Vapor-Liquid Equilibria for Binary

sn-water Systems
RIKI KOBAYASHIl AND DONALD L. KATZ
University of Michigan, Ann Arbor, M i c h .

on the vapor-liquid phase relations of hydrocarbon-

W O R
water
K systems was initiated by Scheffer in 1913 on the hexme-water ( 3 1 ) and the pentane-water ( 5 2 ) systems. His studies
were primarily confined to the phase relations of the systems in
the region bounded by the vapor pressure curve for the pure
hydrocarbon and the conditions under nhich three phases coexist
-a vapor phase, a lighter liquid phase rich in hydrocarbon, and a
heavier liquid phase rich in water. Scheffer found that as the
temperature of the hydrocarbon-water mixtures under the coexistence of three phases was increased, a temperature was reached a t
which the intensive properties of the vapor phase and the lighter.
liquid phase became continuously identical. The conditions
under which this critical phenomenon occurs have been referred to
as the three-phase critical conditions and the composition of
the identical phases as the three-phase critical composition ( 1 9 ) .
The solubility of methane in water has been reported a t 25' C.
by Michels, Gerver, and Bijl ( 2 1 ) up to a pressure of 6800
pounds per square inch and a t the same temperature by Frolich
et al. ( 1 2 ) up to a pressure of 2060 pounds per square inch.
The studies of the saturated water content of hydrocarbon gases
were undertaken in connection with the dehydration of natural
gases to prevent the formation of natural gas hydrates. Lauhlere
and Briscoe ( 1 6 ) and Deaton and Frost ( 9 ) determined the saturated concentration of water in natural gases up to 100" F. and
600 pounds per square inch. These data on natural gases were
supplemented by those of Russell, Thompson, Vance, and Huntington (26) for pressures up to 2000 pounds per square inch.
Sage, Lacey, and coworkers have determined the dew point
composition of the methane-water (a$) and the ethane-water
( 2 4 )systems from 100" to 460" F. up to 10,000 pounds per square
inch. Reamer e l al. (25) have also determined the concentration
of water in the n-butane-water system in the vapor and the lighter
liquid phases in the three-phase region. Similar data on the
concentration of water in the vapor and the lighter liquid phases
for the propane-water system have been reported by Poettman
and Dean ( 2 3 ) . Data on the water content of a natural gas
saturated with water and the solubility of the same natural gas
in water and in brine solutions up to 250' F. and 5000 pounds per
square inch have been presented by Dodson and Standing (10).
McKetta and Kat2 (19, 2'0) made an extensive study of the
methane-n-butane-water system in the two -phase and threephase regions, and developed general plots for the estimation of
the solubility of water in hydrocarbon gases and liquids (20).
Culberson, Horn, and McKetta ( 6 ) reported data on the solubility of ethane in water up t o 1200 pounds per square inch and
methane in water a t 77" F. up to 10,000 pounds per square inch.
Culberson and McKetta (7, 8) have recently extended their data
on the solubility of methane in water and ethane in water over the
temperature range from 100' t o 340' F. up to 10,000 pounds
per square inch.
I n this investigation vapor-liquid equilibria data were obtained
in the two-phase and three-phase, regions for the propane-water
system a t temperatures from 54' to 300' F. and pressures from
100 to 2800 pounds per square inch. The system has been studied
with relative thoroughness, especially in the region surrounding
205.7' F. and 637 pounds per square inch, the three-phase critical
Present address, Department of Chemical Engineering, The Rice Instit u t e , Houston, Tex.
1

440

conditions. This paper also present.8 a correlation for the water

content of hydrocarbon-rich phases and a procedure for extending
and smoothing the data on solubility of volatile hydrocarbons
in water.
EXPERIMENTAL DETERMINATION OF PROPANE-WATER
SYSTEM

This vapor-liquid equilibria study was conducted using a batch

operation. Propane and water were placed in a pressure cell
in the desired amounts and the contents of the cell were brought
to phase equilibrium by mechanical agitation. A thermostatically controlled air bath surrounding the cell maintained it a t
thermal equilibrium. The resulting phases were sampled under
equilibrium conditions by injecting mercury into the cell as the
individual samples were being removed from it.

