Phase Equilibria of Oil, Gas and Water/Brine Mixtures

from a Cubic Equation of State and Henrys Law

YAU-KUN LI and LONG X . NGHIEM
Computer Modelling Group, 3512-33 Street N . W. , Calgary, Alberta T2L 2A6
This paper presents the predictions and calculations of the phase equilibria of oil, gas and water/brine mixtures where
the oil and gas are modeled by a cubic equation of state and where the gas solubility in the aqueous phase is estimated
from Henrys law. Henrys law constants for a variety of compounds of interest to the petroleum industry are correlated
against pressure and temperature. The scaled-particle theory is used to take into account the presence of salt in the
aqueous phase. An extensive match of experimental data is presented, showing the adequacy of the proposed model for
Henrys law constant.
On donne dans ce travail les pridictions et les calculs dkquilibre de phase des mClanges pktrole, gaz et eau-saumure,
00 le pktrole et les gaz sont reprksentis par une Cquation ditat cubique et ou la solubilite des gaz dans la phase aqueuse
est estimie a Iaide de la loi dHenry. Les constantes de Henry sont corrClCes pour une large gamme de composis
dintiret pour Iindustrie pktroliere, en fonction de la pression et de la tempkrature. On utilise la thiorie des particules
ajusties pour tenir compte de la prisence de sel dans la phase aqueuse. On prksente une vaste comparaison de donnies
expkrimentales qui montre la validiti du modkle propost5 pour les constantes de la loi dHenry.
ater exists abundantly in hydrocarbon reservoirs, either
W as a fluid originally in place or as an injected fluid
from an enhanced oil recovery process. The exclusion of
water from phase equilibrium predictions may lead to results
which are inconsistent with field observations since large
amount of light hydrocarbons and carbon dioxide can be
dissolved in the aqueous phase. In addition, the presence of
salt in the aqueous phase must also be taken into account
because of its strong effect on the gas solubility.
Cubic equations of state (EOS) have been used ex-
tensively to model the oil and gas phases in phase equi-
librium computations. Several attempts have been made to
model the aqueous phase with the same EOS (Heidemann,
1974; Peng and Robinson, 1976b; Evelein et al., 1976).
However, these authors found that accurate predictions of
the aqueous-phase compositions are difficult to achieve. To
overcome these difficulties, special modifications to the
EOS parameters are required for the aqueous phase (Erbar
et al., 1980; Peng and Robinson, 1980). Furthermore, the
inclusion of the salt effect in an EOS is not obvious.
Another approach, which was used by Luks et al. (1976),
Heidemann and Prausnitz (1977), Mehra et al. (1982) and
Nghiem and Heidemann (1982), consists of using Henrys
law to model the gas solubility in the aqueous phase, and an
EOS for the other phase(s). Luks et al. (1976) performed
calculations for nitrogen-oxygen- water and air-water
mixtures. Heidemann and Prausnitz ( 1977) calculated the
compositions of combustion gases consisting of nitrogen,
carbon dioxide and water. Mehra et al. 11982) estimated the
gas solubility in the aqueous phase from Cysewski and
Prausnitzs (1976) correlation. Since there did not appear to
be any safely generalized correlations for Henrys law
constants at this time (OConnell, 1980), Nghiem and
Heidemann (1982) carried out flash calculations for mix-
tures of crude oil and water with Henrys law constants
determined from experimental data. However, only carbon
dioxide was assumed soluble in the aqueous phase, and the
presence of water in the hydrocarbon-rich phases was ne-
glected. All the above references did not consider the effect
of salt on the gas solubility.
In this paper, correlations for Henrys law constants with
respect to pressure and temperature for a variety of com-
pounds of interest to the petroleum industry are developed
using published experimental data. The effect of salt on the
gas solubility in the aqueous phase is handled by using
the scaled-particle theory (SPT) to modify Henrys law
constants derived for pure water.
A robust algorithm for three-phase flash calculations
involving an aqueous phase is also discussed.
Phase equilibria
EQUILIBRIUM EQUATIONS
For a liquid-gas- water system with n, components, the
(1)
necessary conditions for phase equilibrium are:
lnfI v - I nf,[ =0
lnfiw - I nfi e =0
i =I , . . ,n, . . . . . . . . . . . . .
and
i =1,. . ,n, . . . . . . . . . . . . . ( 2 )
wheref,, (m =e , v, w ) is the fugacity of component i in
phase m. The subscripts e , v and w denote respectively the
liquid, vapor and aqueous phase. In this paper, the term
liquid phase refers to the dense phase which is not rich in
water. The latter is referred to as the aqueous phase.
In phase equilibrium computations, it is convenient to
define two sets of K-values (equilibrium ratios) as follows:
(3) K,, =y,,/y,,
i =I , . . ,n, . . . . . . . . . . . . . . . . .
and
(4)
i =I , . . ,n, . . . . . . . . . . . . . . . . .
where y,, denotes the mole fraction of component i in
phase m.
K,,, =y I w/ y , e
486 THE CANADI AN J OURNAL OF CHEMI CAL ENGI NEERI NG, VOLUME 64, J UNE 1986
The material balance on component i requires that
Z , =F, y, , +F, y, , +F,V,,,
i =I , . . . , n, . . . . ( 5 )
where z , is the feed composition (global mole fraction), and
where F,,, is the mole fraction of phase m.
The mole fraction y,,,, are related to z, and F,,, through the
following relationship
~, , 11 =~ , , , , z , / ~ Kl yFq
i =I , . . . . n, . . . . . . . . . (6)
Y m =e , V , M J
4 =e , V, M'
where,
. . . . . . . . . . . . . .
