Fluid Phase Equilibria 340 (2013) 4245

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Fluid Phase Equilibria

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Isobaric vaporliquid equilibrium for binary system of methanol and acetonitrile

Yumei Li a,b , Peng Bai a, , Qionghong Zhuang a
a
b

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
Department of Chemistry, Dezhou University, Shandong 253023, PR China

a r t i c l e

i n f o

Article history:
Received 18 June 2012
Received in revised form 2 December 2012
Accepted 6 December 2012
Available online 17 December 2012
Keywords:
Methanol
Acetonitrile
Vaporliquid equilibrium

a b s t r a c t
Isobaric vaporliquid equilibrium (VLE) data for methanol and acetonitrile system was measured at
101.3 kPa by using equilibrium still. The results show that methanol and acetonitrile system can form a
minimum temperature azeotrope. Thermodynamic consistency of the experimental data was conrmed
by means of Herington semi-empirical method. The experimental values obtained were correlated by
using the Margules, Van Laar, Wilson and NRTL activity-coefcient models, respectively. The binary interaction parameters of the activity-coefcient models were determined. The average absolute deviation in
boiling point and vapor-phase composition were determined by comparing the experimental values with
those calculated by the activity-coefcient models. The calculated maximum average absolute deviations
were 0.25 K and 0.0056 for the boiling point and vapor-phase composition, respectively. Therefore, it was
shown that the four activity-coefcient models used satisfactorily correlate the experimental results of
methanol and acetonitrile system.
2012 Elsevier B.V. All rights reserved.

1. Introduction

2. Experimental

Methanol and acetonitrile have been used extensively as

solvents and important ne chemicals in the chemical and pharmaceutical production process [14]. Several processes in chemical
industries produce mixtures of methanol and acetonitrile, so separation of them is indispensable. Availability of accurate and
quantitative information on the phase equilibrium of binary or
multicomponent mixtures is essential for designing distillation
processes of liquid mixtures [5,6]. To our knowledge, no isobaric
VLE data are available for methanol and acetonitrile mixture. In
this paper, we present isobaric vaporliquid equilibrium measurements for the mixture of methanol and acetonitrile at 101.3 kPa
to provide a benecial reference for separation of methanol and
acetonitrile.
The experimental VLE data of the binary systems investigated
were found to be thermodynamically consistent and the activity
coefcients have been calculated and correlated with the following
equations: Margules and Akad [7], Van Laar [8], Wilson [9] and
NRTL [10].

2.1. Chemicals
Chemicals used: All the reagents were analytical purity grade.
Methanol and acetonitrile were purchased from Tianjin University
Ke Wei Company. The purities of all the chemicals were checked
by a gas chromatograph (GC) equipped with a ame ionization
detector. The water content in chemicals was determined using
a Karl Fischer moisture titrator. The purity and water content are
listed in Table 1. The chemicals were degassed and subsequently
dried over molecular sieves (Nankai University 3A) for 24 h prior
to use. The purity of chemicals was further conrmed by comparing the experimental densities, the refractive indexes and the
normal boiling points with those reported in [11,12], as they are
listed in Table 2. The densities of the pure components were measured at 293.15 K using an DA-510 densimeter, and the refractive
indexes were measured at 293.15 K using an ATAGO RX-5000.
The accuracy in density, and refractive index measurements are
2.0 105 g/cm3 and 0.00001, respectively. Temperature was
controlled to 0.01 K with a thermostated bath.
2.2. Apparatus and procedure

Corresponding author. Tel.: +86 022 27406369.

E-mail address: dzhlym@126.com (P. Bai).
0378-3812/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2012.12.003

The equilibrium still, the same as in the previous work [13],

was employed to measure isobaric VLE data at 101.3 kPa, and the
favorable performance of the apparatus was veried in the previous
measurement.

Y. Li et al. / Fluid Phase Equilibria 340 (2013) 4245

1.0

Table 1
Purity and water content of pure components.

