285

Fluid Phase Equilibria, 69 (1991) 285-301

Elsevier Science Publishers B.V., Amsterdam

Phase equilibria in binary and higher systems

methanol + hydrocarbon(s)
Part I. Experimental determination of liquid-liquid
and their representation using the NRTL equation

equilibrium data

G. Hradetzky and D.A. Lempe

Technical University Merseburg, Department of Chemical Engineering, Geusaer Strasse,
O-4200 Merseburg (Germany)

(Received June 1, 1990; accepted in final form July 30, 1991)

ABSTRACT
Hradetzky, G. and Lempe, D.A., 1991. Phase equilibria in binary and higher systems
methanol + hydrocarbon(s). Part I. Experimental determination of liquid-liquid equilibrium data and their representation using the NRTL equation. Fluid Phase Equilibria, 69:
285-301.

New measurements of the liquid-liquid

equilibrium were carried out in the binary
system methanol + hexane in the temperature range from 293 K up to the critical solution
temperature, and in the ternary system methanol + hexane + cyclohexane in the temperature
range 293-313 K. A double-plait point appearing in the ternary system could be determined
exactly with the help of a special ampoule technique. This system shows a remarkably strong
temperature dependence of the LLE.
The LLE data were correlated using the NRTL equation with temperature-dependent
parameters. Reliable results were obtained for the LLE data of the binary and ternary
systems. Systematic deviations arise if the modelling of the VLE data is additionally
included.

INTRODUCTION

Methanol-hydrocarbon
mixtures are of current interest either for technical use (e.g. as a fuel substitute) or for thermodynamic modelling (combination of VLE, LLE and VLLE). Whereas numerous experimental LLE
data of the binary systems methanol + alkane exist, even if they are often
contradictory (see for example Hijlscher et al., 1986), only little information
is known about the LLE equilibrium in the ternary system methanol
(1) + hexane (2) + cyclohexane (3).
0378-3812/91/$03.50

0 1991 Elsevier Science Publishers B.V. All rights reserved

In 1989 Alessi et al. published data in a temperature range (up to 298 K)

in which only an open miscibility gap appears, running straight between the
binary subsystems methanol + hexane and methanol + cyclohexane. But
the temperature range up to 313 K (i.e. the range between the critical
solution temperatures of the binary subsystems) is more interesting because
the binodal curves contract more and more with increasing temperature
and form a double-plait point at a specific temperature. At still higher
temperatures two separated closed miscibility gaps appear and above the
critical solution temperature of the methanol + hexane system one small
miscibility gap exists on the side of the binary subsystem methanol +
cyclohexane which disappears at the critical solution temperature of this
binary system.
Because of this very strong change in the size of the miscibility gap
within a relatively small temperature interval of about 20 K the experimental LLE data of this system should be of special interest in connection with
the critical evaluation and examination of phase equilibrium models.
The LLE data of the binary system methanol + hexane, published together with those of the system methanol + cyclohexane (Hradetzky and
Bittrich, 1986), were measured once more in order to overcome the
contradictory literature data (Sorensen and Arlt, 1979; Hiilscher et al.,
1986; Alessi et al., 1989) and to guarantee a consistent connection to the
ternary LLE data.

EXPERIMENTAL

Pure substances
Methanol was from Leuna-Werke AG (Leuna, Germany) (stated purity
> 99.9%) and was used without further purification. The water content was
< 50 ppm detected by the Karl Fischer method.
Hexane and cyclohexane were UV-gra$e materials from PCK Schwedt
AG (Schwedt, Germany) dried over a 3 A molecular sieve, and were of a
GLC purity of 99.5% and > 99.9% respectively. Hexane was additionally
fractionated.
Binary sys tern
The cloud points were determined visually in 20 ml glass ampoules. The
ampoules were closed using standardized ground-glass stoppers, sealed by
a very fine Teflon ring (see Glindemann and Wohlfarth, 1986).

287
molar ratio
x
.
0
+

307 .

CHlHx

0 HO0
5195
10/90
20180
35165

T/K
306.
I
305.

304.

303.

I
0.3

Ok

0.5

0.6

0.7

-XMeOH

Fig. 1. Pseudobinary T-x curves of the system methanol + hexane + cyclohexane for different ratios of hexane/cyclohexane
as the base for ternary binodal curves.