0-150 OR

0-1000 PSI

0-3000 PSI GAU6E

TO T R A I N
TO BURETTE
F R O M MERCURY S O U R C E

Figure 1. Flow Sheet of VaporLiquia Equilibria Apparatus

The flow sheet of the vapor-liquid equilibria apparatus is
shown in Figure 1. The electrically powered stirrer, which is
mounted entirely within the cell, has been deleted from the drawing to show the relative locations of the sampling ports within
the cell. The high pressure equilibrium cell has a glass window
which permits the observation of liquid levels. The cell was
constructed by Chaddock ( 4 ) and the auxiliary apparatus was
built by McKetta ( 1 9 ) . Some revisions of the apparatus were
made by the authors in order to adapt the equipment to the study
of the propane-water system.

A portable pressurizing unit constructed for general use was

utilized to compress mercury and gas during the charging and
sampling operations. Ports located a t four different and appro-

INDUSTRIAL AND ENGINEERING CHEMISTRY

February 1953

priate positions in the cell were uced for charging, sampling, and
discharging the contents of the cell. In Figure 1, V , L,,and F . 1
designate the vapor, lighter liquid phase, and the heavier liquid
phase sampling ports, respectively. The difierent sampling
ports provide a means for sampling each phase through a different
port located in its own phase to avoid contamination of the
sample lines by a second phase.
The vapor phase sampling line, V-T4-16, was wrapped with
a n electrical rasistance heater in order to superheat the vapor
sample leaving the cell. It is especially important that the con?
densation of the vapor phase be prevented when sampling in the
three-phase region, as complete condensation of that phase could
occur with a very slight cooling below the equilibrium temperature. The resulting change in phase would cause the loss of
water from the sample in the sample lines. Heating the vapor
s a m p h g line also hastened the purging of any excess water remaining in the lines from previous runs.

i'

I
A

D
R
D

Figure 2.

E
G
H

NEEDLE VALVE,VAPCR
NEEDLE VALVE, LIQUID
ASOARITE TOWER
D E H m R l T E TOWERS
WATER-PROOFED
CONNECTIONS
TRAP
SETTLING BULB
V
VACUUM

MERCURY BUBBLER
MERCURY MANOMETER
M CALIBRATED BOTTLE
N
THERMOMETER
0
G L A S S CASE
P
WIRE GUARD
U
DRYING TUBES
PUMP
J

_ _

Analytical Train for Analysis of HydrocarbonRich Phases

The equilibrium cell was evacuated and flushed several times

with propane gas a t the beginning of each series of isothermal
runs and whenever the cell was contaminated with other gases.
The individual constituents, propane and water, were charged
into the cell in quantities that would satisfy the desired conditions
of pressure, number of phases, and quantity of each phase. Before the beginning of the stirring operation the liquid sampling
lines were filled with clean, dry mercury to displace any other
liquids in them and to block off the lines during the agitation
period. The agitator was operated intermittently for a t least 2
hours under constant conditions of pressure and temperature
before any samples were taken. Using a stirring period of 2
hours, it was found that the final phase concentrations of the
dilute components were reproduced, regardless of whether a
given equilibrium pressure was approached from a pressure
greater or less than the final equilibrium pressure.
A quiescent period of 15 minutes was allowed after agitation
periods before the samples were displaced from the cell. The
samples were transferred directly from the cell to the analytical
apparatus through steel tubing of small diameter. The vapor
phase was sampled through V-T4-l6, the lighter liquid phase
through Lz-11-12, and the water-rich liquid phase through
Li-15-14-13.

The same analytical procedure was used to analyze the vapor

phase and the lighter liquid phase, as both are propane-rich.
Figure 2 shows the train used to analyze these two phases.

44 1

mosphere, it was necessary to prove the effectiveness of Dehydrite as a drying agent a t reduced pressures. No loss in
weight of previously used drying tubes could be detected after
the pressure within the drying tubes had been maintained a t
less than 0.1 mm. of mercury absolute pressure for 12 hours.
Figure 3 shows the apparatus utilized in the analysis of the
water-rich liquid phase.