Methanol
Acetonitrile

Purity (mass%)
Suppliers

GC

>99.7
>99.5

99.75
99.61

Water (mass%)

0.8

0.03
0.03

0.6

y1

Component

0.4

360

T/ K

43

355

0.2

350

0.0
0.0

0.2

0.4

345
340

0.6

0.8

1.0

Fig. 2. yx Diagram for the methanolacetonitrile system at 101.3 kPa.

335
330
0.0

x1

Table 3
Experimental VLE data for the methanolacetonitrile binary system at 101.3 kPa.

0.2

0.4

x1

0.6

0.8

1.0

y1

Fig. 1. Vaporliquid equilibrium phase diagram for the methanolacetonitrile system at 101.3 kPa.

The experiments were accomplished at 101.3 kPa. A mercury

thermometer calibrated by Shanghai Metrology Institution was
used for temperature measurement within accuracy 0.01 C. The
actual atmospheric pressure was measured by a mercury barometer whose accuracy was 50 Pa with a control system whose
uncertainty is 50 Pa. Equilibrium conditions were assumed when
constant temperature and pressure were obtained for 25 min
or longer, and to verify the equilibrium state, condensate was
analyzed every 10 min until the variation of the vapor phase composition of the last three samples is less than 0.001 (mole fraction).
Then the samples of liquid and condensate were taken simultaneously for analysis. The sampling was carried out with special
syringes that allowed withdrawal of small volume samples (0.5 L).
At least two analyses were made for each sample.

T (K)

x1

y1

1

338.41
338.04
336.96
337.02
337.09
337.71
338.09
339.38
340.55
344.6
350.19
355.66

1.000
0.962
0.866
0.805
0.766
0.646
0.602
0.437
0.310
0.171
0.054
0.000

1.000
0.945
0.860
0.814
0.785
0.706
0.687
0.600
0.529
0.380
0.189
0.000

1.000
0.998
1.030
1.051
1.064
1.119
1.158
1.324
1.535
1.750
2.225

2
2.535
1.863
1.705
1.640
1.464
1.376
1.188
1.074
1.047
0.994
1.000

could be obtained by using y1 x1 versus x1 diagrams in order

to determine x1az at y1 x1 = 0 together with T versus x1 diagrams
where Taz should be minimum at x1az . The composition and boiling
temperature of the azeotrope obtained were: 0.84 and 63.85 C,
respectively.
3.2. Thermodynamics consistency verication
To conrm thermodynamic consistency of experimental data,
all experimental data were veried by means of the Herington
semi-empirical method [12], in which the value of (D J) must be
less than 10.

3. Results and discussion

3.1. Experimental results
The vaporliquid equilibrium data, T, xi and yi , along with the
calculated activity coefcients,  i , are gathered in Table 3. The
corresponding phase diagram was shown in Figs. 1 and 2. As
can be seen from Fig. 2, there is intercrossing point between the
equilibrium curve and the diagonal line, which reveals that there
exists azeotrope in the methanol + acetonitrile binary system at
101.3 kPa. It can be also seen that the binary system exhibited
positive deviation from Raoults law and a minimum temperature
azeotrope was found (Fig. 1). The location of the azeotropic points


I 

D =  100, J = 150

Tmin

1

1

where
I = 0 ln(1 /2 ) dx1 ,
= 0 ln(1 /2 ) dx1 ,  =
Tmax Tmin , Tmax and Tmin were the highest and the lowest
boiling point in the system, respectively (K).
The results of thermodynamic consistency test are demonstrated in Fig. 3 and Table 4. The calculation result was that

Table 2
Density , normal boiling point Tb , and refractive index nD of pure components.
Component

Methanol
Acetonitrile
a
b

Taken from Ref. [11].

Taken from Ref. [12].