The ampoules were kept at the desired temperatures with an experimental error of 0.01 K in a water bath which was stirred intensively. The
temperatures were measured using mercury thermometers with an uncertainty of 0.01 K, certified by the Bureau of Standards (ASMW) of the
former G.D.R. The reproducibility of the cloud-point temperatures was
better than 0.03 K.
Ternary system

The visual titration method of the cloud-point determination usually

applied for measuring the composition of binodal curves was too inaccurate. Therefore the ampoule method described above was also used in this
case. For that the T-x curves of pseudo-binary mixtures with constant mole
ratios of hexane : cyclohexane were observed as shown in Fig. 1. The points
of the corresponding isotherms were obtained from the pseudo-binary T-x
curves by graphic interpolation. The inaccuracy of the points on the
binodal curves determined in this way is estimated to be about xi =
kO.0025. The pseudo-binary T-x curves were measured at the following
hexane : cyclohexane mole ratios: 95 : $90 : lo,80 : 20,65 : 35,60 : 40,40 : 60.
The LLE points were determined at 293.15 K, 303.15 K, 305.70 K and
313.15 K with the help of gas chromatography. A GCHF 18.3 (Chromatron

288
320

310

t
T/K
300

270

260

i
0

0.2

0,4

0.6

0.8

'MeOH

Fig. 2. Experimental cloud points (ampoule method) of the systems methanol + hexane and
methanol + cyclohexane and their modelling by NRTL.

Berlin) was used under the following conditions:

column
stationary phase
column temperature
detector

3 m, inner diameter 3 mm
7% FFAP on Chromosorb W/HP
333 K
heat conductivity detector

carrier gas
samples

hydrogen, 0.7 1 h-l

0.3 /.&I

It was necessary to work with chromatographic factors which were varied

according to the methanol content of the samples. The average inaccuracy
of the mole fraction determination by GLC was estimated to be kO.003.

RESULTS

The solubility data of the system methanol + hexane obtained in these

measurements are illustrated in Fig. 2, together with the data of the system
methanol + cyclohexane published by Hradetzky and Bittrich (1986).

TABLE 1
Experimental solubility data for the system methanol (1) + hexane (2)
x(2)

T(K)

x(2)

T(K)

0.4700
0.5000
0.5500
0.6000
0.6199
0.6249
0.6500
0.6599
0.6750
0.6800
0.7000
0.7249
0.7500
0.7750
0.7861
0.8001
0.8000
0.8164
0.8300
0.8286
0.8501
0.8700
0.8800
0.8850
0.8900
0.9000
0.9098
0.9200

306.45
306.33
305.92
304.89
304.35
304.24
303.19
302.91
302.12
302.00
300.95
298.97
296.96
293.88
292.77
290.95
290.92
288.95
286.14
285.65
283.05
279.35
274.35
272.50
271.95
267.33
261.85
255.15

0.4500
0.4001
0.3700
0.3250
0.2900
0.2750
0.2603
0.2500
0.2250
0.2000
0.1748
0.1600
0.1506
0.1470
0.1400
0.1372
0.1335
0.1300
0.1151
0.1101
0.1003
0.0911
0.0700

306.51
306.39
306.19
305.53
304.47
303.68
302.75
302.05
299.57
296.45
291.59
287.95
285.85
284.45
283.15
281.59
280.11
278.75
273.35
270.95
266.07
259.85
245.15

Table 1 shows the numerical values of the cloud points in the system
methanol + hexane. The critical solution point determined graphically is
given by T = 306.50 K and xMeOH= 0.55. In the system methanol +
cyclohexane the corresponding data are T = 318.93 K and xMeoH = 0.51.
The compositions of the ternary binodal curves determined graphically
from the cloud-point measurements are given in Table 2 while the ternary
tie-line data obtained by GLC are summarized in Table 3.
Figures 3-7 show the LLE of the ternary system for temperatures
between 293 K and 313 K. The comparison of these experimental data with
those of Alessi et al. (1989) at 293.15 K shows good agreement.
In Fig. 5 the LLE is illustrated at the temperature of the double-plait
point (305.70 K). The composition of this point is xHx = 0.350 and xcn =
0.104.

