 (2013) 234245.
[8] H. Guerrero, C. Lafuente, F. Royo, L. Lomba, B. Ginner, Energy Fuels 25 (2011)
30093013.
[9] TRC, Thermodynamic Tables Non-Hydrocarbons, Thermodynamic Research
Center, Texas A&M University, College Station, TX, 1966.
[10] M.J. Lee, C.H. Hu, Fluid Phase Equilib. 109 (1995) 8398.
[11] S.M. Hwang, M.J. Lee, H.M. Lin, Fluid Phase Equilib. 172 (2000) 183196.
[12] C. Eon, C. Pommier, G. Guiochon, J. Chem. Eng. Data 16 (1971) 408410.
[13] NIST Chemistry WebBook, NIST Standard Reference Database No. 69-March
2003 Release, National Institute of Standard and Technology, USA, 2003.
Available from http://webbook.nist.gov/chemistry/.
[14] K.A. Kobe, A.E. Ravicz, S.P. Vohra, J. Chem. Eng. Data 1 (1956) 5056.
[15] C.F. Spencer, R.P. Danner, J. Chem. Eng. Data 17 (1972) 236241.
[16] J.G. Hayden, J.P. OConnell, Ind. Eng. Chem. Process Des. Dev. 14 (1975)
209216.
[17] K. Kojima, H.M. Moon, K. Ochi, Fluid Phase Equilib. 56 (1990) 269284.
[18] A.L. McClellan, Tables of Experimental Dipole Moments, W.H. Freeman and Co.,
San Francisco, London, 1963.

Acknowledgements
The authors gratefully acknowledge the nancial support from
the National Science Council, Taiwan, through Grant No. NSC1022622-E011-006-CC1. The authors thank to Prof. J. Ward, Prof. I.L.
Chien, and Prof. C.L. Chen for valuable discussions and also thank to
Dr. B.S. Gupta for density measurement.