Fluid Phase Equilibria, 40 (1988) 279-288

Elsevier Science Publishers B.V., Amsterdam

LIQUID-LIQUID

CURVES FOR BINARY SYSTEMS

DONACIANO

COEXISTENCE

BERNABE, ASCENCION

279
Printed in The Netherlands

ROMERO-MARTINEZ

and ARTURO

Xnstituto Mexican0 de1 PetrHeo, Subdirecci6n de LB. P., Eje Central Lizaro
07730 MPxico, D. F (MPxico)
(Received May 11, 1987; accepted in final form September

TRl!JO*

Grdenas

152,

29, 1987)

ABSTRACT
Bernabe, D., Romero-Martinez,
A. and Trejo, A., 1988. Liquid-liquid
binary systems. Fluid Phase Equilibria, 40: 279-288.

coexistence

curves for

The liquid-liquid
coexistence curves of polar+non-polar
binary systems have been
determined experimentally. The polar compounds studied were ethanenitrile, methanol and
N-methylpyrrolidone,
whereas the non-polar compounds were chosen from the n-alkane
series. The upper critical solution temperature
for each set of mixtures increases with
increasing n-alkane chain length, and the critical composition of the polar component also
increases in this fashion.

INTRODUCTION

The experimental investigation of phase equilibria in fluid mixtures has

revealed a wide variety of phase behaviour. The importance of such investigations extends into the fields of both industrial applications and science; this
is demonstrated
by the continuous flow of publications in this field. In
particular, a knowledge of liquid-liquid
equilibria (LLE) is of the utmost
importance for the design, operation and optimization of different kinds of
separation equipment. Equally important is the information on the interactions between unlike molecules, which may be derived from LLE data of
carefully selected mixtures through the use of theories of the liquid state or
solution models.
There exist several possible types of liquid-liquid
coexistence curves,
which have been studied and discussed in the literature. It is well known that
many binary liquid mixtures that form a single, homogeneous phase will
separate into two liquid phases when cooled below a characteristic temper-

* Author to whom correspondence

037%3812/88/$03.50

should be addressed.

0 1988 Elsevier Science Publishers

B.V.

280

ature, i.e. the mutual miscibility of the components decreases with decreasing temperature. The characteristic temperature is the maximum of the
coexistence curve and is called the upper critical solution temperature
(UCST). In other cases, the mutual miscibility of the components decreases
with increasing temperature; thus, the coexistence curve shows a minimum
corresponding to the lower critical solution temperature (LCST). Some other
systems present closed coexistence curves, hence possessing both upper and
lower critical points.
Binary systems that present liquid-liquid
coexistence curves with UCS
phenomena are more abundant than any of the other behaviours mentioned
above. This is verified from the wealth of experimental data compiled by
Francis (1961) and by Sorensen and Arlt (1979/1980).
Upper critical
solution phenomena characterize binary mixtures formed by a polar compound and a non-polar compound, where specific interactions between
unlike pairs of molecules are absent.
In this report of our work on the LLE of binary mixtures, we present
experimental
results of the coexistence curve for systems formed by
ethanenitrile, methanol or N-methylpyrrolidone
as the polar compound, and
an n-alkane containing between 5 and 13 carbon atoms as the non-polar
compound. Previous work on the liquid-liquid phase behaviour of this type
of system included measurements of the upper coexistence temperature for
26 mixtures composed of n-alkanenitriles
and n-alkanes (McLure et al.,
1982); the binary mixtures studied contained ethanenitrile, propanenitrile,
or n-butanenitrile,
and an n-alkane containing between 5 and 18 carbon
atoms.

TABLE 1
Sources, grades and estimated purity of materials used in the liquid-liquid

determinations

Substance

Source and grade

Estimated purity (mol W)

Ethanenitrile
Methanol
N-Methylpyrrolidone
N-Pentane
n-Hexane
n-Heptane
n-Nonane
n-Undecane
n-Tridecane

= h.p.1.c.
b h.p.1.c.
L.R.
d L.R.
e pure
a h.p.1.c.
e pure
e pure
e pure

99.9
99.8
98.0
99.0
99.0
99.6
99.0
99.0
99.0

a Baker. b Merck. Matheson Colleman & Bell. d Sigma. e Phillips Petroleum.

281
EXPERIMENTAL

Materials

The source, grade and estimated purity of each substance used are listed
in Table 1. All compounds were further purified by placing them in contact
with a drying agent. The polar compounds were dried with a molecular
sieve, whereas the n-alkanes were dried with sodium.

400

375

x
:

350

325

300

Fig. 1. Experimental
alkane (2) systems.

coexistence

temperature-composition

curves for ethanenitrile

(l)+ n-

282

Coexistence temperatures
The liquid-liquid coexistence curves of the three sets of binary systems
were determined using the sealed-tube technique (Trejo, 1979; McLure et
al., 1982). The samples were prepared by weight in Pyrex glass tubes. Two
stainless-steel ball-bearings were placed inside the sample tube for stirring of
the mixture during measurements. Each sample was thoroughly degassed by
several freeze-pump-thaw
cycles before being flame sealed under vacuum.