290
TABLE 2
Cloud points in the system methanol + hexane + cyclohexane on lines of constant molar ratio
of hexane (Hx)/cyclohexane (CH)
T(K)
303.15

305.70

306.15

molar ratio Hx/CH

x (MeOH)

x (MeOH)

80/20
65/35
58/42
95/5
90/10
80/20
65/35
58/42
40/60
95/5
40/60

0.362
0.343
0.335
0.467
0.490
0.530
0.470
0.438
0.330
0.515
0.346

0.711
0.705
0.705
0.643
0.613
0.560
0.603
0.622
0.691
0.590
0.682

The plait line was constructed from all critical points. It is remarkable
that the acute-angled contact of the two binodal curves at the double-plait
point, as mentioned by Francis (1963) or obtained by calculation (Lempe,
1983), is found experimentally.
The complete binodal surface of the ternary system is shown in a
three-dimensional representation in Fig. 8. From this the double-plait point
in the minimum of the critical curve and the strong temperature dependence of the heterogeneous liquid region can be seen.

MODELLING

The experimental data are applied as a basis of the modelling of the

LLE using the NRTL equation (Renon and Prausnitz, 1968), known to be
flexible enough for those objectives. It is an important aspect that the
representation
of either the ternary system or the binary subsystems is
guaranteed by a common parameter set. But often the real behaviour of
the subsystems is described wrongly (even the sign of the deviation of the
ideal mixtures does not match) if the model parameters are determined
directly from ternary experimental tie-lines (see for example Lempe et al.,
1983).
Therefore the NRTL parameters were not derived from ternary data as
Alessi et al. (1989) did using a computer program developed by Sorensen et
al. (1979), but by fitting the binary solubility data in both partially miscible
subsystems methanol + hydrocarbon and VLE data p-x at different temperatures in the totally miscible subsystem hexane + cyclohexane.

291
TABLE 3
Tie-line data of the system methanol (l)+ hexane (2)+cyclohexane

(3) estimated by GLC

T(K)

x'(l)

x'(2)

x (3)

x (1)

x (2)

x(3)

293.15

0.185
0.203
0.212
0.215
0.221
0.233
0.237

0.172
0.248
0.319
0.412
0.444
0.530
0.671

0.643
0.569
0.469
0.373
0.335
0.237
0.092

0.821
0.813
0.805
0.799
0.802
0.799
0.807

0.037
0.057
0.077
0.103
0.110
0.136
0.166

0.142
0.130
0.118
0.098
0.088
0.065
0.027

303.15

0.236
0.251
0.293
0.299
0.321
0.332
0.335
0.338
0.349
0.355
0.361

0.105
0.154
0.283
0.234
0.348
0.380
0.374
0.376
0.396
0.497
0.567

0.659
0.595
0.424
0.497
0.331
0.288
0.291
0.286
0.255
0.14
0.02

0.773
0.765
0.734
0.746
0.714
0.708
0.707
0.708
0.702
0.703
0.716

0.031
0.048
0.105
0.081
0.145
0.165
0.163
0.164
0.178
0.226
0.250

0.196
0.187
0.161
0.173
0.141
0.127
0.130
0.128
0.120
0.071
0.034

306.15

0.255
0.284
0.316
0.331
0.348
0.411
0.436

0.084
0.156
0.224
0.218
0.265
0.281
0.290

0.661
0.560
0.460
0.451
0.387
0.308
0.274

0.759
0.736
0.695
0.704
0.679
0.648
0.624

0.027
0.058
0.100
0.096
0.129
0.166
0.190

0.214
0.206
0.205
0.200
0.192
0.185
0.186

313.15

0.328
0.340
0.343
0.344
0.374
0.375
0.439
0.445
0.461

0.031
0.046
0.042
0.044
0.060
0.067
0.081
0.088
0.084

0.641
0.614
0.615
0.612
0.566
0.558
0.480
0.467
0.455

0.705
0.692
0.697
0.684
0.668
0.676
0.616
0.612
0.594

0.014
0.022
0.019
0.030
0.032
0.035
0.055
0.062
0.063

0.281
0.286
0.284
0.286
0.300
0.289
0.329
0.326
0.343

From systematic investigations of the stability behaviour (Novak et al.,

1974, 1987; Lempe, 1983), it follows that the temperature dependence of
the NRTL energy parameters Agii and Agji, which is not principally
necessary for the calculation of miscibility gaps with an upper critical
solution point, should also be used in those cases. Figure 9 shows in a
rji - 7ij diagram (aij = 0.2) that a linear temperature dependence of the

CH
10

20

30

40

50

60

MeOH
70

80

90

Fig. 3. Experimental LLE data (mol%) of the system methanol+ hexane+cyclohexane

at
293.15 K: 0 -0,
GLC tie-lines; X, cloud points by titration; 0, cloud points by the
ampoule method; 0, data measured by Alessi et al. 1989.