 (293.15 K) (g cm3 )

Tb (101.3 KPa) ( C)
a

nD (293.15 K)
b

Experimental

Literature

Experimental

Literature

Experimental

Literaturea

0.79182
0.78338

0.7913
0.7822

65.26
82.51

64.70
81.6

1.32835
1.34358

1.3286
1.34411

44

Y. Li et al. / Fluid Phase Equilibria 340 (2013) 4245

1.0

Table 5
The Antoine constants of pure substances.

ln( 1/ 2)

0.5

Component

Methanol
Acetonitrile

7.4182
6.34522

1710.2
1388.446

22.25
34.856

0.0
355

-0.5
350

-1.0
0.2

0.4

0.6

0.8

1.0

0.0

345

x1
340

Fig. 3. Diagram of ln( 1 / 2 ) to x1 .

335
0.0

Table 4
Thermodynamic consistency test of VLE data.

0.2

0.4

0.6

0.8

1.0

x1 y1

Tmax

Tmin

 (K)

355.66

338.5

17.16

0.0086

0.4432

1.9404

7.6393
Fig. 4. Tyx diagram for the methanolacetonitrile system at 101.3 kPa: (, )
experimental data and () Wilson equation.

|D J| = 5.6989 < 10, which indicated that all experimental data

were in accordance with thermodynamic consistency.
3.3. Correlation of binary vaporliquid equilibrium
The general equilibrium relationship between the vapor phase
and liquid phase can be expressed as:

V p = xi i s ps exp
yi 
i
i i

Vil (p psi )

(1)

RT

The Poynting factor, the exponential term in Eq. (1), is close to

unity at low pressure and the vapor phase is assumed to be an ideal
gas and the pressure dependence of the liquid phase fugacity is
neglected. Eq. (1) can be simplied to
pyi = psi i xi

(2)

where P and T are the total pressure and the temperature in the
equilibrium system. xi and yi are the liquid and vapor phase mole
V is the fugacity coefcients
fractions in equilibrium, respectively. 
i
s is the fugacity coefcient
of component i in the vapor mixture, 
i

of pure vapor i at equilibrium system temperature T and saturation

vapor pressure psi , Vil is the mole volume of pure liquid i, R is the
universal gas constant,  i is the activity coefcient of component i.
psi is the saturated vapor pressure of pure component i at the system
temperature, calculated with the Antoine equation
lg psi (kPa) = A

B
T (K) + C

(3)

where A, B, and C are Antoine constants and T is the temperature

in Kelvin. The Antoine constants were obtained from the literature
[12], and were presented in Table 5.
Because the experiment was carried out at 101.3 kPa, the vapor
phase could be regarded as ideal gas, the parameters could be
regarded as constant values. In order to nd parameters of the equations, activity coefcients were correlated with the Margules, Van
Laar, Wilson and NRTL equations. Estimation of the parameters of
the equations was based on minimization of the following objective
function (OF):
OF =


k

exp 2
)k

(ln ical ln i

(4)

where k is the number of data points and i the number of components in the mixture. The experimental and calculated values are
exp
denoted by the superscripts exp and cal, respectively. i is cal-

culated with Eq. (2) and ical is calculated with Margules, Van Laar,
Wilson and NRTL models. The correlated interaction parameters,
together with the average deviations of temperature and the vaporphase composition for the methanol and acetonitrile binary system
at 101.3 kPa between the experimental and the calculated values
obtained from Margules, Van Laar, Wilson and NRTL models, were
shown in Table 6. The correlated interaction parameters obtained
through simplex search were, then, used to calculate y1cal , T cal , 1cal
and 2cal under corresponding liquid compositions and pressure
(101.3 kPa) and the results calculated were given in Table 7. The

Table 6
Margules, Van Laar, Wilson and NRTL parameters and mean absolute deviations of the binary system.
Model
Methanol (1) + acetonitrile (2) at 101.3 KPa
A12 = 0.884
Margules
A12 = 0.834
Van Laar
12 = 0.688
Wilson
g12 g22 = 1993.75
NRTL
c

k: number
  of data
 points.
a


T  =  Texp Tcal  /kc .
  

y = yexp ycal  /kc .

