F&d

Phase Equilibria, 43 (1988) 105-113

105

Elsevier Science Publishers B.V., Amsterdam -

Printed in The Netherlands

PHASE EQUILIBRIA FOR FOUR BINARY SYSTEMS

CONTAINING PROPYLENE
KAZUNARI OHGAKI, HIDEAKI TAKATA, TAKASHI WASHIDA
and TAKASHI KATAYAMA
Department

of Chemical

Engineering,

Faculty of Engineering

Science,

Osaka

Unicersq,

Toyonaka, Osaka 260 (Japan)

(Received May 14, 1987; accepted in final form February 11, 1988)

ABSTRACT
Oh&i. K., Takata, H., Washida, T. and Katayama, T., 1988. Phase equilibria for four binary
systems containing propylene. Fluid Phase Equilibria, 43: 105-113.
Isothermal vapor-liquid equilibria (P-X, JJ) for four binary systems of propylene with
methanol, acetone, diethyl ether and propylene oxide were measured using a swing method at
25 o C. Also, the saturated molar volume of the liquid phase for each system was obtained by
a weighing method. The data obtained were correlated by use of the Soave-Redlich-Kwong
equation. The P-x, y relations were described satisfactorily, except for the methanol-propylene system.

INTRODUCTION

The high-pressure phase equilibrium is one of the most important properties used in separation processes. Furthermore, phase equilibria of strongly
non-ideal mixtures supply important information for studying equations of
state.
The phase equilibria of asymmetric binary systems (molecules differing
markedly in size, shape and interaction energy) containing propylene are
rarely investigated due to experimental difficulties: only the solubilities of
propylene in methanol and acetone have been measured at -30.4 and
- 50.4 C (Hakuta et al., 1970). In this study a new experimental method,
the so-called swing method (Yasuda et al., 1975), was used for measuring
phase equilibria for asymmetric binary mixtures. One of the characteristics
of this method is that a small amount of sample of each phase is drawn out
from a line attached to twin high-pressure vessels for each phase without
disturbing the phase equilibrium. By use of this method, isothermal
vapor-liquid equilibria for four binary systems of propylene (with methanol,
0378-3812/88/$03.50

0 1988 Elsevier Science Publishers B.V

106

acetone, diethyl ether and propylene oxide) were measured in a pressure

range of O-1.1 MPa at 25C.
Also, using different apparatus a weighing method was used for measuring the saturated molar volume of the liquid phase. From the above results,
the isothermal pressure-saturated
liquid molar volume-vapor
and liquid
phase composition ( P-uL-x, y) relation was obtained for each system.
EXPERIMENTAL

P-x, y measurement
The experimental apparatus for P-x, y measurement is shown schematically in Fig. 1. The apparatus consisted of twin vessels (each having sight
glasses and an internal volume of - 100 cm3), a pressure measurement part
and a composition analysis part. The second cell F was connected to the
first cell F via two flexible tubes. The second cell moved up and down to
replenish the contents of the tubes and to mix the contents of the two cells.
There were four sampling ports (d and e for the vapor phase, f and g for the
liquid phase) in the flexible tubes. Therefore, a small amount of sample for
each phase could be removed without disturbing the phase equilibrium. The
sample removed from the sampling port was expanded in a Pyrex flask I and
recirculated for gas mixing with a blower H. Reproducibility in the composition analysis was within 0.5% for the component of lower concentration. As
the method of composition analysis applied in this study is essentially the

Fig. 1. Schematic diagram of experimental apparatus: A. air piston guage; B. hand pump; C,
quartz Bourdon guage; D, pressure transducer; E, solvent vessel; F, equilibrium cell; G,
water bath; H, blower; I, container; J, gas chromatograph; d-g, sampling ports.

same as described in a previous paper (Ohgaki et al., 1982a), the details are
not mentioned here.
Tbe equilibrium pressure was measured to within an accuracy of 0.1%
with a combination of a pressure transducer D and a quartz Bourdon gauge
C calibrated by an air piston gauge A, all manufactured
by the Ruska
Instrument Co. The twin cells, valves and lines connected to the cells were
all immersed in a water bath controlled at 25.00 i_ O.OlC. As the procedures of both pressure and temperature measurements have been described
previously (Ohgaki et al., 1982b). readers are referred to this paper for
details.
Liquid density meusuremrnt
In addition to the P-x, y measurement, the saturated molar volume of
the liquid phase was measured by a weighing method. The equipment for
volume measurement is shown in Fig. 2. The volume of the vessel used for
density measurement was cahbrated by the liquid density of each solvent
(Reid et al., 1977) and propylene (Angus et al., 1976) with an accuracy of
kO.0248. To establish the equilibrium, the contents of the vessel were
agitated with stainless steel beads. We could ascertain that the vessel was
filled with saturated liquid mixture only by observation of the boundary
between vapor and liquid phases through a clear tube. After the ball valve
shown in Fig. 2 had closed, the clear tube was removed from the vessel. The

Fig. 2. Vessel for molar volume measurement.