K, , I i = I 11, (7)
The thermodynamic equilibrium equations (Equations I
In K, , +In - In =0 i =I , . . . , n , ... (8)
InK, , , +l n+,,, - I n+,, =0 i =1 . . . . . n, . . (9)
where +,,,, denotes the fugacity coefficient of component i in
phase m.
and 2) can also be rewritten as follows:
By definition, the mole fractions satisfy
11,
C - I =o m =e , v , w . . . . . . . . . . . . . . (10)
C F,,, - I =o m =e , V , ~ . . . . . . . . . . . . . ( 1 1 )
By using Equations (6) and (lo), the following equations
1'1
m
can bederived:
" I ( K, " - 112,
n,.
' ( ' I v - '") =I = ' I F1 +F, K, , +F,,,K,,.
=0. . . (12)
i = I
A three-phase flash calculation corresponds to solving the
2n,. +3 nonlinear equations (Equations 8, 9, 1 I - 13) for the
2n,. +3 primary unknowns K, , , K,,, F1 , F, and F,. The
mole fractions y,," can betreated as dependent variables from
Equation (6). For the components j which are assumed not
soluble in the aqueous phase, take K,,, =0 and remove the
corresponding Equation (9) from the equation set. The
system of equations can be solved by either Newton's
method or the quasi-Newton successive substitution method
discussed in Nghiem and Li (1984) and Mehra et al. (1984).
Since the aqueous phase is not modeled by an EOS, some
modifications to the calculation procedure of Nghiem and Li
(1984) are required. These are described in Appendix A.
Note that the procedure does not require good initial guesses
of the primary variables, nor a prior knowledge of the
number of phases in equilibrium.
THERMODYNAMIC MODELS
As discussed earlier, the liquid and vapor phases are
modeled by a cubic EOS, and the solubility in the aqueous
phase is handled by Henry's law.
Henry's law for a component sparingly soluble in the
aqueous phase gives
i f w ....................... (14)
where the bold subscript w denotes the water component,
and the regular subscript w denotes the aqueous phase. Hi is
f i w =yI I YHi
the Henry's law constant of component i in the aqueous
phase. The variation of Henry's law constant with respect to
pressure and temperature follows the differential equation
(Smith and Van Ness, 1975)
V,? h , , - hP
+- RT?
dT . . . . . . . . . . .
d(ln Hi) =-dp RT
where vIm is the partial molar volume of component i in the
aqueous phase at infinite dilution, h,, is the enthalpy of
component i in the gas phase, and hp is the enthalpy of
component i in the aqueous phase at infinite dilution. The
term h, , - hp depends strongly on temperature, and no
general correlation describing its change with respect to
temperature is available. It has also been found that vlx is
usually not very sensitive to pressure. Therefore, for a given
temperature T , integration of Equation (15) from p" to p
gives
........... (16)
where HP is the Henry's law constant at the reference
pressure pp. Equation (16) can also be written as
. . . . . . . . . . . . . . . . . . (17)
In HI =In HY +vP(p - pY) / ( RT)
In H, =In H,*+v, "p/(RT)
In H,* =In HP - vl Spy/ (RT) . . . . . . . . . . . . . . . . . (18)
where
In this study, Equation (17) is used to correlate Henry's
law constants from solubility data. H,* is referred to as the
reference Henry's law constant. The molar volume at
infinite dilution v;" is computed from the correlation of
Lyckman et al. (1965) reported by Heidemann and Prausnitz
(1977) in the form:
(2) Pr i Vi =0.095 +2.35($) TP ..............
RTci
where C is the cohesive energy density of water given by:
C =(h, - h i +p",: - RT) / v: . . . . . . . . . . . . . (20)
p i is the saturated vapor pressure of water at the tem-
perature T, v: is the molar volume of water at p: and T, and
h i - hz is the enthalpy departure of liquid water at p i
and T.
The fugacity of the component water in the aqueous phase
can readily be obtained from the fugacities of the solutes
using the Gibbs-Duhem equation as in Prausnitz (1969):
0
p v,
f Ww =yWw+i pi exp [IpL ~ d p ] ...............
where +: is the fugacity coefficient of pure water at p i , and
vi is the molar volume of pure water.
In this paper, the vapor pressure of water p i and ( h: -
h i ) are calculated respectively from the Frost- Kalkwarf-
Thodos and the Yen- Alexander equation reported in Reid
et a]. (1977). The molar volume vi is estimated from a
correlation due to Chou reported in Rowe and Chou (1970).
Alternatively, these values can also be obtained from steam
tables. The fugacity coefficient is obtained from the
following correlation which was found to match reasonably
well the data of Canjar and Manning (1967):
+i =0.9958 +9.68330 X 10-5T' - 6.1750
X IO-'T'* - 3.08333 X 10-'"Tf3;
T' >90F ........................ (22a)
(22b) =I ; T' 5 90F ........................
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64, JUNE 1986 487
106
Z
z
8
103
W
a
1 I I I I
0 50 100 150 200 250
102 I
TEMPERATURE, C
Figure 1 - Variation of the reference Henrys Law constant, HF,
with temperature.
7 =1.8T - 459.67
(22c)
where T is the temperature in K, and 7 the temperature
in OF.
. .. . . .. . . . . . , .. . . .. .. .
