You are on page 1of 12

Fluid Phase Equilibria 165 1999.

197208
www.elsevier.nlrlocaterfluid

Experimental investigation of the vaporliquid equilibrium at 313.15


K of the ternary system tert-amylmethyl ether
TAME . q n-heptaneq methanol 1
Cesar
R. Chamorro, Jose J. Segovia, Mara
C. Martn,
Miguel A. Villamanan

Laboratorio de Termodinamica,
Depto. Ingeniera
E.T.S. de Ingenieros Industriales,

Energetica
y Fluidomecanica,

Uniersidad de Valladolid, E-47071, Valladolid, Spain


Received 12 October 1998; accepted 29 June 1999

Abstract
Experimental isothermal Px data at 313.15 K for the ternary system tert-amylmethyl ether TAME. q nheptaneq methanol. and for one of the unmeasured constituent binary systems, tert-amylmethyl ether
TAME. q methanol. are reported. Data reduction by Barkers method provides correlations for g E using the
Margules equation for the binary systems and the Wohl expansion for the ternary system. Wilson, NRTL and
UNIQUAC models have been applied successfully to both the binary and the ternary systems. The presence of
azeotropes in the ternary system and constituent binaries are studied as well as the presence of immiscible
zones. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Data; VLE low pressure; Hydrocarbons; TAME; Excess Gibbs energy; Azeotropes; Correlations

1. Introduction
tert-amylmethyl ether TAME. complements the use of methyl tert-butyl ether MTBE. as an
alternative oxygenate additive in unleaded gasolines. This work will contribute with an experimental
investigation of the thermodynamic parameters of VaporLiquid Equilibrium VLE. at 313.15 K of
the ternary system TAMEq n-heptaneq methanol and the binary system TAMEq methanol.
Methanol is present in the catalytic reaction to synthesize TAME from the isoolefine isopentene.
To design separation processes properly in the purification of TAME from methanol impurities,
acurate VLE data are necessary. Thermodynamic phase behaviour of both components with gasoline
)
1

Corresponding author. Tel.: q34-983-423-364; fax: q34-983-423-363; e-mail: miguel.villamanan@eis.uva.es


This paper is part of the Doctoral Thesis of C.R. Chamorro.

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 2 6 8 - X

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

198

hydrocarbons, represented here in a qualitative way by n-heptane, requires VLE equilibrium


measurements of the corresponding generated ternary system whose data are reported here Chamorro
w1x, Chamorro et al. w2x.. A similar study has been done by our group concerning MTBE Segovia w3x,
Segovia et al. w48x..
2. Materials
All the chemicals used here were purchased from Fluka Chemie and were of the highest purity
available, chromatography quality reagents of the series puriss. p.a.. with a stated purity ) 97.0%
GC. for TAME, ) 99.5% GC. for n-heptane and ) 99.8% GC. for methanol. Only TAME was
distilled, at atmospheric pressure, through a packed column, the first and last portions of the distillate
were discarded and the intermediate fraction distilling at constant temperature was collected.
All reagents were thoroughly degassed using a modified distillation method based on the one
suggested by Van Ness and Abbott w9x. The purity of the products after degassing was checked in our
laboratory by gas chromatography, and the values obtained were ) 99.8% GC. for all the
compounds.
In Table 1, the vapor pressures of the pure constituents measured in this work are compared with
those reported in the literature to check for complete degassing.

Table 1
Average values of experimental vapor pressures Pisat . for the pure compounds measured in this work and literature values
Pisat . lit.., molar volumes of pure liquids Vi L . and the second virial coefficients Bii , Bi j . at 313.15 K used for the data
reduction of the measured systems
Pisat
Pisat

kPa.
lit. kPa.

Vi L cm3rmol.
Bi1
Bi2
Bi3
a

TAME is1.

n-Heptane is 2.

Methanol is 3.

19.567
19.587 a
19.540 b

12.351
12.331c
12.348 d
12.335e
12.300 f
12.363 g
150 j
y2211k
y2521k
y622 k

35.463
35.475 c
35.431f
35.445a
35.453 h
35.470 i
42 j
y923 k
y622 k
y1964 k

136 j
y1988 k
y2211k
y923 k

Reported by Toghiani et al. w28x.