Prior to the agitation period of each run the water-rich liquid

phase sample line was evacuated from valve 13 (Figure I), to
stopcock S (Figure 3 ) . The entire line was then filled with
mercury through valve 13 (Figure 1 ) . The water-rich phase
sample was passed through the cooler at the equilibrium pressure
and flashed to the barometric pressure at needle valve S (Figure
3). The mercury leveling bulb was adjusted continually to
maintain the gas pressure in the buret at precisely the barometric
value. The water jacket surrounding the gas buret was maintained at a constant temperature near room temperature. When
the,desired amount of sample had been displaced from the cell,
valve 13 (Figure 3) was closed and the sample in the lead lines
allowed to cool to room temperature. Valve S (Figure 3 ) was
then opened slowly to allow the liquid in the lead lines to expand
to atmospheric pressure. Finally mercury was introduced
through valve 13 (Figure 1 ) to displace all the liquid and gas in
the lead lines into the buret. In this way, any of the gas leaving
the solution which remained trapped in the lead lines was ultimately caught in the gas-water buret. To see if the flash vaporization a t valve S occurred
under equilibrium conditions, mercury was
dropped for several
minutes through the buret
to agitate the flash liquid.
No change in the volume
of the flash gas or liquid
could be detected.

t- I'I

The volume of the flash

liquid and flash gas, the
equilibrium cell temperature and pressure, the
temperature of the buret
water jacket, and the
1
barometric pressure were
MERCURY
recorded. The propane
SOURCE
d i s s o l v e d i n t h e flash
Figure 3. Apparatus for
liquid was computed using
Analysis
of Water-Rich
Liauid Phase
the solubility data of
propane in water a t atR. Concentric-tube cooler
mospheric pressure (17),
S. Needle valve
U . 70-mm. borosilicate glass
the volume of the flash
tubing
U . Gas-water buret
liquid, and its density.
V. Cooling water
The vapor pressure data
W. Metric scale
IX. Air inlet
of pure water were used to
Y . Mercurv leveling bulb
correct for the water present in the equilibrium
flash vapor. The compressibility factor of propane gas was
applied to correct for the nonideal volunietric behavior of the
flash gas. A material balance of the propane and water
made on the over-all sample yielded the final composition of the
sample.
I

EXPERIMENTAL MEASUREMENTS

The vapor and liquid phases were expanded from the equilibrium pressure to the pressure of the analytical train a t valves 16
and 12, respectively. The expanded sample was passed through
two U-tubes in series and the dehydrated propane gas was
measured in a calibrated glass bottle. Dehydrite (magnesium
perchlorate) was used as the dehydrating agent. The gain in
weight of the U-tubes, the pressure rise of the gas in the bottle
and the temperature of the gas collected in the bottle were recorded. The compressibility factors of propane gas a t atmospheric and lower pressures were applied in the calculation of the
phase composition from the observed data.
Because the dehydration of the propane was conducted a t
pressures ranging from less than 0.1 mm. of mercury to 1 at-

The equilibrium temperature of the cell was measured by

means of two calibrated copper-constantan thermocouples inserted into the walls of the equilibrium cell. The thermocouples
were calibrated to an accuracy of 0.1' F. in a water bath and in
an oil bath with high precision thermometers which are periodically calibrated by the National Bureau of Standards. The temperature of the cell did not vary over 0.3' F. during the equilibrating and sampling operations or temperatures up to 200" F. and
not over 0.5" F. for the higher temperatures.
The equilibrium pressures were measured by means of steel
tube Bourdon gages calibrated at frequent intervals by a dead
weight tester. Three different gages of different ranges were used.
The accuracies of the pressure readings were estimated to be
within = k l % of the readings taken with the 0 to 150 pounds per

'

INDUSTRIAL AND ENGINEERING CHEMISTRY

442

00040

Vol. 45, No.

PROPANE-WATER

,012

1
SYSTEM

140

160

,010
00036
W

4
z

008

5 ,006

$00032

goo028

IL

Io

E
& 00024

004

-I

1
0

,002

.00020

40
40

60

Figure 4.

