A High Pressure Solubility Apparatus for Gases of High Solubility

W. HAYDUK, H. ASATANIS and Y. MIYANO”

Department of Chemical Engineering, University of Ottawa, Ottawa, Ontario K I N 6N5
An apparatus is described for measuring gas solubilities at high pressure for gases of moderate to high solubility.
Solvent, supplied by a metering pump, is continuously saturated with gas as it flows down a spiral rod. Gas is conti-
nuously supplied by means of a calibrated piston pump to provide a constant pressure. The solubility is determined
from the relation between the solvent rate and the gas consumption required to achieve saturation. The solubilities of
two chemically reactive gases, propene and isobutene, are reported for the solvents n-butanol, chlorobenzene and
n-octane for three temperatures, 298, 323 and 343 K, and a range of pressures from 0.2 to 1.9 MPa.

On decrit un appareillage de mesure des solubilites des gaz B haute pression pour des gaz ayant une solubilite moyenne
ou ClevCe. Le solvant, fourni par une pompe B debit CtalonnC, est sature en continu avec le gaz, alors qu’il s’kcoule
d’un serpentin. Le gaz est fourni en continu par une pompe pistons calibrks pour obtenir une pression constante.
La solubilitC est dCterminCe B partir de la relation entre le taux de solvant et la consommation de gaz requis pour rkaliser
la saturation. Les solubilitks de deux gaz rCactifs chimiques, le propbne et I’isobutkne, dans les solvants n-butanol,
chlorobenzkne et n-octane, sont donnees pour trois temperatures, 298, 323 et 343 K , et une gamme de pressions de
0,2 a 1,9 MPa.

Keywords: high pressure gas solubility apparatus; propene, isobutene; n-butanol, chlorobenzene, n-octane.