Calculated from the Antoine equation using constants reported by Cervenkova and Boublik w29x.
c
Reported by Segovia w3x.
d
Reported by Montero w30x.
e
Calculated from the Antoine equation using constants reported in Ref. w31x.
f
Calculated from the Antoine equation using constants reported by Reid et al. w32x.
g
Reported by Reid et al. w33x.
h
Reported by Goral
et al. w34x.
i
Reported by Boublik et al. w35x.
j
Reported in Ref. w36x.
k
Calculated by Hayden and OConnell w18x from Dymond and Smith w19x.
b

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

199

3. Experimental method
A static VLE apparatus, consisting of an isothermal total pressure cell, has been employed for
measuring the VLE of binary and ternary mixtures. The apparatus and measuring technique are based
on that by Van Ness et al. Gibbs and Van Ness w10x; DiElsi et al. w11x. and whose performance has
been described in a previous paper Lozano et al. w12x..
The piston injectors are three 100-cm3 positive displacement pumps Ruska, mod. 2200-801. with
a resolution of 0.01 cm3 and an estimated total uncertainty of "0.03 cm3, allow the injection of
known volumes of the pure components, previously degassed, into the cell immersed in a high
precision water bath Hart Scientific model 6020. assuring an stability of 0.5 mK and thermostated at
313.15 K.
The cell is a cylindrical stainless steel piece with a capacity of about 180 cm3 and provided with a
magnetic stirrer externally operated. An initial amount of about 50 cm3 of one component is injected
into the evacuated cell, the vapor pressure is recorded, and successive increases in composition of a
second or a third component are generated until we nearly fill the cell completing a desired
composition range. The total amount of mass injected is accurately determined from the volume
differences read between two stop-points of the piston, the temperature of the injector and the value of
the density for that pure component allowing us assuring four digits in the value of the mole fraction.
The stop-point for advancing the piston is in all cases determined by an accurate break-point torque
wrench, set to overbalance the frictional effect of the packing around the piston.
Experimental values of total vapor pressure for the binary mixtures were obtained with two
different runs, the first one adding the second component to the first one up to a concentration close to
x 1 s 0.4, and the second run adding the first component to the second one up to x 1 s 0.6, completing
in this way the whole concentration range. For the ternary mixtures data were obtained by addition of
a pure species to a mixture of the other two at a fixed temperature. Six runs dilution lines. were done
starting the corresponding binary system at mole fractions close to 0.3 or 0.7 and adding the third
pure component up to a mole fraction of 0.5.

Table 2
Total-pressure VLE data for TAME 1.qmethanol 2.. at 313.15 K
x1

y 1,calc

P kPa.

x1

y 1,calc

P kPa.

0.0000
0.0487
0.1002
0.1506
0.1989
0.2493
0.2996
0.3499
0.3990
0.3999
0.4496
0.4498
0.4995

0.0000
0.0967
0.1616
0.2055
0.2368
0.2628
0.2845
0.3036
0.3209
0.3212
0.3380
0.3381
0.3548

35.467
37.574
38.860
39.555
39.910
40.060
40.061
39.939
39.751
39.740
39.456
39.459
39.082

0.5003
0.5498
0.5504
0.5977
0.6006
0.6508
0.6988
0.7466
0.7997
0.8469
0.9003
0.9494
1.0000

0.3550
0.3722
0.3724
0.3897
0.3908
0.4111
0.4332
0.4595
0.4968
0.5419
0.6186
0.7396
1.0000

39.066
38.598
38.603
38.048
38.019
37.296
36.433
35.376
33.822
31.998
29.113
25.353
19.573

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

200

Table 3
Total-pressure VLE data for TAME 1.q n-heptane 2.qmethanol 3.. at 313.15 K
x1

x2

y 1,calc

y 2,calc

P kPa.