TABLEI.

100

120

140

160

180

200

EXPERIMEXTAL
DATA IN THREE-PHASEREGION

63.0
64.1
83.1
87.0
102.5
111.6
111.8
127.7
128.2
144.1
144.1
170.0
179.0
179.2
187.6
188.6
190.3
192.8
193.0
201.6
201.7

Pressure
Lb./Sq. Inch' Abs.

Composition of
Vapor Phase, Mole
Fraction Water

Concentration of Water in Vapor Phase

113.8
0.002322
114.6
0.002370
151.8
0.003582
159.7
0.003708
195.0
0.004855
220
0.00552
220
0.00549
270
0.00696
271
0.00696
328
0.00854
328
0.00863
0.01097
437
0.01175
488
487
0.01177
529
0.01263
535
0.01278
540
0.01282
0,01282
561
0.01270
562
0,01212
613
0.01208
612

Concentration of Wal>ei-in E'ror lane -Rich Li.quid Phase

Propane-Rich
Liquid Phase
107.1
0.0001368
58.4
142.5
78.5
0.0003340
142.5
0.0003403
78.7
195.0
0.000614
101.9
195.6
0.000626
101.9
272
0.001368
128.5
271
0.001378
128.8
0.001995
330
144.6
0.003555
438
170.0
443
0.003682
171.0
0.00542
535
188.6
551
0.00605
191.4
0.00544
549
191.6
0.00659
572
195.6
0,00764
611
201.7
0.00769
612
202.15
0.01001
633
205.4
0.00995
638
206.1a

Concentration of Propane in Water-Rich Liquid Phase

Water-Rich
Liquid Phase
82.2
42.3b
101
53.9
142
78.1
143
79.1
191
100.2
191
100.6
284
132.9
300
137.7
366
154.2
391
160.3
446
172.2
482
179.7
538
189.6
543
191.1
608
201.7
632
205.4
a Critical region.
6 Quadruple point by extrapolation.

60

80

100

120

TEMPERATURE,

2;

Concentration of Water in Propane-Rich

Phases in Three-phase Region

Temp.,
O F.

'

80

Figure 5.

'E

I80

200

Concentration of Propane in Water-Rich

Phase in Three-phase Region

square inch gage, *0.667% of the readings taken with the 0 t o

1000 pounds per square inch gage, and &0.5y0 of the readings
taken with the 0 to 3000 pounds per square inch gage. During
equilibrating and sampling, the pressures were maintained with
variations from the equilibrium pressures not exceeding the abovementioned uncertainties of the gage readings.

TABLE
11. EXPERIMENTAL
DATAI N TWO-PHASE
REGION
(Concentration of water in propane-rich phases)
Propane-Rich
CompositionPhase
of
Temp.,
Pressure
O F.
Lb./Sq.Inoh' Abs.
Mole Fraction Wate;
102
100
0.00954
141
100
0.00492
0.00696
533
100
818
100
0.000587
1015
100
0.000540
0.000673
2018
100
2023
100
0.000591
0 000643
2798
100
2798
100
0.000623
I

150
150
150
150
150
150
150

146
217
289
856
1564
2484
2803

0.02649
0.01702
0.01200
0.002328
0.002224
0.002060
0.002046

190
190
190
190
190
190

190
309
465
1342
2003
2803

0.04967
0.02910
0.01722
0.00502
0.00475
0.00463

205.7
205.7
205.7
205.7
205.7
205.7
205.7
205.7
205.7

207
445
603
637
696
755
1217
2023
2803

0.0637
0.02639
0.01568
0.00998
0.00813
0.00779
0.00726
0.00674
0.00640

230
230
230
230
230
230
230
230

252
446
630
718
823
1530
2023
2704

0.08094
0.04325
0.02659
0.02028
0.01366
0.0133
0.00959
0.00919

260
260
260
260
260
260
260
260

439
675
812
1411
2023
2023
2755

0.07856
0.04660
0.03599
0.02499
0.01843
0.01646
0.01490
0.01649

300
300
300
300
300
300

622
928
1217
1441
2023
2803

996
~ .