T he term “gas solubility” is usually applied to the

equilibrium between substances which are in the liquid
and gas states at normal conditions. Usually the difference
between the normal boiling points of the solvent and the gas
is very large. In that case, the gas solubilities are usually
low, or less than 0.01 mole fraction. On the other hand, when
the gas normal boiling point is relatively high, its solubility
also is relatively high. Gases such as the C, and C,
hydrocarbons are highly soluble, especially in non-polar
solvents. At a low temperature, 273 K for example, the
solubility of butane in hydrocarbon solvents is greater
than 0.50 mole fraction. Such high solubilities for butane
as well as other gases may also be obtained at normal
temperatures (about 300 K), but at high pressures. We are
interested in gas solubilities at high pressure because
most industrial absorption equipment is operated at high
pressure and because such equilibria are generally of scien-
tific interest.
There are a number of different types of equipment for
measuring gas solubilities at high pressure. A relatively
simple method involves equipment for slowly bubbling the
gas through the solvent and then measuring the increase in
weight of the saturated solution (Gerrard, 1976). Much more
complex devices use cells whose volume can be changed.
Mercury is introduced into the cell, or a piston moves to
change the cell volume (Mehra and Thodos, 1965; Zais and
Silberberg, 1970; Meskel-Lasavre et al., 1981). Internal
mixers or external circulation devices are also usually
required to assist in reaching equilibrium. Methods for sam-
pling and analyzing the gas and liquid phases are usually
needed. Gas chromatography is frequently used for analysis.
Another method for determining the composition of the solu-
tion involves charging the gas from a pressure container of
known volume. Sometimes the gas and solvent are charged
into the apparatus using calibrated piston pumps. It is
apparent that many variations in design of high pressure solu-
bility devices are used.
-
$Currently at Mitsubishi Kasei Corporation. Research Center, loo0
Kamo\hida-Cho, Yokohama 227, Japan
*Research collaborator from Department of Applied Chemistry, Okayama
Unireruty of Science, 1-1 Ridai-Cho, Okayama 700, Japan.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, OCTOBER, 1991
We wished to design and construct a special type of solubility
apparatus for high pressure which would be useful for rapid
solubility measurements requiring no more than two hours per
measurement. It was to be simple in construction and operation
and accurate enough ( 2 2 % ) to give useful results. For some
years we have utilized a low pressure solubility apparatus based
on that originally described by Morrison and Billet (1948;
1952). We have provided innovations for improving the
accuracy and ease of measurement. In our apparatus, a constant
flow of degassed solvent enters a spiral glass tube for contacting
the gas. A supply of gas is trapped in a glass burette over mer-
cury, which in turn, is contained in a levelling bottle. At steady-
state the volumes of gas consumed are read at suitable time
intervals. The innovations we have made consist of using a
calibrated syringe-pump to supply the degassed solvent, and
a motorized variable-speed screw device for raising the mer-
cury level as described by Asatani (1983). The design of our
high pressure solubility apparatus, is very similar to that previ-
ously described for low pressures. The apparatus, constructed
of stainless steel to withstand the higher pressure (used from
pressures of 0.1 to 3 MPa), is described later.
The principle of our solubility method is based on meas-
uring the relatively large consumption of gas during the dis-
solution process, volumetrically . The ratio of gas volume
to solvent volume at the experimental conditions, or essen-
tially the Ostwald coefficient, ranges in our work from about
10 to 150. Thus it is readily possible to determine the neces-
sary solvent and gas volumes accurately. The method for
calculation of solubility at elevated pressures involves the
volumetric rate of input of gas and solvent into the equilibra-
tion cell, the rate of accumulation of saturated solution and
the solvent partial pressure in the gas phase. First, an approx-
imate solubility expressed as the mole fraction and written
in terms of the gas and solvent molar volumes, is indicated:
xp z (vG/VG)/(vG/?‘G) + ( v L / V L ) ) . . . . . . . . . . (1)
Equivalently:
xp = I 1 + [(vLVG)/(v&)])-l . . . . . . . . . . . . . . (2)
For a more accurate determination of solubility it is neces-
sary to consider the displacement of gas by liquid solution
1193
in the equilibration cell. An additional volume of gas must 40 I i I t i r 3 1/h1
dissolve corresponding to the volume of liquid solution accu- -
0 VAPOR P R E S S U R E O F LIQUEFIED GAS
mulating in any given time interval. Also, the gas in the cell /’
must necessarily be saturated with solvent vapor. Hence, the ----IDEAL SOLUBILITY
determination of the equivalent volume of pure gas dissolved
involves the solvent partial pressure as well as the partial 1,o -
volume of liquefied gas in the liquid solution:
v& = vG + ( V L + V L G ) ( P - p l ) / P . . . . . . . . . . . . (3) c ! ? :
r
-
Initially, of course, the solubility is unknown; hence, the cal- go4
v , *
culations are repeated until the values satisfy the necessary LA
W
CT
equations. There usually is a small decrease in volume on n -
formation of the liquid solution from its liquefied gas and
solvent components. This shrinkage is considered negligibly I I 1 I < ( I _
small, however, for the purpose of calculating solubility. 01 I