1.0000
0.6981
0.6780
0.6603
0.6275
0.5943
0.5584
0.5220
0.4884
0.4528
0.4186
0.3835
0.3497
0.0000
0.3008
0.2940
0.2888
0.2750
0.2564
0.2398
0.2258
0.2111
0.1960
0.1809
0.1655
0.1504
1.0000
0.7023
0.6859
0.6670
0.6303
0.5966
0.5619
0.5267
0.4914
0.4562
0.4209
0.3860
0.3510
0.0000
0.3046
0.2970
0.2896
0.2745
0.2590
0.2439
0.2286

0.0000
0.3019
0.2932
0.2856
0.2714
0.2570
0.2415
0.2257
0.2112
0.1958
0.1810
0.1658
0.1512
1.0000
0.6992
0.6836
0.6714
0.6392
0.5959
0.5573
0.5248
0.4908
0.4556
0.4204
0.3846
0.3497
0.0000
0.0000
0.0234
0.0505
0.1028
0.1508
0.2003
0.2505
0.3007
0.3508
0.4011
0.4507
0.5005
0.0000
0.0000
0.0252
0.0498
0.0996
0.1505
0.2002
0.2504

1.0000
0.7732
0.5753
0.4845
0.3927
0.3424
0.3086
0.2849
0.2681
0.2531
0.2403
0.2281
0.2168
0.0000
0.4202
0.2494
0.2016
0.1507
0.1265
0.1156
0.1091
0.1035
0.0983
0.0934
0.0886
0.0840
1.0000
0.4349
0.4186
0.4004
0.3671
0.3389
0.3118
0.2864
0.2626
0.2403
0.2192
0.1994
0.1803
0.0000
0.2864
0.2580
0.2353
0.1998
0.1732
0.1528
0.1357

0.0000
0.2268
0.1762
0.1539
0.1327
0.1226
0.1170
0.1142
0.1127
0.1119
0.1116
0.1115
0.1117
1.0000
0.5798
0.3621
0.3032
0.2444
0.2216
0.2145
0.2117
0.2103
0.2095
0.2090
0.2084
0.2077
0.0000
0.0000
0.0141
0.0297
0.0576
0.0807
0.1022
0.1219
0.1399
0.1563
0.1716
0.1859
0.1995
0.0000
0.0000
0.0355
0.0628
0.1031
0.1314
0.1522
0.1692

19.561
17.923
23.564
27.088
31.527
34.351
36.379
37.809
38.788
39.596
40.208
40.724
41.134
12.348
15.148
24.709
29.379
35.647
39.226
40.850
41.715
42.350
42.840
43.187
43.472
43.694
19.565
36.338
36.444
36.562
36.770
36.926
37.074
37.214
37.332
37.439
37.529
37.597
37.647
35.467
40.048
40.641
41.074
41.706
42.135
42.441
42.680

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

201

Table 3 continued.
x1

x2

y 1,calc

y 2,calc

P kPa.

0.2133
0.1984
0.1827
0.1674
0.1525
0.0000
0.0000
0.0244
0.0504
0.0992
0.1489
0.2014
0.2497
0.3002
0.3502
0.4004
0.4497
0.4999
0.0000
0.0000
0.0251
0.0503
0.0997
0.1502
0.2001
0.2500
0.3002
0.3500
0.4003
0.4502
0.5000

0.3008
0.3495
0.4011
0.4513
0.5002
1.0000
0.6962
0.6793
0.6612
0.6272
0.5925
0.5560
0.5223
0.4871
0.4523
0.4173
0.3829
0.3479
0.0000
0.3016
0.2940
0.2865
0.2716
0.2564
0.2414
0.2263
0.2112
0.1962
0.1810
0.1659
0.1509

0.1209
0.1081
0.0958
0.0848
0.0750
0.0000
0.0000
0.0108
0.0228
0.0460
0.0702
0.0963
0.1211
0.1479
0.1760
0.2063
0.2386
0.2745
0.0000
0.0000
0.0163
0.0325
0.0634
0.0938
0.1227
0.1506
0.1780
0.2048
0.2318
0.2588
0.2865

0.1836
0.1955
0.2063
0.2151
0.2224
1.0000
0.2552
0.2520
0.2481
0.2394
0.2295
0.2186
0.2083
0.1977
0.1871
0.1765
0.1660
0.1552
0.0000
0.2572
0.2447
0.2328
0.2117
0.1922
0.1745
0.1581
0.1426
0.1281
0.1144
0.1015
0.0895

42.889
43.053
43.214
43.345
43.452
12.358
45.572
45.254
44.823
43.927
43.012
42.028
41.081
40.064
39.016
37.926
36.785
35.572
35.456
45.611
45.266
44.915
44.274
43.628
43.002
42.396
41.776
41.140
40.479
39.771
39.020