0.10146
0.06360
0.04496
0.03875
0.03105
0.02684

'

INDUSTRIAL AND ENGINEERING CHEMISTRY

February 1953

443

2.303 R T

Figure 6.

Concentration of Water in Propane-Rich Phases in Two-Phase Region

PRESSURE, PSlA

Figure 7.

Concentration of Propane in Water-Rich Liquid Phase in Two-Phase Region

MATERIALS USED

EXPERIMENTAL RESULTS

The propane used in this investigation was supplied through

the courtesy of the Phillips Petroleum Go., Bartlesville, Okla.
The propane was reported to contain not less than 99 mole % propane. The principal impurities were approximately 0.2% of
other hydrocarbons, mainly ethane and isobutane. Before the
propane was charged into the cell, it was passed through a high
pressure filter charged with activated carbon, Ascarite, and sodium hydroxide.
The distilled water, obtained from the departmental source,
was tested for chlorides, boiled several minutes prior to use, and
injected into the cell while still above 160' F.

The experimental vapor-liquid equilibria data for the propanewater system are presented in the three-phase region from 54' F.
to the three-phase critical of 205.7' F. and 637 pounds per square
inch absolut,e in Table I and Figures 4 and 5. The experimental
data in the two-phase region from 100 to 2800 pounds per square
inch are presented at isotherms of loo", 150, 190', 205.7',
230, 260, and 300' F. for the propane-rich phases in Table I1
and Figure 6, and at isotherms of 54", loo', 133", 190', 205.7",
230', 260, and 300' F. for the water-rich phase in Table I11
and Figures 7 and 8. The graphically smoothed data in the
three-phase region for all three phases are presented in Table IV.

INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y

444

TABLE
111.

EXPERIMEXTAL

Vol. 45, No. 2

DATAI N TWO-PHASE
REGION

(Concentration of propane in water-rich liquid phase)

Pressure,
I,h./Sq. Inch A h .

Composition of WaterRich Liquid Phase,

Alole Fraction Propane

54.0
54.0
54.0
54.0

617
617
1222
1988

0.0002963
0.0003029
0.0002906
0.0002948

100
100
100
100
100
100
100
133.0
133.0
133.0
133.0

72
117
428
622
1531
2012
2687

0.0000863
0.0001552
0.0002046
0.0002178
0.0602151
0.0002239
0.0002304

188
1199
1810
2787

0.0001499
0.0002249
0.0002267
0.0002364

181
307

O.OOO1146
0.0001763

190
190
190
190

131
224
359
990
1523
2012
2787

205.7
205.7
205.7
205.7
205.7
205.7

230
400
478
910
1810
2787

230
230
230
230
230
230

222
504
810
1128
1810
2787

2 60
260
260
260
260
260

170
332
511
751
1232
1810
2787

0 . WOO796
0.0001330
0.0001960
0,0002580
0.0002703
0.0002745
O.M)02880
0.0001261
0,0002162
0.0002449
0.0002842
0.0003008
0.0003134
0,0001301
0.0002633
0.0003243
0.0003414
0,0003542
0.0003765
0.0001001
0.0001964
0.0002892
0.0003665
0 0004197
0.0004393
0.0004766