Henrys law constants for gas solubility in water
HENRYS LAW CONSTANTS FROM SOLUBILITY DATA
Henrys law constants are obtained by matching the pre-
dicted results to experimental binary solubility data. The gas
phase is modeled with the Peng-Robinson EOS (Peng and
Robinson, 1976a). The compositions of the aqueous and gas
phases were matched by regressing on the EOS interaction
coefficient di j between water and the solute, and the refer-
ence Henrys law constant H:given in Equation (17). Since
the Henrys law constants will beused to predict gas solu-
bilities at reservoir conditions, more emphasis was given to
matching the experimental data at pressures higher than
6.9 MPa whenever these are available. Hence the values of
H: obtained do not correspond to Henrys law constants at
zero pressure (i.e., p o =0 in Equations 16 and 18) discussed
in the literature.
Figure 1 shows the variation of H? with respect to tem-
perature for a number of compounds. The dashed curves in
Figure 1 represent extrapolated values of H?. As depicted in
this figure, H: generally exhibits a maximum when plotted
versus temperature. Jonah (1983) has found that In (Hi/fs)
Y I
METHANE-WATER SYSTEM
- - I
MOLE PERCENT OF METHANE IN
VAPOR PHASE
0
Figure 2 - Vapor-phase composition of methane- water system.
varies linearly with the inverse of the absolute temperature
for the systems he investigated. Here, fs denotes the pure-
solvent fugacity. For the binary systems considered in this
paper, it has been found that In (H:/fi) deviates slightly
from the suggested linear behavior, and follows more accu-
rately a second order polynomial in l/T. The coefficients of
these polynomials as well as the Peng-Robinson EOS in-
teraction coefficients obtained by regression are given in
Table 1. The sources of the experimental data used in the
regression are also reported. The fugacityf; is obtained by
multiplying given in Equation (22) by the water satur-
ation pressure pa. Because of space limitation, the match is
presented only for a few binary systems in the following.
Figures 2 and 3 depict the vapor and aqueous phase
compositions of the methane- water binary system. Figures
4 to 6 compare the experimental and calculated composition
of the propane which exhibits a three-phase separation.
Figures 7 and 8 show the experimental and calculated results
for the carbon dioxide-water system. For this system it was
found that a temperature-dependent interaction coefficient is
required to achieve a good match of the experimental data.
The results show that the use of the Peng-Robinson EOS
with Henrys law provides adequate predictions of the
behavior of binary systems involving water. Although not
shown here, similar predictions were also obtained for the
other systems shown in Table 1. It has also been found that
Henrys law is applicable to the systems considered up to a
temperature of about 200C and a pressure around 100 MPa.
MULTICOMWNENT SYSTEMS
For multicomponent systems, it is assumed that the
488 THE CANADI AN J OURNAL OF CHEMICAL ENGINEERING, VOLUME 64, J UNE 1986
TABLE I
Reference Henry's Law Constants and Water Interaction Coefficients
T: temperature, K
fi: fugacity of saturated water, atm
H?: reference Henrv's constant, atm
Coefficients Binary
interaction
Comoonent A B C coefficient Data used in regression
Methane
Ethane
Propane
n-Butane
n-Pentane
n-Octane
Carbon dioxide
Carbon monoxide
Nitrogen
10.9554
13.9485
14.6331
13.4248
16.0045
3 I .943 1
I 1.3021
10.7069
10.7090
11.3569
13.8254
14.4872
13.8865
16.2281
28.6725
10.6030
11.1313
11.4793
1.17105
1.66544
1.78068
1.71879
2.13123
4.37707
1 .20696
I .08920
I .I6549
0.4907
0.491 I
0.5469
0.5080
0.5000
0.4500
0.200
0.2750
Culberson & McKetta (195 I ); Olds et al. (1942)
Culberson & McKetta (1950); Reamer et al. (1943)
Kobayashi & Katz (1953)
Reamer et al. (1944, 1952)
Gillespie & Wilson ( I 982)
Brady et al. (1982)
Wiebe & Gaddy (1939); Todheide & Franck (1963);
Gillespie & Wilson (1980)
Saddington & Krase (1934); Rigby & Prausnitz (1968)
Takenouchi & Kennedy (1964)
'0.2, T 5 373 K; 0.49852-0.008 ( TI, T >373 K.
80
METHANE - WATER SYSTEM
MOLE PERCENT OF METHANE IN
AQUEOUS PHASE
Figure 3 - Aqueous-phasecomposition of methane- water system.
Henry's law constants developed for binary systems still
apply. This is equivalent to assuming that the interaction
between the solutes is negligible, which is true at infinite
dilution.
The phase behavior of the methane-n-butane- water
system was predicted with HT given in Table 1 and the
Peng-Robinson EOS. The predictions match very well the
experimental data of McKetta and Katz (1948) (Figure 9).
A typical application of the calculation method to a
reservoir fluid is given in Appendix B.
Modeling of gas solubility in brines
OUTLINE
In this section the scaled-particle theory (SPT) is used to
modify the Henry's law constants developed previously to
take into account the presence of salt in the aqueous phase.
HENRY'S LAW CONSTANTS FROM SCALED-PARTICLE THEORY
Only the necessary equations concerning the SPT of
fluids are reported in this section. More details on the
subject can be found in Reiss et al. (1960), Lebowitz et al.
(1965) and Pierotti (1963, 1967, 1976).
The SPT can be used to obtain an expression for Henry's
law constant
(23)
Hivs - ( : ; ) (Goi)
ln-- - + RT ....................
RT
where Gbi is the Gibbs energy (work) required to create a
cavity in the solvent of suitable size to accommodate a
solute molecule, GGi is the molar Gibbs energy resulting
from the interaction of the solute molecule with the
surrounding solvent molecules, and where v, is the molar
volume of pure solvent.