Temperature was measured by a calibrated standard PRT-100 SDL model 5385r100. using as
indicator an AC resistance bridge ASL model F250. resolving 1 mK in the reading of temperature
and estimating an overall uncertainty of "10 mK. The measurement of the pressure was done
indirectly through a differential pressure cell and indicator Ruska models 2413-705 and 2416-711,
respectively.. Once air balances the vapor pressure of the cell a Bourdon fused quartz precision
pressure gauge Texas Instruments mod. 801. reads the pressure with an estimated uncertainty of "5
Pa for the 125 kPa range.
3.1. Experimental results and correlations
The use of the measuring technique described above allows a static equilibrium between phases,
assuring a true thermodynamic equilibrium. Direct sampling, particularly of the vapor phase, upsets
the equilibrium, the mass of vapor in the cell is very small; yet an appreciable mass must be

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

202

withdrawn to yield an amount of condensate suitable for accurate analysis. However, as a consequence of Duhems theorem, sampling of the phases is not, in fact, necessary. Given a set of
equilibrium x, P data at constant T, thermodynamics allows calculation of the y-values. Thus, the
equilibrium vapor need not be sampled for analysis and the data are thermodynamically consistent
per se. Van Ness et al. w13x; Van Ness w14x.
Data reduction for the binary and ternary mixtures was done by Barkers method w15x according to
well established procedures Abbott and Van Ness w16,17x. developing a computer program described
in detail earlier. Lozano et al. w12x.
The non-ideality of the vapor phase was taken into account with the virial equation of state,
truncated in the second term. The second virial coefficients Bii . are indicated in Table 1. They were
calculated by the Hayden and OConnell method w18x using the parameters given by Dymond and
Smith w19x. Correction for the vapor phase was also applied to x.
The quality of the data of the present VLE technique for ternaries has been assessed previously and
reported in Refs. w38x.
The ternary system TAMEq n-heptaneq methanol has been measured together with the binary
system TAMEq methanol at 313.15 K. The other binary systems involved in this ternary TAMEq nheptane and n-heptaneq methanol have been already published Chamorro et al. w2x; Segovia et
al.w8x., using the same experimental procedure and data reduction.
Data for this ternary system are adequately correlated by the three-parameter Wohl equation, Eq.
1. Van Ness and Abbott w13x., which also includes the parameters of the corresponding binaries.
g 123 s

gE

g q g 13 q g 23 q C0 q C1 x 1 q C2 x 2 . x 1 x 2 x 3
1.
RT 12
Correlations for the g i j are given by Eq. 2.; parameters C0 , C1 and C2 are found by regression of
the ternary data. The Margules equation with three parameters, Eq. 2. , has been chosen for the
binaries.
gE

s A ji x i q A i j x j y l x i x j x i x j
2.
Rt
Binary and ternary systems have also been correlated using Wilson w20x, NRTL w21x and
UNIQUAC w22x models, whose expressions for the excess Gibbs energy are indicated by the Eqs.
3. 5., respectively.
gi j s

gE
RT
gE
RT

s y x i ln
i

/
x j Ai j

3.

A ji Gji x j
s xi
i

4.

Gk i x k
k

RT

s x i ln
i

wi
xi

qi

qi x i ln q
2
i

y qi x i ln
i

/
qj A ji

where, Gji s expya ji A ji ., qi s qi x i .r j q j x j .; w i s ri x i .r j r j x j . and z s 10.

5.

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

203

Table 4
Summary of the data reduction results and azeotrope situation obtained for the binary system TAME 1.qmethanol 2.. at
313.15 K
Margules 3p.
A12
A 21
l
a 12
rms D P kPa.
max D P kPa.
x 1 azeotrope.
P azeotrope. kPa.
a
b

Wilson

1.5372
1.5096
0.5045

0.3996
0.4189

0.007
0.023
0.2737
40.076

0.081
0.180
0.2788
40.014

NRTLa

NRTLb

UNIQUAC

0.8593
0.9015

0.9723
1.0111

0.2146
1.2523

0.47
0.113
0.252

0.6138
0.007
0.014
0.2736
40.072

0.203
0.455
0.2870
39.948

This column contains a 12 s 0.47 as recommended, but the fitting is rather poor.
This column contains a simultaneous adjustment of the three parameters.