300
300
300
300
300
300
300

265
471
694
987
1565
1810
2787

0.0001666
0.0003031
0.0004130
0.0004876
0.0005801
0.0006078
0 0006861

Temp.,

170
170
100
190

190

260

PRESSURE, PSlA

Figure 8. Concentration of Propane in Water-Rich

Liquid Phase in Tw-o-Phase Region at Low Pressures

Tal~lesV and VI list the graphically smoothed equilibrium

concentrat,ion of water in the propane-rich phases and the propane
respect,ively.
~~D~~~~~
~~
~ ~R~~~~~~
~ FOX~Lk121,
~ in the
~~ A-ater-rich
~ ~ phase ~in the
- two-phase
~
pregion,
)
~
T
~11. ~s
~
, Ix ~
THREE
PHASES
Figures 9 and 10 present the smoothed data of Tables T and
VI along isobars, with Figure 10 showing the niinimum isohaik
Composition, Xole Fraction
Pressure.
Water in
Propane in
solubility for all pressures above 300 pounds per square inch.
Temp.,
I,b./Sq.
Water in
propane-rich
water-rich
F.
Inch. Ahs.
vapor phase
liquid phase
liquid phase
THESO1,UBILITY O F \%-ATER I S H Y I ) R O C b R B O N - r t I C H II-I.4SES.
42.3
82.2
0,00140
0 . 000105
0 000366
I n the three-phase region, the so1ubilit~-of water in the propane60.0
108.5
0.00218
0.000187
0.000264
rich liquid phase and in the vapor phase describes a continuous
80.0
146.0
0.00335
0.000344
0.000219
100.0
191.5
0.00466
0.00061;
0.000203
envelope (Figure 4), which closes a t t.he three-phase critical con120
246
0.00625
0.00109
0.000199
ditions. A t the three-phase critical conditions the intensive
140
311
0.00813
0.00184
0.000202
160
389
0.01002
0,00291
0.000212
properties of these two phases become continuously identical.
170
432
0.01097
0.00358
0 000223
180
483
0.01191
0.00446
0.000236
The critical composition occurs a t the highest. temperature
538
0.01280
0.00558
0.000250
190
a t which t,he three phases coesist. At the critical composition,
195
468
0.01278
0.00632
0.000256
200
602
0.01237
0.00723
0.000264
t.he rates of cha.nge of the concentration of the vapor phase
205.7
637
0,00998
0.00998
0.000272
and t.he lighter liquid phase
I 3-phase critical.
with respect to temperature are
minus and plus infinity, reTABLE
I-. GRIPHICSLLY
SMOOTHED
DATA
IK TM-O-PHASE
REGION
spectively.
Pressure,
Temperature, F.
Figure 6 indicates that the
Lb./Sq.
100
130
160
190
205.7
220
250
280
310
Mole Fraction Water in Propane-Rich Phases
solubility of water in the proInch Abs.
0.1330
0 4920
0.7727
0,02360
0 0505
0.0962
0.2999
pane-rich phases is related to
0.00979
0.04678
0.1489
0 02382
0.0647
0 2449
0.3837
0.000605 0.01104
the volumetric behavior of the
0.2547
0 01500
0 1618
0.03034
0.0984
0.04246 0.0562
0.000605 0,00139
0,1892
0 1205
0.03034 0.04083 0.0726
0.000604 0.001380 0 002911 0.02123
same phases. As the concen0.1489
0.02218 0.03041 0 , 0 5 5 2
0 0931
0.000604 0.001374 0 002877 0.01503
0.1222
trations of water in these
0.000604 0.001365 0 002838 0.005507 0.01563 0.02264 0.04935 0 0764
0.1146
0.00998 0.01941 0.04065 0 0711
0.000603 0.001361 0 002829 0.00547
phases are low, the volu0.1030
0.00815 0.01486 0.03622 0 0637
0.000603 0.001358 0 002819 0.00542
0.0887
0.00782 0.01124 0,02898 0 0540
0.000602 0,001355 0 002799 0 00635
metric behavior of these phases
0 00767 0.01001 0.02323 0 04581 0.0778
0.000601 0.001352 0 002773 0.00527
0.00752 0.00964 0.01897 0 03917 0,0687
0,000600 0,001349 0 002760 0,00521
mag be expected to be similar
0.0518
0
01563
0
02992
0.001340
0,00.509
0,00705
0 002729
0.00933
0.000698
to that of pure propane ( 1 2 ) .
0.000597 0,001327 0 002698 0.004978 0.00703 0,00895 0.01455 0 02642 0.04405
0.000596 0.001321 0 002655 0.004809 0.00665 0.00845 0,01370 0 02280 0 3642
From thermodynamic consid0.000594 0.001315 0 002600 0,004571 0 00619 0.00787 0.01265 0 02009 0.03112
(%rations,both the volumetric
O

INDUSTRIAL AND ENGINEERING CHEMISTRY

February 1953

TEMPERATURE, DEG.

Figure 9.