375

350

5
h-

3%

300

275

0.5

Xl

Fig. 2. Experimental coexistence

(l)+ n-alkane (2) systems.

temperature+zomposition

curves for N-methylpyrrolidone

283

The measurement of temperature was carried out with a Hewlett-Packard

quartz thermometer, model 2804A. The samples were brought into thermal
equilibrium in a water bath for temperatures up to 340 K and a ethylene
TABLE 2
Experimental coexistence temperature-composition data for ethanenitrile (1) + n-alkane (2)
systems

T 6)

Xl

n-Pentane
329.11
336.19
339.12
339.36
340.26
340.49
340.48
340.20
339.57
338.11
336.11
328.44
321.34
312.27

0.2146
0.2972
0.3819
0.3894
0.4644
0.4862
0.5457
0.6093
0.6526
0.6975
0.7316
0.8013
0.8407
0.9008

n-Heptane
328.37
338.26
348.58
349.32
351.68
353.74
356.94
356.84
357.30
356.89
356.43
356.05
353.43
348.93
341.76
336.56
333.33
332.87
321.94

0.1591
0.2181
0.3153
0.3231
0.3669
0.4071
0.5522
0.5705
0.6250
0.6738
0.7202
0.7391
0.7977
0.8382
0.8494
0.8921
0.9060
0.9076
0.9303

T 6)

n-Hexane
319.80
332.51
341.75
341.96
342.07
344.56
345.98
348.29
348.34
348.51
348.65
348.51
348.31
347.22
342.32
333.74
313.56

0.1465
0.2050
0.2955
0.2979
0.2996
0.3460
0.3808
0.5013
0.5096
0.5764
0.6000
0.6111
0.6564
0.7098
0.7996
0.8531
0.9123

n-Tridecane
340.82
358.28
363.45
372.10
372.60
386.68
398.98
394.67
396.27
398.57
399.16
399.46
399.25
397.14
384.76

0.1873
0.2791
0.2886
0.3401
0.3471
0.4825
0.5096
0.5702
0.6108
0.6648
0.7527
0.8050
0.8505
0.8944
0.9465

284

glycol bath for measurements above 340 K. The coexistence temperatures

were determined by observing the onset of mixing, marked by the presence
of opalescence, after the samples had been subjected to changes in temperature with heating rates of about 0.03 K mm-. Repeated measurements of
the temperature at which the liquid-liquid meniscus of the same sample
disappeared gave the same value within fO.O1 K. Thus, the coexistence
temperatures reported here are a mean of several determinations for each
one of the compositions studied.
RESULTS AND DISCUSSION

The experimental coexistence temperature-composition

data are given in
Tables 2-4 for ethanenitrile, methanol and N-methylpyrrolidone
with n-al-

TABLE 3
Experimental
systems
T (K)

coexistence

temperature-composition

XI

n-Pentane
276.89
283.71
287.49
288.29
288.68
289.28
289.20
289.19
288.67
288.35
283.92
279.93
269.99

0.220
0.313
0.374
0.413
0.438
0.480
0.491
0.565
0.600
0.702
0.760
0.803

n-Nonane
329.61
340.88
349.83
354.54
355.78
355.94
355.75
355.22
354.36
341.44

0.192
0.281
0.395
0.511
0.604
0.659
0.700
0.751
0.803
0.902

0.100

data for methanol

(1) + n-alkane

T K)

XI

n-Heptane
322.18
326.79
327.69
328.57
329.03
329.17
328.83
328.53
326.71
325.10
319.97
314.69

0.277
0.376
0.394
0.449
0.508
0.555
0.587
0.661
0.701
0.745
0.826
0.852

n-Undecane
348.11
356.56
364.34
370.32
374.44
376.13
376.16
375.78
374.94
370.59
363.15

0.200
0.310
0.395
0.499
0.596
0.698
0.750
0.803
0.851
0.900
0.920

(2)

285
TABLE 4
Experimental coexistence
alkane (2) systems

TW

temperature-composition

data for N-methylpyrrolidone

x,

n-Pentane
309.12
319.45
323.76
324.14
324.18
324.20
323.14
324.36
323.54
319.32
309.51
290.72

0.1030
0.1999
0.3000
0.3502
0.3791
0.3990
0.4323
0.4501
0.4960
0.5980
0.7010
0.8012

n-Nonane
318.66
327.16
332.36
332.98
333.05
332.95
332.85
332.66
332.07
325.87
306.62