Table 2 gives experimental values of total pressure and the corresponding compositions of the
liquid and vapor phases for the binary system TAMEq methanol. , reduced by Margules equation.
Table 3 gives the same type of information for the ternary system TAMEq n-heptaneq methanol.,
where Wohl expansion has been used in the data reduction.
Results of data correlation for the binary system TAMEq methanol are summarized in Table 4.
The results of the correlations for the other binaries involved in the ternary system TAMEq nheptaneq methanol. have been published previously Chamorro et al. w2x; Segovia et al. w8x.. For the
ternary system, the results of the correlation are given in Table 5. All these tables contain values of
the adjustable parameters of the different models which lead to the correlated results using Barkers
Table 5
Summary of the data reduction results obtained for the ternary system TAME 1.q n-heptane 2.qmethanol 3.. at 313.15
K
Wohl a
C0
C1
C2
A12
A 21
A13
A 31
A 23
A 32
a 12
a 13
a 23
rms D P kPa.
max < D P < kPa.
a

Wilson

NRTLb

UNIQUAC

0.7071
1.0561
0.4133
0.4044
0.0594
0.0296

0.4237
y0.1962
0.9958
0.9585
2.6495
2.7360
0.3
0.6138
0.4356
0.212
0.774

1.4011
0.5517
0.2205
1.2379
0.0616
1.1425

1.7416
2.6007
2.3999

0.159
0.470

0.118
0.407

0.620
2.096

The values for the correlation parameters of the two constituent binaries, not reported in this paper, were taken from Refs.
w2,8x.
b
The recommended value of a 12 s 0.3 has been taken, since it has been found that the outcome of the fitting was the same
using an adjusted ad hoc value.

204

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

Fig. 1. Comparison for the binary system TAME 1.qmethanol 2.. at 313.15 K of the pressure residuals, P y Pcalc ,
defined as differences between experimental pressures, P, and calculated pressures, Pcalc . A"0.1% band of the experimental pressure in each point is indicated on the diagram.

method. The root mean square of the difference between experimental and calculated pressures rms
D P . and the maximum value of these pressure residuals max < D P <. are indicators of the quality of
the agreement with data.
As an example of the fits of models to the data, Fig. 1 shows a plot of P y Pcalc . vs. x 1 for the
binary TAMEq methanol. using Margules equation with three parameters. It can be seen that both
branches, necessary to measure the binary, have a good match close to equimolar concentrations,
showing the figure at that point a comparison of the residual with 0.1% of the experimental pressure.

4. Discussion
The ternary system TAMEq n-heptaneq methanol. and its constituent binaries are specially rich
in a variety of fluid phase behaviour. The binary system studied TAMEq methanol. at 313.15 K
presents a positive deviation from the ideality and the results of the correlation give a root mean
square pressure residuals of 7 Pa with a maximum value of the absolute deviation of 14 Pa, using
NRTL model when the third parameter a i j is also adjusted. Table 4 also shows the result with the
recommended value of 0.47 providing a poor fitting of the data. The values obtained with Margules
equation of three parameters are rather similar and worse correlations are obtained with Wilson and
UNIQUAC models. This system exhibits an azeotrope in the alcohol rich region at x 1 s 0.2737 and
P s 40.076 kPa, which agrees with literature values of Gmehling et al. w23x and Coto et al. w24x which
situate it at x 1 s 0.2731 and x 1 s 0.2749, respectively. These literature azeotrope compositions in
fact does not come from direct experimental data at 313.15 K as ours, but have been obtained by
linear interpolation of reported data available at other temperatures, since it has been observed a linear
variation of the azeotrope composition value with temperature. A view of the results here discussed
together the ones obtained with the other reduction equations used in this paper are given in Table 6.
The quality of data are shown in Fig. 1 by the study of their dispersion in all the composition range
and Fig. 2 displays the azeotropic Pxy behaviour of the mixture.
In contrast to previous binary system, the TAMEq n-heptane. system shows a rather ideal
behaviour without any azeotrope and a very good miscibility as can be expected and was reported by

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

205

Table 6
Values of the azeotrope composition, x 1, and total vapor pressure, P, for the binary system TAME 1.qmethanol 2.. at
313.15 K, calculated with different correlation models, and comparison with values reported from literature
Margules
Wilson
NRTL
UNIQUAC
Reported by Gmehling et al. w23x
Reported by Coto et al. w24x
a
b

x1

P kPa.

0.2737
0.2788
0.2736
0.2870
0.2731a
0.2749 a

40.076
40.014
40.072
39.948
b
b

Obtained by interpolation of values at different temperatures.