0.01 00 4 0.I 0.4 1

Then a more accurate solubility may be determined by means
of the following equation:
XI, = (1 + [(vLvG)/(v;;vL)]]-’
. . . . . . . . . . . . . . (4)
Finally, the application of Henry’s law to gas solubilities
will be briefly considered. From a theoretical view point
Henry’s law is a limiting law (Battino, 1984):
hi = limit ~fF/x;)
........................
xi -0
However, there may be applications when extrapolation of
solubilities from a partial pressure of 101.3 kPa to much
higher partial pressures is expedient. The higher pressures
may be those found in certain chemical processes, for which
solubility data are required but not directly available. A
method for representing Henry’s law using logarithmic scales
relating partial pressure and mole fraction was utilized as
early as 1957 (Friend and Adler, 1957). One advantage of
this type of representation is that a wide range of solubili-
ties can be summarized by means of a single diagram. In
addition, an “ideal” solubility as originally defined by Hil-
debrand and Scott (1950) is found useful:
xi = p / P Y .................................
The effect of pressure on the solubility relation is influenced
by whether the solubility is above, equal to, or below the
ideal solubility as shown in Figure 1. It is possible, there-
fore, to anticipate the solubility at higher pressures by making
reference to the ideal solubility.
Experimental
A schematic diagram of the equipment is shown in
Figure 2. The gas solubility apparatus is suitable for pres-
sures to 20 MPa, for gases of high solubility and involves
a low, but constant, flow of degassed solvent. The degassed
solvent is provided to the equilibration cell, which initially
contains the solute gas at the experimental pressure, by means
of a high precision micro-metering pump (Milton Roy,
Riviera Beach, FL). The micro-metering pump is capable
of producin very constant flowrates, even for rates as low
B
as 0.05 cm /min. The solvent is introduced into the equili-
bration cell by means of a syringe needle and allowed to flow
along the outside surface of a 1/8-in diameter stainless steel
rod coiled in the form of a spiral spring. The syringe needle
is actually spot-welded to the spiral rod to ensure that the
solvent flows along the (bottom) surface of the rod. It was
previously observed that under certain circumstances drops
1194 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, OCTOBER, 1991
MOLE F R A C T I O N
Figure 1 - Typical representation of the relation between gas par-
tial pressure and mole fraction solubility for a highly soluble gas
using log-log scales.
14
I
--I 4
10
3
l5
-I
16
(6)
L
i 8
J
Figure 2 - High pressure solubility apparatus. 1 = Gas supply,
2 = Constant temperature fluid, 3 = Pressure transducer, 4 = Gas
volume regulator, 5 = Tape heater, 6 = Sealing device,
7 = Equilibrium cell, 8 = Liquid sampler, 9 = Check valve,
10 = Metering pump, 1 1 = Solvent burette, 12 = Degassing
flask, 13 = Liquid trap, 14 = Vacuum line, 15 = Helium supply,
16 = Extension rods.
were formed which simply fell to the bottom of the cell and
were not properly saturated with gas. Because of the high
interfacial area between the gas and solvent, the solvent is
completely saturated by the time it reaches the bottom end
of the rod. Tests were performed to ensure that this was the
case.
As the gas dissolves, the gas pressure as measured by a
calibrated pressure transducer (Heise, Model 623 supplied
by Intertechnology, Ottawa, Ontario), is observed to decrease
slightly. A piston pump, containing a supply of gas at the
experimental temperature and pressure, is then operated to
force more gas into the equilibration cell to keep the pres-
sure essentially constant at the desired value. Volume rea-
dings of residual gas in the piston pump when taken at regular
time intervals are essentially linear when plotted as a
 function of time or quantity of solvent used. From an accu- TABLE1
rate knowledge of the solvent rate and average gas dissolu- Properties of Gases and Solvents
tion rate, it is possible to calculate the gas solubility.
For gases:
A description of the operation of the solubility apparatus T(K) e*(m3/kmol . K) f* V,(m'/kmol)