Lebowitz et al. (1965) have derived an expression for Gbi
for gas solubility in mixed solvents. When the mixed solvent
is brine, this expression takes the form:
0, =; qw c pj(u;)"
n =1,2,3 . . . . . . . . . . (25)
i
THE CANADIAN J OURNAL OF CHEMICAL ENGINEERING, VOLUME 64, J UNE 1986 489
220
200
180
PROPANE- WATER
SYSTEM -
- Kobayashi 8 Kat z (19531
V 71.1DC A137.8OC
0 104.4C
160
- 0 87.8C 0 154.4C
MOLE PERCENT OF PROPANE IN
VAPOR PHASE
Figure 4 - Vapor-phase composition of propane- water system.
220 PROPANE -WATER SYSTEM
200
180
160
140
a
L
; 120
3
m 100
m
80
a
60 Koboyashi 8 Kat z (1953)
0 15.6OC A 137.8OC
V 7 1 . VC 0 4 5 4 4 0 ~
40
0 104 4 O C
20
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.C
MOLE PERCENT OF PROPANE IN
AQUEOUS PHASE
Figure 5 - Aqueous-phase composition of propane - water system.
. . . . . . . . . . . . .
a; =up/u, k =i , j (26)
r), =Nu: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (27)
u, and a, are respectively the molecular diameter of solute
i and of species j in the solvent, a, is the molecular diameter
of pure water; N is the Avogadros number; p, is the molar
density of species j in the solvent. The summation in
Equation (25) is over all species in the solvent, e.g. for gas
solubility in NaCl aqueous solutibn, the summation involves
the solutes, pure water, Na ions and C1- ions. Masterton
and Lee (1970) showed that the solutes may be excluded
from the summation, and their approach is used in this
study. (The term solutes in this paper refers to the com-
pounds soluble in the aqueous phase which are also present
in the vapor and/or liquid phases).
Shoor and Gubbins (1969) proposed the following
expression for the interaction Gibbs energy Gu,:
5
A
PROPANE -WATER
4
d
=, 3 -
W
3
v)
Vapor
a -
v) phase
w 2 -
a a.
0 Kaboyar hi 0 Kat z (19531
Cal cul at i ons
MOLE PERCENT OF PROPANE
I
CRI TI CAL POINT
Aqueous phase
C3 - r i ch l i qui d
phase
Aqueous
phase
Vapor
phase
J -uulJ
40 60 80 100
TEMPERATURE,OC
Figure 6 - Thrce-phase composition and temperature of propanc-
water system.
TABLE 2
Scaled-Particle-Theory Parameters
u, nm e l k , K IOa, cm/molecule
Water 0.275 85.3 I ,590
Carbon dioxide 0.332 300.0 2.590
Methane 0.413 160.0 2.700
Nitrogen 0.373 95.0 I .730
Na 0.190 147.4 0.210
C1- 0.362 225.5 3.020
NOTE: N =6.02283 X 10; p w =1.84 X lo- (erg-cm) cm; I nm
= m.
...............................
El , = (29)
a; =F(a, * +0, 3/ 2 . . . . . . . . . . . . . . . . . . . . . . . (30)
where p, is the dipole moment of water, a, is the polariza-
bility of solute i , k is Boltzmanns constant, E, is a parameter
which characterizes the strength of the dispersion force, and
where F is unity. Schulze and Prausnitz (1981) found
that better predictions could be obtained by making F
temperature dependent, i.e.,
. . . . . . (31) F(T) =16280/T2 - 141.75/T +1.2978
with T in K.
Schulze and Prausnitz (1981) reported SPT parameters
for the calculation of Henrys law constant for nine gases in
water. Masterton and Lee (1970) tabulated the parameters
for nine ions for the prediction of gas solubility i n aqueous
salt solutions. Values of those parameters which are used in
the present study are listed in Table 2. The values a, of the
ions shown were calculated from the Mavroyannis- Stephen
theory as described in Shoor and Gubbins (1969). Parame-
ters for other compounds can befound in Hirschfelder et al.
(1964) and Weast and Astle (1979).
Equations (25) and (28) require the molar volume of
water and the ions. For aqueous NaCl solutions, these are
estimated as follows
p y =(1 - G) f i s / Mu (32)
PNa+ =pel- =6 f i r / h f N & (33)
.......................
....................
490 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64. JUNE 1986
TABLE 3
Solubility of Nitrogen in Aqueous Sodium-Chloride Solution
Mole % nitrogen in aqueous phase
H20 1 rn NaCl 4 m NaCl
T, P
C MPa Measured Calculated Measured Calculated Measured Calculated
51.1
102.5
125.0
10.13
20.27
30.40
40.53
50.66
60.80
10.23
20.37
30.60
40.83
50.97
61.20
10.44
20.67
30.90
41.04
51.37
61.61
0.0799
0.1454
0.2017
0.2490
0.2920
0.3350
0.0777
0.1447
0.2005
0.2520
0.2980
0.3370
0.0808
0.1492
0.2047
0.2570
0.3060
0.3510
0.0822
0. I479
0.2027
0.2499
0.2914
0.3282
0.0812
0. I501
0.2106
0.2641
0.31 15
0.3548
0.0903
0.1682
0.2368
0.2975
0.3533
0.4035
0.0593
0.1076
0. I497
0.1860
0.2216
0.2530
0.0603
0.1113
0.1538
0.1920
0.2252
0.2600
0.0632
0. I102
0.1533
0.1883
0.223 I
0.2550
0.0627
0.1130
0.1551
0.1916
0.2239
0.2528
0.0628
0.1162
0.1633
0.2052
0.2426
0.2769
0.0694
0. I298
0. I833
0.2308
0.2749
0.3146
-
0.0500
0.0700
0.0878
0.1034
0.1 179
0.0523
0.073 I
0.0899
0.1047
0.1205
0.0567
0.0740
0.0921
0.1041
0.1227
-
-
0.0296
0.0534
0.0736
0.0912
0.1070
0.1214
0.0306
0.0569
0.0803
0.1012
0.1200
0.1373
0.0336
0.0632
0.0896
0.1133
0.1353
0. I552
Average error (%) 6.77 9.47 12.94
Measurements are from OSullivan and Smith (1970).