Not determined by the referred authors w23,24x at 313.15 K.

Chamorro et al. w2x. The remaining binary system methanolq n-heptane. presents a large immiscibility gap between x 1 s 0.2263 and x 1 s 0.8714 as has been determined by us Segovia et al. w8x..
The molar excess Gibbs function, g E , shows a positive deviation from ideality with maximum
values close to equimolar concentrations at 1672 Jrmol for methanolq n-heptane., 910 Jrmol for
TAMEq n-heptane. and 107.4 Jrmol for TAMEq n-heptane.. This behaviour of g E shows
quantitatively the strong gradation of the nature of the binary mixtures, ranging from nearly an ideal
solution in the case of TAMEq n-heptane. to the high non-ideality with separation for methanolq
n-heptane..
Concerning the measured ternary system, the results of the correlation give a root mean square
pressure residuals between 0.118 kPa for Wilson equation and 0.620 kPa for UNIQUAC, being the

Fig. 2. Total vapor pressure as a function of the liquid, x 1, and vapor composition, y 1, of TAME for the VLE of the binary
system TAME 1.qmethanol 2.. at 313.15 K. The azeotrope showed occurs at x 1 s 0.2737 and P s 40.076 kPa.

206

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

Fig. 3. Isobar lines in kPa as a function of the ternary liquid composition, x i , for the VLE at 313.15 K of the ternary system
TAME 1. q n-heptane 2.qmethanol 3...

former the best fit for all the miscible region. Figs. 3 and 4 show, respectively isobar and the iso-g E
lines as a function of the ternary liquid composition.

Fig. 4. Iso-g E lines in Jrmol as a function of the ternary liquid composition, x i , for the VLE at 313.15 K of the ternary
system TAME 1.q n-heptane 2.qmethanol 3...

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

207

The investigated ternary system TAMEq n-heptaneq mehtanol. shows good miscibility in the
whole range of our measurements, nevertheless, it is to expect a really very narrow immiscible zone
close to binary line of methanolq n-heptane. which is impossible to precise with our experimental
technique due to the very low concentrations of TAME at which it appears. In fact, very low
quantities of TAME representing according to our measurements values lower than 0.1 molar destroys
the immiscibility of the binary methanolq n-heptane..
The search for ternary azeotropes either homogeneous or heterogeneous using the calculation
procedures indicated by Gmehling and Menke w25x; Demirel w26x and Chapman and Goodwin w27x
have been negative in all the concentration range for the correlated data by Wilson, NRTL or
UNIQUAC. Concerning the g E function the maximum value occurs at the maximum value for the
binary methanolq n-heptane. already given.

5. Nomenclature
A i j , A ji
Bii , Bi j , Bj j
C 0 , C1 , C 2
gE
g
i, j
lit
max
P
Pisat
R
rms
T
Vi L
x
y
Greek letters
D
l

adjustable parameters of the correlation models


second virial coefficients
parameters in Eq. 1.
molar excess Gibbs energy
value of g ErRT for a binary or a ternary mixture
constituent identification: 1, 2 or 3
literature value
maximum value of the indicated quantity
total pressure
vapor pressure of pure constituent i
universal gas constant
root mean square
absolute temperature
molar volume of pure liquid i s 1,2,3
mole fraction, liquid phase
mole fraction, vapor phase
signifies difference
parameter in Eq. 2.

Acknowledgements
Support for this work came from the DGICYT, Direccion
y
General de Investigacion
Cientfica

Tecnica
of
the
Spanish
Ministery
of
Education,
Project
PB-95-0704
and
from
Junta
de
Castilla
y
Leon

Consejera
de Educacion
y Cultura. project VA 42r96.

C.R. Chamorro et al.r Fluid Phase Equilibria 165 (1999) 197208

208

References
w1x
w2x
w3x
w4x
w5x
w6x
w7x
w8x
w9x
w10x
w11x
w12x
w13x
w14x
w15x
w16x
w17x
w18x
w19x
w20x
w21x
w22x
w23x
w24x
w25x
w26x
w27x
w28x
w29x
w30x
w31x
w32x
w33x
w34x
w35x
w36x

C.R. Chamorro, PhD Thesis, University of Valladolid, Spain, 1998.


