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ETHANOL-WATER
SYSTEM
Vapor-Liquid Properties
at High Pressures
e.
Vapor-liquid equilibria up to 15 atmospheres were reported by Grumbt (3). However, a study of his data shows
serious scattering of the points and self-inconsistencies which
he attributed to refluxing in the vapor line of his apparatus.
The vapor-liquid equilibria of the system were determined
a t several constant temperatures with an all-steel recirculation
type apparatus. The development of this apparatus and the
high-pressure vapor-liquid equilibrium of the benzene-toluene
The photograph shows a control panel for continuous rectification of
190 proof alcohol from wheat mash, a t the plant of Joseph E.Seagram &
Sons, Inc.: section of column may be seen in the background.
1
2
701
702
-A . VAPOR- L iaum
EQUIL IERIUM
OF
C R I T I C A L TFhPER.4 TURES
*-f-f3''
E THANO1 - WA TER
CONSTANT TEMPERAT U K S
4.VAPOR-LIQUID
ro
20
30
40
so
60
70
80
30
10
20
30
40
50
60
70
80
90
EQUILIBRIUM
OF
-7
20
30
4,O
50
Figure 1
CALCULATED F
EXPERIMENTAL
THANOL IN
IO
(1
NOYES 8 WARFEL (
iiauio
60
70
80
90
The experimental vapor-liquid equilibrium data are summarized in Table I and plotted as isothermal Y-X curves on
Figure 1A. To develop the constant pressure Y-X plot of
Figure lB, pressure isotherms were plotted and then curves
of vapor composition against pressure for several constant
liquid compositions were constructed. Interpolation of the
latter curves gave the isopiestic Y-X graph (Figure 1B).
CRITICAL TEMPERATURES
an over-all length of about 60 mm. The observed temperatures (after emergent stem corrections) were accurate
to approximately 1" C.
The constant volume behavior of this system as the critical
state is approached was found to differ somewhat from that
characteristic of pure compounds and hydrocarbon mixtures.
The tubes were charged with alcohol solution to approximately one third their volume a t room temperature and were
then sealed. I n the determination idiich followed, the liquid
volume or meniscus level rose with temperature. TT'ithin
the last 1" C. below the critical, the meniscus rose from about
two thirds of the tube height to completely fill the tube.
The vapor phase apparently became zero, and disappearance
of the meniscus could not be observed. On slow cooling from
1' C. above this temperature, a white cloud 1%-ouldsuddenly
appear, quickly condense, and reveal a liquid meniscus.
These rising and falling temperatures differed by less than
1' C. for all cases in which the tubes were charged to between
20 and 40 per cent of their volume a t room conditions. This
temperature is therefore taken as the true critical. Further
support of this hypothesis is obtained from a study of relations for relative vapor and liquid volumes a t constant total
June, 1943
703
CRITICAL PRESSURES
275
12.6
26.0
40.0
24.5
34.4
42.5
1176
1341
1492
TABLE11. SUMMARIZED
DATAFOR CRITICALTEMPERATURES
AND PRESSURES
Weight
Ethanoy
Mole 7
Ethan07
100
94.0
88.7
84.0
79.0
74.1
69.2
64.4
61.0
55.1
49.6
45.1
40.0
35.8
26.9
24.0
18.7
100
86.1
75.5
67.3
59.4
52.8
46.8
41.5
38.0
32.4
27.8
24.4
20.6
17.9
12.6
11.0
8.3
Critical
Temp
C."
243.0
248.0
253.1
259.2
264.2
270.3
277.3
284.4
288.4
296.5
307.5
311.6
317.6
325.7
334.8
339.8
344.9
Weight %
Ethanol
100
86.5
80.0
63.9
46.0
30.9
16.3
Critical
Mole 7 Pressure
Etheno? Lb./Sq. Ih.
100
71.5
61.0
40.9
25.0
14.9
7.1
925
1100
1220
1618
2060
2440
2830
704
LITEHATUHE CITED
I
M O L E PER C h N T E T H A N O L
Figure 3
Figure 4