TABLE 4
Solubility of Methane in Aqueous Sodium-Chloride Solution
Mole % methane in aqueous phase
Hz0 1 m NaCl 4 m NaCl
T, P
C MPa Measured Calculated Measured Calculated Measured Calculated
51.1 10.13 0.1427
20.27 0.2279
30.40 0.2870
40.53 0.3340
50.66 0.3730
60.80 0.4090
102.5 10.23 0.1355
20.37 0.2205
30.60 0.2870
40.83 0.3330
50.97 0.3850
61.20 0.4190
125.0 10.44 0.1434
20.67 0.2321
30.90 0.2960
41.04 0.3430
51.37 0.3960
61.61 0.4300
Average error (%)
0.1416
0.2253
0.2822
0.3257
0.361 1
0.3907
0.1269
0.2149
0.2816
0.3348
0.3787
0.4165
0.1389
0.2399
0.3180
0.3808
0.4350
0.481 I
4.10
0.1076
0.1695
0.2138
0.2500
0.2790
0.3070
0.1693
0.2219
0.2570
0.2890
0.3200
0.1058
0.1752
0.2223
0.2600
0.2940
0.3250
-
0.1116
0.1774
0.2224
0.2567
0.2847
0.3084
0.1006
0.1705
0.2235
0.2660
0.301 1
0.3315
0.1097
0.1898
0.2519
0.3021
0.3455
0.3825
6.30
-
0.0805
0.0997
0.1 154
0. I303
0.1444
0.0826
0.1079
0.121 I
0.1319
0.1433
0.0825
0.1005
0. I164
0. I322
0.1438
-
-
0.0576
0.0914
0.1144
0.1320
0.1464
0. I587
0.0528
0.0895
0. I174
0. I396
0. I580
0.1739
0.0572
0.0990
0.1316
0.1579
0. I805
0.1997
20.033
Measurements are from OSullivan and Smith (1970).
where M, and MNaCl are respectively the molecular weight of
water and NaCl, fi I is the mass density of the aqueous NaCl
solution and where 6 is the weight fraction of NaCl in water.
As pointed out by Pierotti (1967), the use of the SPT does Some predictions of gas solubilities in water and/or
not require explicit ionization information about the salt brines with the SPT are presented in Schulze and Prausnitz
since the latter is included in the solvent density fis. Thus, (1981), Shoor and Gubbins (1969) and Masterton and Lee
an accurate value fi, is required. In this study, bs is estimated (1970). However, because of the uncertainties in the
from the correlation of Rowe and Chou (1970). SPT parameters (Schulze and Prausnitz, 1981) and because
FITTING SCALE-PARTICLE THEORY HENRYS LAW CONSTANTS
TO EXPERIMENTAL DATA
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64, JUNE 1986 49 I
CARBON DIOXIDE- WATER SYSTEM
25' 50' 75' 100' 150' 200' 250' C
500 Witbe ( 1942)
- CARBON DIOXIDE- WATER SYSTEM
-
-
50' 1000 450' 200' 250' C
o m Wi tbe B Gaddy (19391
0 x 0 A 0 v T6dheidt B Fr anck(1963)
A v Taktnouchi 8 Kt nnt dy(l 96
I - Caiculatianr
Two phase regi on
McKet t a, Jr. 6 Katz ( 1948)
.2 Hydrocarbon ri ch liquid phasm
Vapor pharm
MOLE PERCENTOF WATER IN VAPOR PHASE
Figure 7 - Vapor-phase composition of carbon-dioxide- water
system.
o A o v TSdheide B Franch ( 1963)
A v Taktnouchi B Kt nnt dy(1964)
t
I I I I I 1
1 2 3 4 5 6
MOLE PERCENT OF CARBON DIOXIDE
IN AQUEOUS PHASE
Figure 8 - Aqueous-phase composition of carbon-dioxde - water
system.
of several approximations made in the theory (Masterton
and Lee, 1970) there are usually disagreements between
predicted and measured values.
In this paper, to reduce these uncertainties, Henry's law
constants from the STP are first fitted to the values calcu-
lated from Equation (17) for gas solubility in pure water.
The adjustable parameter is the molecular diameter ui of the
solute which has a strong influence on the SPT predictions
(Schulze and Prausnitz, 1981). Subsequently, the SPT
parameters of the ions and the density of the aqueous
salt solution are used in Equations (24), (25) and (28) to
calculate the Henry's law constants in the presence of salt.
For a given pressure and temperature, the determination
40
30
METHANE - n-BUTANE -WATER SYSTEM
Two DhaSe n ai o n
- Cal cui at l ons
CALCULATED CRITICAL LOCUS
\
Three phase regi on
I
0.1 1 10
MOLE PERCENT OF WATER
Figure 9 - Composition of water in vapor and hydrocarbon-rich
liquid phase: methane-n-butane- Water system.