energy parameters is not sufficient for describing a closed binary miscibility

gap (here, for example, water + tetrahydrofuran, data from Sorensen and
Arlt, 1979) if aij = constant, because the curve of the critical solution
points is almost linear and two cross-sections are necessary.
If the UNIQUAC model (Abrams and Prausnitz, 1975) is applied,
analogous results are obtained (Lempe, 1983; Lempe et al., 1983) in a
corresponding In 7ji - In 7ij diagram. In this diagram the critical curve is
fixed for the system discussed in the special case because the individual rr
and qi values of the pure components influence this curve while the NRTL
equation leads to generally valid nomographs.
Straight lines passing through the origin in the 7ji - rij diagram of the
NRTL equation or in the In 7ji - In Tij diagram of the UNIQUAC equation correspond to temperature-independent
energy parameters Agij and
Agji while arbitrary straight lines in these diagrams correspond to a linear
temperature dependence of the energy parameters.
That means the linear equation

(1)

293

6
/

V!sL/

\/

LA\,,

CH

MeOH
10

20

Fig. 4. Experimental
303.15 K: 0 -0,
ampoule method.

30

40

50

60

70

80

90

It
LLE data (mol%) of the system methanol + hexane + cyclohexane a
e
GLC tie-lines; X cloud points by titration; 0, cloud points by thl

is valid if

Tij
=Aij/T and

(2)

~ji = Aj,/T

and, with To= 273.15 K,

Aij=Agij/R = A;+A;(T- To)

(3)

Aji=Agji/R=A;+A;(T-T,,)
because by combining these equations the following relations are obtained:

A;-A;T,,
B= A;-A;T,,= constant
(4)
A = A;(A; -AFT,)-A;(A; -A;T,)
= constant
As-ACT0
Temperature-independent

B=Ag/Az= constant

energy parameters
and A =0

then lead to

(5)

294

CH

MeOH
10

20

30

40

50

60

70

80

90

Fig. 5. Experimental LLE data (mol%> of the system methanol+ hexane + cyclohexane at
305.70 K: 0 -0,
GLC tie-lines; qI, cloud points by the ampoule method; ---, plait line.
Double-plait point at x(MeOH) = 0.546 and &-Ix) = 0.350.

Analogous relations are valid for the UNIQUAC

(UNIQUAC) instead of 7ij (NRTL)).
However a good representation of the LLE requires
temperature-dependent
energy parameters even in the
critical solution point. Conversely, in order to keep the
of the Ag,, and the Agji as an alternative, the parameter
as linearly temperature-dependent
czij = cz; + a;( T - To)

equation

(-In

7ij

more than linear

case of an upper
linear dependence
aij was also used

(6)
In the UNIQUAC equation the coordination number could be introduced as temperature-dependent
for this purpose.
By using these six parameters (which seems to be a general minimum
number of parameters for a sufficient flexibility of the different semiempirical model equations) the NRTL model represents the experimental solubility curves in both methanol + hydrocarbon systems very well, even in the
critical region (Fig. 2).
The additional use of NRTL parameters in the subsystem hexane +
cyclohexane obtained from experimental VLE data, p-x, at different
temperatures (data from Gmehling et al., 1980), allows the ternary LLE to
be predicted.

295

CH

Fig. 6. Experimental LLE data (mol%) of the system methanol+ hexane+cyclohexane

GLC tie-lines; I , cloud points by the ampoule method.
306.15 K: 0 -0,

at

Starting with positive and negative initial values for the parameter aij
the fitting procedure (a least-squares method using the activities and not
the mole fractions in the objective function, because they are in better
correspondence with the thermodynamic background) results in the parameter sets summarized in Table 4.
The combination with model parameters for negative ii values, however, only leads to better prediction of the ternary LLE data than is
normally expected in such cases (Fig. 10). The double-plait point was
predicted within +0.3 K.
A comparison with the parameters of Alessi et al. (1989) is not directly
possible because the values of alj are not given in their publication.
Supposing constant aij values, a graph of the model parameters shows the
typical non-linear temperature dependence (here with extrema) discussed
above. These results are observed far enough from the critical points of the
binaries that they should not be caused by the well-known problems of the
representation of the critical region.
Conversely, the use of the model parameters derived in the present work
also results in a satisfactory representation of the experimental data of
those authors, as shown in Fig. 11 for 284.15 K (the lowest temperature
discussed by the authors).

296

CH

10

20

30

40

50

60

70

80

90

MeOH

Fig. 7. Experimental LLE data (mol%) of the system methanol+ hexane+cyclohexane

at
GLC tie-lines; X, cloud points by titration; q, cloud points by the
313.15 K: 0 -0,
ampoule method; 0, plait point extrapolated.