follows. About 30 cm3 of solvent is deaerated by boiling
under vacuum for about 20 min. It is then transferred slowly Propene 298.15 - 1 .Ol2(lo5) -2.209 24.115
to an evacuated column filled with glass beads for a second 323.15 26.224
stage of deaeration. After deaeration, it is necessary to allow 343.15 27.903
some gas to enter the column of deaerated solvent for the Isobutene 298.15 -2.343(lOs) -2.251 23.818
purpose of providing a positive pressure for pumping the sol- 323.15 25.981
vent. Helium gas is used because of its extremely low solu- 343.15 27.691
bility in all solvents. The glass beads serve to prevent For solvents
convection in the interstitial spaces and hence to prevent con- T(K) Density* ( p , kg/m') V,(m3/kmol)
tamination of the degassed solvent with dissolved helium,
particularly for the solvent near the bottom of the column. Chlorobenzene 298.15 1100.8 0.1023
Only a small amount, about 1-5 cm3, of the solvent is 323.15 1073.3 0.1049
actually used during an experiment. Therefore, the solvent 343.15 1051.7 0.1070
is considered to remain completely deaerated for the dura- n-Octane 298.I5 698.7 0.1635
tion of an experiment. The solute gas is provided from a 323.15 678.1 0.1685
stainless steel, high pressure piston pump from Ruska 343.15 661.3 0.1727
(Houston, TX), 100 cm3 in volume. The gas pump is sup- n-Butanol 298.15 806.0 0.09196
plied with a vernier to read the position of the piston to 323.15 786.6 0.09423
0.02 cm3. The pressure is measured by means of the pres- 343.15 770.3 0.09622
sure transducer to 0.07 kPa (0.01 psi).
The dissolution process is a dynamic one. After the initial *Hayduk et al. (1988)
evacuation, the cell is pressurized with gas and the solvent
flow is started. As the pressure is observed to drop, the gas from Aldrich Chemicals (Milwaukee, WI), is also specified
pump is operated to raise the pressure to the controlled level. to have a minimum purity of 99.0%.The chlorobenzene and
The time and gas volume are read at regular time intervals. n-butanol, obtained from Canlab (Toronto, Ont.), are both
From six to ten pairs of readings are obtained over a period specified to have a minimum purity of 99.8%.Vapor pres-
of about 90 min. Particularly for isobutylene, it is necessary sure data for the gases and solvents are from the recent
to have a supply of liquefied gas. If supplied directly from literature (Reid et al., 1987).
a cylinder at room temperature, the gas saturation pressure Densities of the solvents, at atmospheric pressure for the tem-
is, under some conditions, less than the pressure of the exper- peratures used in this work, were previously reported
iment. Further, provision is made to collect a sample of the (Hayduk et al., 1988) and are also listed in Table 1 along
saturated solution in a small sample tube at the bottom of with the molar volumes. For the calculation of solubilities
the equilibration cell for GC analysis to confirm the volu- at elevated pressures, the solvents are considered incompres-
metric determination of solubility. For analysis, the saturated sible for the pressures utilized. The densities of the saturated
solution which completely fills the sample tube is evaporated liquefied gas at the experimental temperatures are estimated
again Completely, into an evacuated vessel of about 300 cm3 by means of the Spencer and Danner (1972) equation as
at 323 K , and a sample of the vapor is quantitatively intro- recommended by Reid et al. (1987):
duced into the GC analyzer by means of an injection valve.
These analyses closely confirm the volumetric determina-
tions of solubility.
For the calculation of solubility, the molar densities of the The values for 2, for propene and isobutene, are given by
gases are corrected for non-idealities by means of the second Reid et al. (1987) as 0.2785 and 0.2727, respectively. Thus
virial coefficients. Available data for the second virial coef- the densities of the solutions may be estimated assuming
ficients from Dymond and Smith (1980) for the temperature that there is no volume change on mixing of the liquid
range of interest, are fitted to an equation of the form: components:

............................... (7)
ps = 4, pi + (1 - . . . . . . . . . . . . . . . . . . . (11)

The use of the following equations permits an accurate inter-
polation of the gas molar volumes at the various tempera-
tures and pressures:
VG = 0.5D + 0.5 ( D 2 + 4BD)0.5 . . . . . . . . . . . . .
D = RTIP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Values of the constant e and f,as well as the calculated molar
volumes at the temperatures used in these experiments, cal-
culated for a pressure of 101.3 kPa, are listed in Table l .
The two gases, propene and isobutene, purchased from
Air Products (Nepean, Ont.), both are specified to have a
minimum purity of 99.0%.The n-octane solvent, purchased
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, OCTOBER, 1991
Results and discussion
The Soave-Redlich-Kwong (SRK) equation of state was
used to describe the phase equilibria at higher pressures
(8) (Soave, 1972). The gas phase compositions were not mea-
sured because the solvents were all of low volatility, even
(9) at 343.15 K. Because the gas phase compositions were not
measured, the values of the parameters in the SRK equation
of state were evaluated from the solubilities at atmospheric
pressure for each system and temperature. Therefore, it was
possible to use the parameters thus evaluated to estimate both
the corresponding vapor phase composition as well as the
pressure-composition relationship at the higher pressures.
The definitions of the terms were as originally described and
1195
 TABLE2 TABLE4
Values for SZai and Qbi of the SRK Equation of State (Soave, 1972) Solubilities (1)of Propene in n-Octane, Chlorobenzene and
for Solutes and Solvents (Asatani, 1986) n-Butanol