CARBON DIOXIDE I N AQUEOUS
NoCl SOLUTION
Tokenouchi 8 Kennedy ( 1965)
"' , zo; c
4.28m
1. 09m
O m
--- l - Cal cul at i ons
4 . 2 8 m 1. 09m Om 1. 09m Om
0
I I I I I I I
1 2 3 4 5 6 7
MOLE PERCENT OF CARBON DIOXIDE
IN AQUEOUS PHASE
Figure 10 - Solubility of carbon-dioxide and aqueous NaCl
solution.
of cri for each solute involves the solution of a nonlinear
equation corresponding to the equality of STP Henry's law
constant with the Henry's law constant obtained from
Equation (17). Since no salt is present, the equation is rela-
tively simple and is solved using Newton's method with
492 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64, JUNE 1986
TABLE 5
Compositions of Reservoir and Recombined Fluids at Various Water Cuts
Composition" (mol %)
Reservoir Reservoir
Water cut (%) aqueous-phase oil-phase
Component Oil G 67 89 (mol %) (mol %)
compositionb compositionb
N2
c02
CI
c2
C,
nC4
nCs
n C6
C,--C16
C17-Cxi
H20
Molecular weight
Bubble point (MPa)
c:,
at 65.5" C
0.27
0.26
30.58
4.61
6.06
4.71
4.33
3.18
28.26
12.10
5.66
-
132.2
12.040
0.29
0.38
31.88
4.58
5.94
4.60
4.23
3.10
27.63
I I .83
5.53
-
129.7
12.743
0.34
0.69
35.70
4.49
5.61
4.31
3.95
2.90
25.80
11.05
5.17
-
122.3
14.939
0.0015
0.0088
0.1310
0.0050
0.0017
o.oO05
o.oO01
O.oo00
O.oo00
O.oo00
O.oo00
99.8514
0.27
0.26
30.27
4.57
6.00
4.66
4.28
3. I4
27.98
I I .98
5.60
0.99
131.1
I 1.970
'Dry basis.
hWet basis.
UNSTABLE
STABLE
W- aqueous phase
L = liquid phoso
V = vopor phase
ST= stabi l i ty ?*st
/ ' fl ash calculation
- =i n equiilbrlum
FigureI I - Flow diagram for liquid-vapor-water flash calcu-
lations.
analytical derivative. The initial guess for ui corresponds to
the value reported in the literature (Table 2). Note that ui is
treated as an adjustable parameter and therefore the resulting
value may not have any physical meaning.
Results
The measurements of O'Sullivan and Smith (1970) on the
solubility of nitrogen and methane in aqueous NaCl solu-
tions are matched with the procedure just described. The
results are shown in Tables 3 and 4. Both the solubilities of
nitrogen and methane decrease as the salt concentration
increases (salting out phenomena). The error in the pre-
dictions increases with salt concentration and temperature.
The solubility of carbon dioxide in aqueous NaCl solu-
tions is also calculated and compared to the measurements
of Takenouchi and Kennedy (1965). Adequate predictions
were obtained as shown in Figure 10. Again, the error
increases with salt concentration and temperature.
100 15
Figure 12 - Effect of water cut on producing GOR and bubble-
point pressures of recombined fluids.
The values of ui for the solute obtained from matching
pure-water Henry's law constants are not far from the initial
values reported in the literature. For nitrogen, typical values
of ui are 0.37321 nm at 10.132 MPa and 51.5"C, and
0.36627 nm at 61.606 MPa and 125C compared to a value
of 0.373 nm shown in Table 2. For methane, the fitted ui is
0.34314 nmat 10.132 MPa and 51.5"C, and 0.34703 nmat
61.606 MPa and 125C compared to a reported value of
0.413 nm. For carbon dioxide, the values are 0.33076 nm
at 1 MPa and lOO"C, and 0.2733 nmat 20 MPa and 250C
compared to a reported value of 0.332 nm.
DISCUSSIONS
The SPT provides a simple and adequate method for
correlating Henry's law constants for gas solubility in
brines. Note that in the calculations presented above, only
the ui of the solutes are treated as adjustable parameters to
match the Henry's law constants predicted by Equation (17).
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64, JUNE 1986 493
All other STP parameters are given in Table 2.
The procedure can be applied to any aqueous salt solution
provided the STP parameters for all ions are available, and
the mass density of the solvent is known. In the present
study, the density of brine is estimated from Rowe and
Chous ( 1970) correlation which is developed for pressures
up to 34.3 MPa. However, the pressures in the calculations
went beyond 125 MPa, and some of the inaccuracies in the
predictions may partly be attributed to an inaccurate solvent
density value.
Again, the ui of the ions could also be adjusted to give a
better fit of the experimental data. However, this was not
carried out in this study.
Conclusions
This paper presents a method for predicting the phase
behavior of oil, gas and water or brines where the oil and gas
are modeled with the Peng-Robinson equation of state and
where the gas solubility in the aqueous phase is estimated
from Henrys law constants. The method is simple and
gives adequate predictions for pressure and temperature
conditions encountered in reservoir engineering studies.
Correlations for Henrys law constants and Peng-
Robinson equation of state interaction coefficients are de-
termined for a variety of compounds of interest to the oil
industry. For practical purposes, any hydrocarbon heavier
than pentane may be assumed insoluble in the aqueous
phase. Satisfactory predictions of gas solubility in pure
water up to 200C and 100 MPa have been obtained.
The scaled-particle theory was used to predict the change
of Henrys law constant due to the presence of salt in the
aqueous phase. By adjusting the solute molecular diameter,
adequate predictions of solubility in aqueous NaCl solution
up to a 4 m concentration have been obtained.
Although the reference Henrys law constants in Table 1
were determined with the Peng-Robinson equation of state
for the vapor or liquid phase, they could be used with any
other equation of state. However, the interaction coeffi-
cients in Table 1 are only for the Peng-Robinson equation
of state.