445

Concentration of Water i n Propane-Rich Phases in Two-Phase Region

0
Figure 10.

Concentration of Propane in Water-Rich Liquid Phase in Two-Phase Region Along

Isobars

behavior of the propane-rich phases along isotherms below

205.7 F. and the concentration isotherms of the solubility of
water in the same phases below 205.7 F. are discontinuous.
Raoults law (18) predicts that an isotherm of a log concentration us. log pressure plot is a straight line of slope minus 1
passing through the point representing the vapor pressure of
pure water a t that temperature. The dotted lines of this slope
of Figure 6 indicate portions of these ideal isotherms which
have been used wherever appropriate to aid in drawing the best

curve through the experimental points and in extrapolating the

data. The data indicate both positive and negative deviations
from Raoults law.
SOLUBILITY
OF PROPANE
IN WATER. Figures 7 and 8 represent the original data on the solubility of propane in water along
isotherms from 54 t o 300 F. The concentration of propane in
the water-rich phase in the three-phase region is shown as a
concaved curve with a minimum a t about 250 pounds per square
inch, which terminates at 205.7 F. and 637 pounds per square

TABLE
VI. GRAPHICALLY
SMOOTHED
DATAI N
Pressure,
Lb./Sq.
Inch. Abs.
100
200
300
400
500
600
637
700
800
900
1000
1500
2000
2500
3000

Vol. 45, No. 2

INDUSTRIAL AND ENGINEERING CHEMISTRY

446

60

100

130

0.0002873
O.OOO2670
0.0002679
0.0002687
0.0002696
0.0002703
0.0002706
0.0002711
0.0002717
0,0002722
0.0002728
0,0002748
0.0002760
0.0002768
0.0002775

0.0001273
0.0002045
0.0002060
0.0002076
0.0002091
0.0002106
0.0002112
0.0002122
0.0002137
0.0002152
0.0002166
0.0002221
0.0002264
0.0002287
0.0002302

0.0000876
0.0001603
0.0002003
0.0002043
0.0002075
0.0002090
0.0002108
0.0002124
0.0002145
0.0002164
0.0002182
0.0002228
0.0002276
0.0002307
0.0002355

TWO-PHASE

Temperature, O F.
160
190
205.7
Mole Fraction Propane in Water-Rich
0.0000609
0.0000698
0.0000582
0.0001303
0.0001172
0.0001197
0.0001700
0.0001782
0.0001696
0.0002132
0.0002138
0.0002107
0.0002400
0.0002210
0.0002468
0.0002530
0.0002680
0.0002261
0.0002550
0.0002271
0.0002723
0.0002295
0.0002578
0.0002767
0.0002319
0.0002602
0.0002815
0.0002623
0.0002341
0.0002846
0.0002358
0.0002642
0,0002865
0.0002415
0.0002715
0.0002957
0.0002462
0.0002783
0,0003043
0.0002507
0.0002835
0.0003116
0.0002542
0.0002877
0.0003160

inch absolute. T o preserve the clarity of Figure 7, some of the

isotherms for the temperatures greater than 170 E. have been
omitted a t low pressures but are shown in Figure 8.
As in the case of the solubility of water in the propane-rich
phases, the solubility of propane in the water-rich phase is seen
to be directly related to the volumetric behavior of the propane-

REQIOY

220
Phase
0.0000562
0.0001180
0.0001708
0.0002173
0.0002550
0.0002798
0.0002878
0.0002952
0.0003053
0.0003115
0.0003155
0.0003257
0.0003357
0.0003445
0.0003526

250

280

310

0.000513
0.0001170
0.0001768
0.0002307
0.0002767
0.0003107
0.0003222
0.0003375
0.0003562
0,0003695
0.0003787
0.0003995
0.0004144
0.0004293
0,0004442

0.0000415
0.0001160
0.0001857
0.0002480
0.0003000
0.0003453
0.0003602
0.0003828
0.0004087
0.0004287
0.0004444
0.0004927
0.0005246
0.0005502
0.0005753

0.0000220
0.0001147
0.0001923
0.0002677
0.0003277
0.0003803
0.0004007
0.0004290
0.0004627
0.0005133
0.0004886
0.0006160
0.0006858
0.0007332
0.0007703

rich phases or t o pure propane. Thus, if the compressibility o f

the propane-rich phase is high, as in the behavior of a gas, the
effect of pressure on the solubility of propane is high. On the
other hand, a low compressibility of the propane-rich pha5e,e.g., that of a liquid,-is marked by a small effect of pressure on
the solubility.