HX

CH

Fig. 8. Temperature dependence of the two-phase region of the system methanol+ hexane
+cyclohexane with the double-plait point DPP in the minimum of the critical line.

297
3

2
1
ij
1

Fig. 9. NRTL nomograph with the curve of critical solution points (c.s.P.); LLE of different
systems in r,i - rij coordinates; a = 0.2.

TABLE 4
Two sets of NRTL parameters (I and II) of the binary systems consisting of the components
methanol (l), hexane (2) and cyclohexane (3)
NRTL
Parameters

i-j

I
II

l-2
l-2

509.802
260.585

1.91353
- 0.23595

492.487
267.625

I
II

l-3
l-3

- 870.722
281.619

27.19785
- 0.25689

1814.06
247.255

I
II

2-3
2-3

- 102.392
71.4350

0.42848
- 0.71355

180.117
- 37.6045

A$(K)

A:

A;(K)

A;

0.825358
- 0.09581
- 33.5358
0.50577
- 1.28317
0.57114

(YE

T
aij

0.3307
- 0.722

0.002682
- 0.006141

0.01929
- 0.8882

0.000306
- 0.001379

0.35
- 0.98

0.00143
0.00286

PROBLEMS AND CONCLUSIONS

The experimental LLE data of the ternary system reported in this work
together with those of Alessi et al. (1989) and the VLE data of Goral et al.
(1983) provide a good basis for testing the efficiency of different model
equations. Therefore this system was proposed by the CODATA Task
Group on Critically Evaluated Phase Equilibrium Data to be applied as
one, of the test systems for modelling of phase equilibria in multi-compbnent systems.

10

20

30

40

50

so

70

80

NRTL

colt.

MeOH

90

Fig. 10. LLE of the system methanol f hexane f cyclohexane (mot%); comparison of experimental and calculated (NRTL) LLE-data at 303.15 and 313.15 K.

exp.1Aiessl

D-.-O

CH

10

20

30

40

50

60

70

80

NRTL

90

et al.

cab,

Me OH

Fig. 11. LLE of the system methanol + hexane + cyclohexane (mol%); ~mparison
mental (AIessi et al. (1989)) and calculated (NRTL) data at 284.15 K,

of experi-

299

ni
-1

01

0,2

I
0.3

I!
Ok

I
0.5

4-

Fig. 12. Influence of the NRTL parameter LYon the calculation of the three-phase pressure
(VLLE) of the systems methanol + hexane and methanol + cyclohexane at 303.2 K.

By using the model parameters given in Table 4to additionally predict

the VLE a systematic deviation of about 8-10% (Ap/p) is observed.
Figure 12 shows that a variation of the NRTL parameter aij within the
usual range of values ( - 1.2.. . +0.6) gives almost the same three-phase
pressure if the energy parameters are obtained from the two mutual
solubilities at a fixed temperature (298.15 K), and the calculated LLE
should be described as a stable equilibrium. This can only be realized,
however, within the aij interval indicated by the dashed lines in Fig. 12,
meaning the common representation of either VLE or LLE data using the
NRTL (or the UNIQUAC) equation in its classical form cannot be realized.
This task should be solved in the following ways.
(1) Extension of the NRTL or one of the other model equations by
additional empirical parameters.
(2) Extension of the model equations by physically founded or, at least,
physically motivated parameters, in this case for example by association
terms for methanol.
In both cases useful results can be obtained. They will be discussed in
detail in a future paper in connection with ternary enthalpy of mixing data,
additionally measured to complete the data sets of this system.

LIST OF SYMBOLS

CH
GLC

cyclohexane
gas-liquid chromatography

300

Hx

LLE
MeOH
THF
VLE
rj, 4i

hexane
liquid-liquid equilibrium
methanol
tetrahydrofuran
vapor-liquid equilibrium
parameters of the UNIQUAC

equation

Greek letters

Tij, Tji, (Y parameters

of the NRTL equation

Superscripts

C
T

temperature
temperature

independent part of the parameter

dependent part of the parameter

REFERENCES
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21: 116.
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New York.
Glindemann, D. and Wohlfarth, Ch., 1986. Flachdichtungsring aus PTFE an Glaskegelverschliissen. Ger. Patent No. DD 262 330 (B 65 D 53/06).
Gmehling, J., Onken, U. and Arlt, W., 1980. Vapor-liquid
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