Qai, fib, 9
Solvent T(K) P(MPa) X Y"
Substance Temperature (K) i = 1,2 i = 1,2
n-Octane 298.15 0.2026 0.2055 0.9916
n-Octane 298.15 0.3720 0.07429 0.4053 0.3920 0.9963
323.15 0.3749 0.07476 0.6079 0.5727 0.9981
343.15 0.3770 0.07506 0.8106 0.7586 0.9991
1.013 0.9020 0.9996
Chlorobenzene 298.15 0.3828 0.07685 323.15 0.3040 0.1836 0.9885
323.15 0.3847 0.07723 0.6079 0.3557 0.9901
343.15 0.3863 0.07747 0.91 19 0.5238 0.9943
n-Butanol 298.15 0.3965 0.07665 1.317 0.7307 0.9972
323.15 0.3927 0.07670 1.601 0.8515 0.9985
343.15 0.3901 0.07666 343.15 0.6079 0.2383 0.9834
Propy lene 298.15 0.4057 0.08069 1.006 0.3742 0.9843
323.15 0.4036 0.07964 1.419 0.5466 0.9902
343.15 0.3996 0.07828 1.723 0.6348 0.9921
Isobuty lene 298.15 0.4042 0.08057 Chlorobenzene 298.15 0.2026 0.1312 0.9921
323.15 0.4033 0.07997 0.4053 0.2754 0.9962
343.15 0.403 I 0.07949 0.6079 0.4248 0.9976
0.8106 0.6445 0.9987
1.013 0.8655 0.9993
TABLE 3 323.15 0.3040 0.1083 0.9870
Values fork,, for Solvent-Solute Systems when the SRK Equation 0.9119 0.3422 0.9933
of State (Soave, 1972) is Utilized (Asatani, 1986) 1.317 0.5378 0.9959
1.621 0.7160 0.9972
Solute Solvent Temperature (K) 343.15 0.5167 0.1327 0.9723
0.9828 0.2358 0.9833
Propene n-Octane 298.15 -0.00786 1.439 0.3765 0.9893
323.15 -0.00547 1.925 0.5394 0.9923
343.15 0.00924
Chlorobenzene 298.15 -0.00402 n-Butanol 298.15 0.2026 0.0787 0.9958
323.15 -0 .OO365 0.4053 0.1707 0.9978
343.15 0.00862 0.6079 0.3007 0.9986
n-Butanol 298.15 0.02100 0.8106 0.4948 0.9990
323.15 0.04244 1.013 0.7155 0.9993
343.15 0.04502 323.15 0.4053 0.0897 0.9879
0.6079 0.1408 0.9919
Isobutene n-Octane 298.15 0.06826 0.91 19 0.2306 0.9945
323.15 -0.00081 1.317 0.3847 0.9960
343.15 -0.00032 1.621 0.5613 0.9967
Chlorobenzene 298.15 0.00747 343.15 0.5198 0.0880 0.9698
323.15 -0.004 12 1.027 0.1878 0.9848
343.15 0.00296 1.637 0.3341 0.9847
n-Butanol 298.15 0.02447
323.15 0.02944 *Calculated
343.15 0.03702
solubility at 101.3 kPa to concentrations reaching as high
as 0.90 mole fraction for pressures approaching the pure gas
as discussed in Reid et al. (1987b). Values of BOi,Qbi and vapor pressure. Solubilities from the literature for a pres-
k , , as determined to best describe the data, are listed in sure of 101.3 kPa are also shown in the diagrams (Hayduk
Tables 2 and 3. et al., 1988). Calculated values for the phase equilibria using
The solubilities as obtained in this work for propene in the SRK equation of state are also shown in Figures 3-5.
n-octane, chlorobenzene and n-butanol, for the temperatures It is apparent that the solubilities of the highly soluble gases,
298.15, 323.15 and 343.15 K and for a range of pressures propene and isobutene, overlap the region normally known
from 0.2 to 1.9 MPa are listed in Table 4. The solubilities as vapor-liquid equilibria. The major difference, perhaps,
of isobutene in the same solvents and for the same tempera- is that the difference in (normal) boiling points between solute
tures are listed in Table 5 for a pressure range from 0.15 and solvent is much larger than that found in most vapor-
to 0.88 MPa. Duplicate determinations were conducted for liquid equilibrium systems.
about 10% of the measurements and, in all cases, the results The advantages of expressing high pressure solubility data
were reproduced within 2 % . Included in Tables 4 and 5 are using logarithmic coordinates will be briefly considered in
the gas phase compositions as calculated using the SRK equa- the light of the data available. It is apparent that even for
tion of state for the corresponding liquid compositions. The these highly soluble gases, the solubilities for all the three
same solubility data are also represented in Figures 3-5, on solvents obey Henry's law at least approximately for pres-
logarithmic scales for gas partial pressure and mole fraction sures to 0.2 to 0.3 MPa for isobutene, and for pressures to
solubility. The pressures cover a sufficient range so that the 0.4 to 0.6 MPa for propene. Hence, if solubility data at
concentration of dissolved gas varies from the saturated 101.3 kPa are available, a reasonably accurate extrapolation
I196 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, OCTOBER, 1991
 TABLE5
Solubilities (x) of Isobutene in n-Octane, Chlorobenzene and
n-Butanol