108

weight analysis was performed with a high-sensitivity balance (maximum

sensitivity 0.1 mg) manufactured by the Chyo Balance Corp. The composition of the liquid mixture was analyzed by gas chromatography. The uL-x
relation for each system was measured at several pressures.
Materials

Propylene having a specified minimum purity of 99.95 mol% was specially

supplied by the Sumitomo Chem. Co., Ltd. Small amounts of impurities in
other chemicals were detected for each material by gas chromatography
(PEG 6000); the ratios of peak areas were 1: 12000 for methanol and
propylene oxide, 1: 10 000 for acetone and 1: 15 000 for diethyl ether.
RESULTS AND DISCUSSION

The isothermal vapor-liquid

equilibrium data (P-x, y) are listed in
Tables l-4 and are shown in Figs. 3 and 4. The Soave-Redlich-Kwong
(SRK) equation (Soave, 1972) was applied to correlate the P-x, y relation
for each system. The solid lines in Figs. 3 and 4 are the correlation results
from the SRK equation with a binary interaction parameter in the quadratic
mixing rule.
The saturated molar volumes of the liquid phase obtained in this experiment are shown in Fig. 5 and the smoothed values are listed in the last
column of each table. The solid lines in Fig. 5 are the smoothed values

TABLE 1
Vapor-liquid
25C

equilibria

and molar volumes

for the system methanol(l)-propylene(2)

P (MPa)

X2

Y2

uL

0.0169
0.4795
0.5922
0.7677
0.9026
0.9966
1.0515
1.0802
1.1240
1.1418
1.1480
1.1566

0.0000
0.0779
0.1044
0.1615
0.2221
0.2803
0.3524
0.4102
0.6005
0.7942
0.9362
1.0000

0.0000
0.9687
0.9755
0.9823
0.9860
0.9884
0.9895
0.9899
0.9906
0.9908
0.9928
1 .oooo

40.73
43.62
44.64
46.85
49.24
51.66
54.46
56.81
64.66
73.12
80.00
83.39

a Smoothed value.

(cm3 mol-)

at

109
TABLE 2
Vapor-liquid
25OC

equilibria and molar volumes for the system acetone(l)-propylene(2)

P (MPa)

x2

Y,

uL [cm3 mol-1

0.0306

o.oOQo

0.0000

74.05

0.2102

0.0758

0.8420

74.38

0.3452

0.1380

0.8995

74.68

0.4901

0.2137

0.9292

75.09

0.5682

0.2655

0.9399

75.41

0.6991

0.3727

0.9546

76.17

0.7474

0.4325

0.9600

76.66

0.7970

0.4909

0.9641

77.18

0.8269

0.5248

0.9669

77.51

0.9071

0.6353

0.9723

7X.67

1.0131

0.8173

0.9823

80.90

1.0716

0.8997

0.9883

82.01

1.1120

0.9531

0.9931

X2.74

1.1566

1 .oOOo

1.0000

X3.39

system at

a Smoothed value.

obtained using an equation of the Redlich-Kister

type. The liquid density
predicted from the S-R-K
equation (k,, was obtained from P-x; y
correlation) is shown as a broken line. Only the propylene oxide-propylene
system could be described satisfactorily.
TABLE

Vapor-liquid

equilibrium and molar volume for the system diethyl ether(l)-propylene(2)

25C
P (MPa)

x2

Y2

uL [cm3 mol-1

0.1692
0.2666

0.0000
0.0929
0.1860

0.0000
0.5701

104.85
103.48

0.7453

102.04

0.3201

0.2475

0.8015

101.04

0.4255

0.3412

0.8582

99.43

0.4917

0.4042

0.8884

9X.28

0.5340

0.4489

0.9030

97.42

0.6354
0.7084

0.5495
0.6138

0.9294
0.9435

95.36
93.94

0.7772

0.6747

0.9549

92.52

0.8898

0.7711

0.9694

90.09
87.21

0.0712

1.0073

0.8753

0.9844

1.0872

0.9405

0.9927

85.27

1.1566

1.0000

1.0000

83.39

Smoothed value.

at

110
TABLE 4
Vapor-liquid
at 25C

equilibrium

and molar volume for the system propylene

P (MPa)

x2

Y2

uL

0.0717
0.1962
0.3304
0.4294
0.5165
0.6067
0.6947
0.8087
0.8764
0.9462
1.0205
1.0726
1.1566

0.0000
0.0691
0.1623
0.2406
0.3182
0.4103
0.4990
0.6247
0.7068
0.7849
0.8692
0.9199
1.0000

0.0000
0.5979
0.7811
0.8418
0.8781
0.9051
0.9235
0.9442
0.9550
0.9665
0.9781
0.9864
1 .oooo

70.62
71.13
71.79
72.37
72.99
73.83
74.79
76.41
77.67
79.00
80.61
81.64
83.39

oxide(l)-propylene(2)

(cm3 mol-)

Smoothed value.