0.2011
0.2996
0.4003
0.5015
0.5350
0.5692
0.6044
0.6492
0.6891
0.7970
0.8938

(1) + n-

Xl

n-Heptane:
312.69
317.62
321.05
324.35
325.13
325.41
325.74
325.73
324.34
320.82

0.1622
0.2006
0.2518
0.3061
0.3502
0.3978
0.4442
0.4958
0.6063
0.7037

n-Undecane
318.94
331.61
337.48
340.28
341.17
341.42
341.36
341.10
338.18
322.22

0.1938
0.3016
0.4030
0.4925
0.5580
0.5954
0.6493
0.6981
0.7960
0.9004

kanes, respectively. Figures 1-3 show the solubility curves for the three sets
of systems. From these results it is evident that the solubility of the
n-alkanes decreases as their chain length increases, hence the upper critical
solution temperatures (UCST) for a given set of systems increases as the
chain length of the n-alkane increases; the critical composition (X,C) of the
polar component also increases in this fashion. This behaviour may also be
observed if, instead of referring the changes to the variation of the n-alkane
chain length, any other convenient property is used (e.g. molar volume or
boiling temperature). Table 5 contains UCST and Xc values for all the
systems studied.
Our UCST values for ethanenitrile with C,, C, and C, agree reasonably
well with the upper coexistence temperatures of McLure et al. (1982) and
with the UCST of Zieborak and Olszewski (1956a). No reported values of
the UCST for ethanenitrile with C,, were found in the literature. The UCST

286

273-

Fig. 3. Experimental
(2) systems.

coexistence temperature-composition

curves for methanol (l)+n-alkane

determined here for methanol with C, agrees well with the value
quoted by Francis (1961) and it is slightly higher than the values reported by
Kiser et al. (1961) and by Zieborak et al. (1956b). Our value of the UCST

value

287
TABLE 5
Comparison of upper critical solution temperatures
for the systems studied in this work
System

This work

(UCST) and critical compositions

Literature

UCST (K)

X,c

UCST (K)

X,E

Ethanenitrile
+n-C,
n-C,
n-C,
n-G

340.21
348.80
357.35
399.83

0.5094
0.5557
0.5972
0.7907

341.2 a
350.2 a
358.0 a, 351.8
_

0.687 =
0.714 d
0.736 , 0.63 b
_

Methanol
+ n-C,

288.32

0.461

0.502 c

n-C,
n-C9
n-C,,

329.27
355.88
376.04

0.551
0.660
0.737

287.40 , 287.90 ,
287
324.4 , 324.2 d,e

N-methylpyrrolidone
+ n-C,
324.35
n-C,
325.76
n-C,
333.19
n-C,,
341.38

(X,C)

0.3478
0.4659
0.5438
0.6148

a McLure et al. (1982). b Zieborak

(1961). e Zieborak et al. (1956b).

376 d.e
_
_
-

0.601 , 0.54 e
_
_
_
_
_

and Olszewski (1956a). Kiser et al. (1961). d Francis

for methanol with C, is 5 K higher than the values given by Kiser et al.
(1961), Francis (1961) and Zieborak et al. (1956b). No comparison is carried
out for the UCST with C, since no data were available from the literature.
Our UCST with C,, agrees very well with the value reported by Zieborak et
al. (1956b). It was not possible to compare our UCST values for N-methylpyrrolidone + n-alkanes due to lack of reported data in the literature for this
set of systems.
The compositions given in Table 5 for ethanenitrile + n-alkane systems by
McLure et al. (1982) correspond to equivolume mixtures, thus a direct
comparison with X,C values of this work is not possible. Our X,C values for
methanol with C, and C, are lower than those reported by Kiser et al.
(1961), although our value with C, agrees with that reported by Zieborak et
al. (1956b). As for the UCST values, no reported data of critical compositions are available in the literature for N-:methylpyrrolidone
+ n-alkane
systems.
LIST OF SYMBOLS

LLE liquid-liquid equilibria

UCST upper critical solution temperature

288

LCST lower critical solution temperature

T
temperature (K)
mole
fraction of component i
X,
critical composition of component
x

REFERENCES
Francis, A.W., 1961. Critical solution temperature. Am. Chem. Sot., No. 31, Adv. Chem. Ser.,
Washington, DC.
Kiser, RW., Johnson, G.D. and Shetlar, M.D., 1961. Solubilities of various hydrocarbons in
methanol. J. Chem. Eng. Data, 6: 338-341.
McLure, LA., Trejo, A., Ingham, P.A. and Steele, J.F., 1982. Phase equilibria for binary
n-alkanenitrile-n-alkane
mixtures. I. Upper liquid-liquid
coexistence temperatures
for
ethanenitrile, propanenitrile and n-butanenitrile with some C5-Cl8 n-alkanes. Fluid Phase
Equilibria, 8: 271-284.
Sorensen, J.M. and Arlt, W., 1979/1980. Liquid-liquid
equilibrium data collection, DECHEMA Chemistry Data Series, Vol V, 3 parts. Frankfurt.
Trejo, A., 1979. A thermodynamic
study of polar+non-polar
fluid mixtures. Ph.D. Thesis,
University of Sheffield, Sheffield.
Zieborak, K. and Olszewski, K., 1956a. Heteropolyazeotropic
systems. II. Acetonitrile-nparaffinic hydrocarbons. Bull. Acad. Pol. Sci. Cl. III, 4: 823-827.
Zieborak, K., Maczynska, 2. and Maczynski, A., 1956b. Heteropolyazeotropic
systems. I.
System methanol-n-paraffinic
hydrocarbons. Bull. Acad. Pol. Sci. Cl. III, 4: 153-157.