Parameters
A21 = 0.889
A12 = 0.940
21 = 0.525
g12 g11 = 1755.63

12 = 1.09

|T|a

|y|b

0.25
0.21
0.22
0.22

0.0048
0.0056
0.0054
0.0044

Y. Li et al. / Fluid Phase Equilibria 340 (2013) 4245

45

Table 7
Correlation results for methanol + acetonitrile system at 101.3 kPa.
x1

1.000
0.962
0.866
0.805
0.766
0.646
0.602
0.437
0.310
0.171
0.054
0.000

Margules

Van Laar

Wilson

NRTL

y1cal

Tcal (K)

1cal

2cal

y1cal

Tcal (K)

1cal

2cal

y1cal

Tcal (K)

1cal

2cal

y1cal

Tcal (K)

1cal

2cal

1.000
0.950
0.853
0.805
0.778
0.708
0.685
0.601
0.524
0.396
0.186
0.000

338.22
337.88
337.42
337.35
337.38
337.70
337.91
339.14
340.82
344.19
349.97
354.80

1.000
1.001
1.016
1.035
1.050
1.118
1.151
1.325
1.526
1.838
2.207
2.421

2.433
2.277
1.950
1.781
1.687
1.451
1.382
1.186
1.090
1.027
1.003
1.000

1.000
0.949
0.851
0.805
0.779
0.712
0.690
0.607
0.527
0.394
0.181
0.000

338.22
337.82
337.32
337.25
337.27
337.62
337.83
339.12
340.89
344.39
350.18
354.80

1.000
1.002
1.019
1.039
1.056
1.129
1.164
1.340
1.532
1.815
2.129
2.302

2.560
2.367
1.977
1.786
1.682
1.432
1.362
1.169
1.079
1.023
1.002
1.000

1.000
0.948
0.852
0.806
0.780
0.713
0.691
0.606
0.526
0.394
0.182
0.000

338.22
337.81
337.30
337.23
337.26
337.62
337.84
339.15
340.92
344.38
350.13
354.80

1.000
1.002
1.020
1.041
1.058
1.131
1.165
1.336
1.526
1.813
2.146
2.337

2.602
2.389
1.975
1.780
1.675
1.428
1.359
1.171
1.082
1.024
1.002
1.000

1.000
0.946
0.853
0.810
0.785
0.717
0.693
0.601
0.517
0.389
0.187
0.000

338.22
337.75
337.24
337.20
337.24
337.66
337.91
339.33
341.11
344.39
349.91
354.80

1.000
1.002
1.024
1.047
1.065
1.134
1.165
1.316
1.489
1.791
2.220
2.506

2.788
2.475
1.956
1.745
1.640
1.408
1.346
1.179
1.094
1.032
1.004
1.000

comparisons of the experimental results with those calculated by

Wilson activity-coefcient models were shown in Fig. 4.
It can be seen from Table 7 that the differences among the vapor
phase mole fraction and boiling temperature calculated by the Margules, Van Laar, Wilson and NRTL models are indistinct. As can be
seen from Table 6, the average values of |T| and |y| were less than
0.25 K and 0.0056, respectively. Thus, all of the four models can correlate the VLE data for the binary systems methanol + acetonitrile
at 101.3 kPa well.
4. Conclusions
Isobaric VLE values were determined experimentally for
methanol and acetonitrile binary system at 101.3 kPa. The results
show that methanol and acetonitrile system can form a minimum temperature azeotrope. Thermodynamic consistency of the
experimental data was conrmed by means of Herington semiempirical method. The VLE values were correlated by the four
activity-coefcient models, namely, Margules, Van Laar, Wilson
and NRTL. The corresponding binary interaction parameters of
the models were obtained. The average absolute deviation in
boiling point and vapor-phase composition were determined by
comparing the experimental values with those calculated by the

activity-coefcient models. The calculated maximum average

absolute deviations were 0.25 K and 0.0056 for the boiling point and
vapor-phase composition, respectively. Therefore, it was shown
that the four activity-coefcient models used satisfactorily correlate the experimental results of methanol and acetonitrile system.
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