0
0.0 0.2

0.4 0.6 0.8 1.0

x2 rY2
Fig. 3. Vapor-liquid equilibria for binary systems at 25 o C: o-o,
a, propylene oxide-propylene.
@-

methanol-propylene;

111

0.0 02

0.4 0.6 0.8 1.0

XzJ2

Fig. 4. Vapor-liquid equilibria for binary systems at 25OC: o-----o,

0 -!
diethyl ether-propylene.

acetone-propylene;

60

40

0.0 0.2

0.4

0.6
X2

0.8 1.0

Fig. 5. Molar volume of liquid phase for each binary

methanol-propylene;
o -0,
propylene oxide-propylene;
~-----a,
diethyl ether-propylene.

system
o-

at 2S C: o----o,
0, acetone-propylene;

112
TABLE 5
Constants
298.75 K

of the SRK equation

evaluated

from saturated

Substance

pressure

and molar volume at

k 12

Methanol
Acetone
Diethyl ether
Propylene oxide
Propylene

0.33103
0.34531
0.39132
0.35396
0.40736

0.06612
0.06820
0.07805
0.0699X
0.08117

(0.0297)
0.0620
0.0176
0.0593
_

a The methanol-propylene
system could not be correlated well by the SRK equation. Critical
properties and acentric factor were obtained from Reid et al. (1977).

Generally, a different
correlation. In the above
equation were obtained
each component and the
Methanol-propylene

k,, value had to be introduced for P-x, y and uL

calculation the parameters 9, and Q, in the SRK
from the saturated pressure and liquid volume of
values are listed in Table 5.

system

The P-x, y relation for the system could not be correlated well since the
SRK equation gave a liquid-liquid equilibrium in the high pressure region.
This system is one of the most difficult to be correlated by the equation of
state. Although the phase behavior was investigated in the wide temperature
range of -50 to about 4OC, liquid separation was not observed at
x2 = 0.2, 0.4, 0.6 or 0.8.
Acetone-propylene

system

This system showed a highly non-ideal behavior caused by the strong

polarity of acetone. In the correlation of P-x, y, the SRK equation
(kr, = 0.062) could not describe the experimental data satisfactorily in the
low pressure range.
Diethyl ether-propylene

system

Although diethyl ether is polar, the P-x, y relation is almost linear, as

can be seen in Fig. 4. The saturated molar volume for this system only
showed a positive drift. The P-x, y relation for the system could be
correlated satisfactorily by the SRK equation ( k12 = 0.0176).

113

Propylene

oxide-propylene

system

The equilibrium properties (P-x, y including u) for this system only

were correlated simultaneously by the equation of state (k,, = 0.0593). In
spite of the considerable polarity of propylene oxide, the system showed
almost ideal behavior.
ACKNOWLEDGMENT

This work was largely supported by a Grant-in-Aid for Scientific

search from the Ministry of Education, Science and Culture, Japan.

Re-

LIST OF SYMBOLS

k
d
uL
x2
Y2

binary parameter in the SRK equation

total pressure (MPa)
saturated molar volume of liquid phase (cm3 mol- )
mole fraction of propylene in the liquid phase
mole fraction of propylene in the vapor phase

REFERENCES
Angus, S., Armstrong, B. and de Reuck, K.M., 1976. International Thermodynamic Tables of
the Fluid State-Propylene,
Pergamon Press, Oxford.
Hakuta, T., Suda, S. and Hiram, M., 1970. Low temperature vapor liquid equilibria-propylene-solvents
binary systems. Mem. Fat. Tech., Tokyo Metro Univ., 20: 85-92.
Ohgaki, K., Nakatani, T., Saito, T. and Katayama, T., 1982a. Isothermal vapor-liquid
equilibria of propylene oxide-ethylene and ethyl ether-ethylene
systems at high presssures.
J. Chem. Eng. Jpn., 15: 91-97.
Ohgaki, K., Nakamura, Y., Ariyasu, H. and Katayama, T., 1982b. Interaction second viriaf
coefficients for six binary systems containing carbon dioxide, methane, ethylene and
propylene at 125 o C. J. Chem. Eng. Jpn., 15: 85-90.
Reid, R.C., Prausnitz, J.M. and Sherwood, T.K., 1977. The Properties of Gases and Liquids,
3rd Edn., Property Data Bank. McGraw-Hill, New York, pp. 629-666.
Soave, G., 1972. Equilibrium constants from a modified Redlich-Kwong
equation of state.
Chem. Eng. Sci., 27: 1197-1203.
Yasuda, Y., Kawade, H. and Katayama, T., 1975. Vapor-liquid and liquid-liquid equilibria
for binary and ternary systems containing methanol. Kagaku Kogaku Ronbunshu, 1:
172-175.