Solvent T(K) P(MPa) X Y*

0.1520 x CHLOROBENZENE
n-Octane 298.15 0.5060 0.9932
0.2026 0.6815 0.9965
0.2442 0.8031 0.9980 0 HENRY’S CONSTANT
323.15 0.1520 0.2580 0.9666 -----IDEAL SOLUBILITY
0.2533 0.4398 0.9825
0.3040 0.5307 0.9875
0.3800 0.6436 0.992 1
0.4560 0.7770 0.9957
0.5652 0.9375 0.9990
343.15 0.2026 0.2208 0.9323
0.3617 0.4184 0.9702
0.5694 0.6185 0.9855
0.8531 0.8949 0.9967 0 01 004 01 04 1
MOLE FRACTION
Chlorobenzene 298.15 0.1520 0.3982 0.9925
0.2026 0.5537 0.9950 Figure 3 - Solubility of isobutene at 298 K and 343 K in n-octane,
0.2280 0.6460 0.9961 chlorobenzene and n-butanol.
323.15 0.1520 0.1835 0.9651 4.0 I 1 I I ! I I I I ,

0.2533 0.3237 0.9811

0.3546 0.5100 0.9844
0.4762 0.7662 0.9952
343.15 0.3516 0.2782 0.9659
0.5208 0.4498 0.9803
0.6586 0.6136 0.9873
0.8754 0.8679 0.9952
n-Butanol 298.15 0.2026 0.2949 0.9959
0.2533 0.4426 0.9969
323.15 0.1520 0.1010 0.9707
0.2533 0.1830 0.9820
0.3546 0.2727 0.9869
0.4053 0.3425 0.9887
343.15 0.3850 0.1849 0.9639
0.6343 0.361 1 0.9723
0.8805 0.7685 0.9896
0d1 004 0.1 04 1
*Calculated MOLE FRACTION
Figure 4 - Solubility of propene at 298 K and 343 K in n-octane,
of the data to somewhat higher pressures appears possible chlorobenzene and n-butanol; legend as in Figure 3.
using Henry’s law. Furthermore, if the temperature is below
the gas critical temperature, the vapor pressure of the gas
provides a good reference point and can be used to deter-
mine an ideal solubility. The nature of the solubility beha-
vior will then be known since the solubility must approach
a mole fraction of unity as the pressure is increased toward
the gas vapor pressure whether its actual values at lower 10
pressures are above or below the ideal solubility. Especially
for associated solvents, the ideal gas solubility is useful in B
z
estimating the effect on solubility of solvent association,
which is usually to reduce the solubility below the ideal value. $04
v,
It is also considered significant that all the solubility data Ln
w
appear consistent in that at all three temperatures the a
a
solubilitiesare consistently equal to or slightly above the ideal
solubilities in n-octane, somewhat below the ideal solubil-
ities in chlorobenzene and significantly below the ideal solu- 01
bilities in n-butanol. The reduction below the ideal solubilities 0 01 0 04 01 04 1
in polar, associating solvents, expressed as solvent associa- MOLE F R A C T I O N
tion Factors, have been found useful in correlating gas solu- Figure 5 - Solubility of propene and isobutene at 323 K in n-
bilities in chemically similar associating solvents. See, for octane, chlorobenzene and n-butanol; legend as in Figure 3.
example, Hayduk and Pahlavenzdeh (1987).
The method of calculation for solubilities involves the
assumption that there is no volume change on mixing of the gas volume in the equilibration cell during a solubility expe-
liquid components of the saturated solution. It is necessary riment. Because the volume of solvent used is relatively small
to correct the volume of gas dissolved for the reduction in compared to the gas volume used, the correction to the gas
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, OCTOBER, 1991 1197
volume is likewise small. Even when the saturated solution Nomenclature
is mostly liquefied gas, the total solution volume is still much
less than the volume of gas utilized. Thus, even an approxi- second virial coefficient, m3/kmol
mate estimate of the liquid volume, and hence reduction in RTIP, m3/kmol
gas volume in the equilibration cell, does not significantly constant in Equation (7), m’/kmol . K
reduce the accuracy of the solubility measurements. We have constant in Equation (7), dimensionless
Henry’s constant, Pa/mol fraction
had an opportunity to measure the actual densities of the gas- binary interaction coefficient in SRK equation
saturated solutions for the same range of pressures and partial pressure, Pa
temperatures used in this work. These density measurements gas partial pressure, Pa
were performed by means of a high pressure digital densi- pressure, Pa
tometer. Because of the detail involved, the results of this critical pressure, Pa
latter investigation will be reported elsewhere. It is signifi- vapor pressure of liquefied gas, Pa
cant, however, that the gas solubilities calculated by utili- vapor pressure of solvent, Pa
zing the true solution densities differed by a maximum of gas constant, 8314 J/kmol K
0.3%,but usually by less than 0.1% from that calculated absolute temperature, K
critical temperature, K
using the assumption of no volume change on mixing of the reduced temperature = T/T,
liquid components of the saturated solution. Nor was there volume of pure gas dissolved at experimental condi-
a systematic deviation. Further, it is noted that there are cor- tions, m 3
relations for partial molar volumes at infinite dilution of dis- corrected volume of pure gas dissolved, m3
solved gases. See, for example, Handa et al. (1982a, b). gas molar volume at 101.3 kPa, m3/kmol
Unfortunately these corrections do not apply to the concen- volume of solvent at experimental conditions, m’
trated solutions or at elevated pressures as found in this work. equivalent volume of liquefied gas corresponding to
It is useful to review the advantages and disadvantages of vL,, m’
the new high pressure solubility apparatus. The main advan- solvent molar volume, m3/kmol
tage is the simplicity of the apparatus, and relatively small mole fraction solubility at gas partial pressure of
101.3 kPa
size. It has no internal moving parts, nor uses mercury. It p /Py, ideal solubility, mole fraction
yields accurate results quickly (within two hours). The solu- = mole fraction solubility at prevailing partial pressure
bility is based on a number of readings of gas volume and = constant in Equation (10)
time rather than on a single value, improving the accuracy
of a results. No analysis normally is required, although an Greek letters
analysis of the gas phase would be required for a highly vola-
tile solvent. Although a micro-metering pump is utilized for 4, = volume fraction of liquefied gas in gas-saturated
the solvent, such a pump is readily available. liquid solution
The main disadvantage of the new apparatus is that it is P = liquid density, kg/m3
not useful for gases of low solubility, that is, for gases whose PI = density of liquefied gas, kg/m3
Ostwald coefficients are equal to, or less than, one. The P2 = density of solvent, kg/m3
P S = density of gas-saturated liquid solution, kg/m3
volume of gas consumed must be greater than the volume fl,,,fl,, = coefficients in SRK equation (Reid et al., 1987b)
of solvent used. It is also a disadvantage that the increasing
volume of solution in the equilibration cell must be deter- Subscripts
mined for accurate solubility measurements. It is a disad-
vantage that the gas pressure must be accurately measured 1 = solute component
and controlled so that the true gas volumetric consumption 2 = solvent component
rate can be determined. Accurate pressure transducers, 1 = 1, 2
selected for the appropriate pressure range, are available,
however. The manual adjustment of the gas volume during References
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Manuscript received March 20, 1990; revised manuscript received
June 29, 1990; accepted for publication August 13, 1990.
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