Appendix A
Three-phase flash calculations for liquid-vapor- water
systems
Procedures for three-phase flash calculations where all phases
are modeled with an EOS can befound in Heidemann ( 1974). Peng
and Robinson (176b), Fussell (1979), Mehraet al. (1982), Michel-
sen (1982b). Risnes and Dalen (1984) and Nghiemand Li (1984).
The algorithmdescribed in the following is a modification of the
method of Nghiemand Li (1984) to handle three-phase liquid-
vapor- water (LVW) flash calculations where theaqueous phase is
not modeled by an EOS. The procedure does not require good
initial guesses of K-values since the latter are obtained fromsta-
bility tests using thetangent plane criteripn. Detailed discussions
on this subject are presented in Nghiemand Li (1984). Michelsen
(1982a) and Baker et al. (1982).
Figure 11 shows a flow diagramof a stagewise procedure for
LVW flash calculations. Notethat thesymbols L and V in the flow
chart could bepermuted since the first two-phase flash calculation
could either bea LW calculation or a VW calculation. When the
cubic EOS yields morethan oneroot in the compressibility factor,
the one corresponding to the lowest Gibbs energy is selected
(Evelein et al., 1976). The stability test of a phase with composition
y consists of solving
d ; ( u ) =In ui +In & ( 6) - In y , - In $, (y) =0 .... (A.1)
i, =u,/$ UL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (A.2)
The +, in Equation (A. I ) are the EOS fugacity coefficients for
u, . The phase with composition y is unstable if, at convergence,
i U , >1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (A.3)
In the stability test of a VW or LW system, it has been found
necessary to prevent convergence to a set of u , corresponding to an
aqueous phase predicted by an EOS, since the latter has been
modeled by Henrys law. For this purpose the following equation
is solved for u instead of Equation (A. I )
i =I , . . . , n , . . . . (A.4)
where y,,,. is thecomposition of water in theaqueous phase from
a two-phase VW or LW calculation.
The algorithmin Figure 1 1 requires the initial guesses K:::,. The
following equations provide a reasonable estimate for K:::?
! , = I
I = I
d : ( u ) =d i ( u ) / l u , - yw,,.I =0
K::, =p/H, i f w . . . . . (A.4)
~j : ! =K , * ~/ H, i z w . . . . . . . . . . . . . . . . . . . . . . . ( AS)
if a VW systemis expected, or
if a LW systemis expected. K,* is Wilsons K-value given by
K,* =( p<. / / p) exp [5.42(1 - T<, / T) ( I +w,)] . . . . . . . (A.6)
Even if VW Kj is selected instead of LW K rl for LW flash
calculations or vice-versa, convergence to thecorrect solution will
still beachieved. However, the procedure may take longer to reach
the solution.
For the water component, a value for Kc,:, is found such that
i Kj:!z, >1 ................................ (A.7a)
, = I
and
$ z,/K::! >1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (A.7b)
I = I
This could easily be achieved by setting Kr,:, equal to a large
number (say >IOOO). Equation (A.7) will guarantee a split of the
feed into two phases when the material balance for two-phase flash
calculations is solved (Nghiemet at., 1983; Rachford and Rice.
1952).
Appendix B
Effect of water on the producing gas-oil ratio
An example illustrating the effect of gas solubility in the aqueous
phase on the producing gas-oil ratio (GOR) froma producing well
is given in the following.
Water is usually produced together with oil, and thegas obtaincd
at surface conditions comes fromboth the oil and the aqueous
phase. Consider a typical reservoir oil (called Oil G) and com-
position shown in the second column of Table 5 . The oil is in
equilibrium with the aqueous phase at reservoir conditions of
14MPa and 65.6C. It is assumed that the solubility of hydro-
carbons heavier than nCs is negligible. The compositions of the
recombined reservoir fluids obtained by blending the oil and gas at
surface conditions (0.101 MPaand 15.5C) at 67% and 89% water
cut (water cut =flow rate of water/(flow rate of water +oil)) are
also shown in Table 5. The molecular weights and bubble-point
pressures for the various fluids, as well as the aqueous phase
composition and the water composition in the oil phase are also
reported. Figure 12 illustrates the change in the producing GOR
with the water cut for thesame system. The computed bubble-point
pressure of the recombined fluid is also depicted. The results show
494 THE CANADI AN J OURNAL OF CHEMI CAL ENGI NEERI NG, VOLUME 64, J UNE 1986
that the effect of gas solubility in the aqueous phase on the
producing GOR cannot be ignored at high water cut.
Acknowledgement
This work was supported by thc Department of Energy, Mines
and Resources of Canada under Contract 01 SG-23294-4-07s I .