C.R. Chamorro, J.J. Segovia, M.C. Martn,
E.A. Montero, M.A. Villamanan,
Fluid Phase Equilibria 156 1999. 7387.
J.J. Segovia, PhD Thesis, University of Valladolid, Spain, 1997.
J.J. Segovia, M.C. Martn,
C.R. Chamorro, M.A. Villamanan,
Fluid Phase Equilibria 133 1997. 163172.
J.J. Segovia, M.C. Martn,
C.R. Chamorro, E.A. Montero, M.A. Villamanan,
Fluid Phase Equilibria 152 1998.
265276.
J.J. Segovia, M.C. Martn,
C.R. Chamorro, M.A. Villamanan,
J. Chem. Eng. Data 43 1998. 10141020.
J.J. Segovia, M.C. Martn,
C.R. Chamorro, M.A. Villamanan,
J. Chem. Eng. Data 43 1998. 10211026.
J.J. Segovia, M.C. Martn,
C.R. Chamorro, M.A. Villamanan,
J. Chem. Thermodyn., 1999, in print.
H.C. Van Ness, M.M. Abbott, Ind. Eng. Chem. Fundam. 17 1978. 6667.
R.E. Gibbs, H.C. Van Ness, Ind. Eng. Chem. Fundam. 11 1972. 410413.
D.P. DiElsi, R.B. Patel, M.M. Abbott, H.C. Van Ness, J. Chem. Eng. Data 23 1978. 242245.
L.M. Lozano, E.A. Montero, M.C. Martn,
M.A. Villamanan,
Fluid Phase Equilibria 110 1995. 219230.
H.C. Van Ness, M.M. Abbott. Classical Thermodynamics of Nonelectrolyte Solutions with Applications to Phase
Equilibria, Mc-Graw Hill, New York, 1982.
H.C. Van Ness, J. Chem. Thermodyn. 27 1995. 113134.
J.A. Barker, Aust. J. Chem. 6 1953. 207210.
M.M. Abbott, H.C. Van Ness, AIChE Journal 21 1975. 6271.
M.M. Abbott, J.K. Floess, G.E. Walsh Jr., H.C. Van Ness, AIChE Journal 21 1975. 7276.
J.G. Hayden, J.P. OConnell, Ind. Eng. Chem. Process Des. Dev. 14 1975. 209216.
J.H. Dymond, E.B. Smith, The Virial Coefficients of Pure Gases and Mixtures A Critical Compilation, Clarendon
Press, Oxford, 1980.
G.M. Wilson, J. Am. Chem. Soc. 86 1964. 127130.
H. Renon, J.M. Prausnitz, AIChE Journal 14 1968. 135144.
D.S. Abrams, J.M. Prausnitz, AIChE Journal 21 1975. 116128.
J. Gmehling, J. Menke, J. Krafczyck, K. Fisher, Fluid Phase Equilibria 103 1995. 5176.
B. Coto, F. Mosner,
C. Pando, R.G. Rubio, J.A.R Renuncio, Fluid Phase Equilibria 133 1997. 89103.

J. Gmehling and B. Menke, Thermodynamik, VCH Verlag, Weiheim, 1992.


Y. Demirel, Fluid Phase Equilibria 86 1993. 113.
R.G. Chapman, S.P. Goodwin, Fluid Phase Equilibria 85 1993. 5569.
R.K. Toghiani, H. Toghiani, G. Venkateswarlu, Fluid Phase Equilibria 122 1996. 157168.
I. Cervenkova, T. Boublik, J. Chem. Eng. Data 29 1984. 425427.
E.A. Montero, PhD Thesis, University of Valladolid, Spain, 1996.
TRC-Thermodynamic Tables Hydrocarbons, Thermodynamics Research Center. The Texas A&M University
System, College Station, Vapor Pressures, 1976.
R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids, Mc-Graw Hill, New York, 1987.
R.C. Reid, J.M. Prausnitz, T.K. Sherwood, The Properties of Gases and Liquids, 3rd edn., Mc-Graw Hill, New York,
1977.
M. Goral,
Fluid Phase Equilibria 102 1994. 275286.
T. Boublik, V. Fried, E. Hala, The Vapor Pressures of Pure Liquids, Elsevier, Amsterdam, 1973.
TRC-Thermodynamic Tables Hydrocarbons, Thermodynamics Research Center. The Texas A&M University
System, College Station, Densities, 1973.