(Vapor-Liquid Equilibria f o r
Binary Hyd rocarbon-Water Systems)
CORRELATION OF DATA

ROCEDURES for correlating data are useful when they permit the prediction of the behavior of systems for which data
are not available or when they may be used to extrapolate experimental data. The water contents of hydrocarbon-rich
phases are correlated, whether the phase be gaseous, liquid,
or in the fluid region.
The hydrocarbon-rich portion of the hydrocarbon-water system
may consist of a liquid phase and a gas phase, or of a single phase.
The proposed correlation uses temperature and the molal volume
of the hydrocarbons in the phase as variables and in this manner
avoids reference to the number of phases in the system and to
pressure.
Several correlations have been made of the saturated water
content a t high pressures of gases such as nitrogen, hydrogen,
methane, ethane, and complex hydrocarbon mixtures ( I , 20,
22, 24). These methods, however, do not treat the vapor phase
and the hydrocarbon-rich liquid phase as continuous phases.
The simplest relation expressing the saturated water content
in the vapor phase, which is generally valid a t low pressures for the
nonpolar gases, is that
Y = P/P
(1)
where y = mole fraction of water in the vapor a t the temperature of the system
p o = vapor pressure of water at the temperature of the
system
P = total pressure of the system
Equation 1 results from the use of Daltons law of partial
pressure and Raoults law, and the liquid phase is substantially
pure water. Under conditions of temperature and pressure
where the vapors no longer behave ideally, Equation 1 leads to
serious error. Saddington and Krase ( 2 7 ) have found that a t
high pressures the saturated water content of nitrogen greatly
exceeds the value predicted from the application of Poyntings
relationship (18),and this has been found to be true for aqueous
hydrocarbon systems ( 2 2 ) . That the relationship cannot explain the increased volatility of water with increased pressure

a t a given temperature indicates that the nonpolar gases actually

have a solvent effect upon the water inolecules a t high pressures.
It is evident that the same attractive and intramolecular forces
come into play a t high pressures in the solubility of a liquid in a
gas as in the solubility of a gas in a liquid. These forces are the
same as those which create critical phenomena,
The experimental data of the propane-water system suggr.t a
correlation based upon the volumetric behavior of the hytli ocarbon-rich phases and temperature as parameters. Figuro 1 1
presents an empirical correlation in which the concentration of
vater in the hydrocarbon is plotted as a function of the anhydrous molal volume of the hydrocarbon for several isotherms along
lines of constant molecular weight. The correlation has been
primarily developed from binary hydrocarbon-water systems,
although available data on complex mixtures have been used.
The molal volume is expressed here in milliliters of anhydrous
hydrocarbon per gram mole of anhydrous hydrocarbon. I t is
permissible to use the anhydrous molal volume rather than the
actual molal volume as a correlating variable because of the low
concentrations of water present in the hydrocarbon-rich phase,
except a t low pressures where the solubility relationships follow
Equation 1. The effect of molecular weight on the isotherms is
almost nonexistent a t high molal volumes (low pressures), but
becomes appreciable as the molal volumes approach those of
light hydrocarbon liquids.
On Figure 11, the saturated concentrations of water in methane
( 2 2 ) and in ethane ( 2 4 ) were obtained from the xork of Olds,
Sage, and Lacey. The solubility of water in propane was obtained from experimental data of the authors and the threephase data of n-butane-water system from Reamer, Olds, Sage,
and Lacey (25). The methane-n-butane-water data were
obtained from the work of McKetta and Kat2 ( 1 9 ) . The threephase points of the last-mentioned work have been distinguished
from the two-phase points on Figure 11. The data on the water
content of a natural gas measured by Dodson and Standing
(10)have been utilized. Additional experimental points on the