Nomenclature
cohesive energy density defined in Equation (20)
defined in Equation (A. I )
defined in Equation (A.4)
interaction coefficient
fugacity of component i in phase m
temperaturc-dependent factor defined in Equation (3 1 )
mole fraction of phase m
molar Gibbs energy of interaction between the solute i and
the solvent
molar Gibbs energy for cavity creation
molar enthalpy of component i in vapor phase
molar enthalpy of component i at infinite dilution
molar enthalpy of water at the given temperature and zero
pressure
molar enthalpy of water at saturation conditions
Henrys law constant of component i
reference Henrys law constant of component i
Henrys law constant of component at a given pressurep;
Boltzmanns constant
Wilsons K-value defined in Equation (A.6)
K-value of component i in phase m
molality
molecular weight
number of components
Avogadro number (= 6.02283 X lo)
pressure
pressure where HY is evaluated
universal gas constant
temperature
temperature in degree F
variable in stability-test equation
composition corresponding to u,
molar volume
molar volume of component i at infinite dilution
mole fraction of component i in phase m
feed (global) composition of component i
polarization of solute i
parameter which characterizes the dispersion strength of
component i
geometric mean of E, and E,
defined in Equation (27)
defined in Equation (25)
dipole moment of water
molar density
mass density
molecular diameter of compound i
dimensionless molecular diameter of compound i defined
in Equation (26)
defined in Equation (30)
fugacity coefficient of component i in phase m
acentric factor of component i
weight fraction of salt in water
Superscripts
s =saturated
(0) =initial guess
Subscripts
i, j. k =indices for component
e =liquid phase
m, q =indices for phase
s =solvent
v =vapor phase
w =aqueous phase
w =water component
References
Baker, L. E., A. C. Pierce and K. D. Luks, Gibbs Energy Anal-
ysis of Phase Equilibra. Soc. Petrol. Eng. J . 22, 731-742
(1982).
Brady, C. J ., J . R. Cunningham and G. M. Wilson, Water-
Hydrocarbon Liquid-Liquid- Vapor EquilibriumMeasurements
to 530F. Research Report RR-62, Gas Processors Association,
Tulsa, OK, September, 1982.
Canjar, L. N. and F. S. Manning, Thermodynamic Properties and
Reduced Correlations for Gases, Gulf Publishing Co., Houston,
Texas, 1967.
Culberson, 0. L. and J . J . McKetta, J r., Phase Equilibria in
Hydrocarbon - Water Systems 11-The Solubility of Ethane in
Water at Pressures to 10 OOO psi, Petrol. Trans. AlME 189,
319-322 (1950).
Culberson, 0. L. and J . J . McKetta, J r., Phase Equilibria in
Hydrocarbon - Water Systems Ill-The Solubility of Methane
in Water at Pressures to 10 OOO psia, Petrol. Trans. AIME 192,
233-266 (1951).
Cysewski, G. R. and J . M. Prausnitz, Estimation of Gas
Solubilites in Polar and Nonpolar Solvents, Ind. Eng. Chem.
Fundam. 15, 304-309 (1976).
Erbar, J . H., A. K. J agota, S. Muthswamy and M. Moshfeghian,
Predicting Synthetic Gas and Natural Gas Thermodynamic
Properties Using a Modified Soave-Redlich-Kwong Equation
of State, Research Report RR-42, Gas Processors Association,
Tulsa, OK, August, 1980.
Evelein, K. A., R. G. Moore and R. A. Heidemann, Correlation
of the Phase Behavior in the Systems Hydrogen Sulfide - Water
and Carbon Dioxide - Water, lnd. Eng. Chem., Process Des.
Dev. 15, 423-428 (1976).
Fussell, L. T., A Technique for Calculating Multiphase
Equilibria, Soc. Petrol. Eng. J . 19 203-210 (1979).
Gillespie, P. C. and G. M. Wilson, Vapor-Liquid Equilibrium
Data on Water-Substitute Gas Components: N2-H20,
H2-H20, CO-H20, H2-CO-H20, and H2S-H20. Re-
search Report RR-41, Gas Processors Association, Tulsa, OK,
April, 1980.
Gillespie, P. C. and G. M. Wilson, Vapour - Liquid and Liquid
- Liquid Equilibria: H20-CH4, H20-COz, H20-H2S,
H20-nCs, H20-CH4-nCs, Research Report RR-48, Gas
Processors Association, Tulsa, OK, April, 1982.
Heidemann, R. A., Three-Phase Equilibria Using Equations of
State, AlChE J . 20, 847-855 (1974).
Heidemann, R. A. and J . M. Prausnitz, Equilibrium Data for
Wet-Air Oxidation, Water Content and Thermodynamic Proper-
ties of Saturated Combustion Gases, Ind. Eng. Chem., Process
Des. Dev. 16, 375-381 (1977).
Hirschfelder, J . O., C. F. Curtiss and R. B. Bird, Molecular
Theory of Gases and Liquids, J ohn Wiley & Sons, N.Y ., 1964.
J onah, D. A., A New Correlation for Henrys Constant for the
Solubility of Gases and Liquids, Fluid Phase Equilibria 15,
173-187 (1983).
Kobayashi, R. and D. L. Katz, Vapor-Liquid Equilibra for
Binary Hydrocarbon-Water Systems, Ind. & Eng. Chem. 45,
Lebowitz, J . L., E. Helfand and E. Praestgaard, Scaled Particle
Theory of Fluid Mixtures, J . Chem. Phys. 43, 774-779
(1965).
Luks, K. D., P. D. Fitzgibbon and J . T. Banchero, Correlations
of the Equilibrium Moisture Content of Air and of Mixtures of
Oxygen and Nitrogen for Temperatures in the Range of 230 to
600 K at Pressures up to I 00 Atm., Ind. Eng. Chem. Process
440-451 (1953).
THE CANADIAN J OURNAL OF CHEMI CAL ENGINEERING, VOLUME 64, J UNE 1986 495
Des. Dev. 15, 326-332 (1976).
Lyckman, E. W., C. A. Eckert and J . M. Prausnitz, Generalized
Reference Fugacities for Phase Equilibrium Thermodynamics.
Chem. Eng. Sci. 20, 685-691 (1965).
Masterton, W. L. and T. P. Lee, Salting Coefficients from Scale
Particle Theory, J . Phys. Chem. 74, 1776- 1782 (1970).
McKetta, J . J . J r. and D. L. Katz, Methan-n-Butane-Water
Systems in Two- and Three-Phase Regions, Ind. & Eng.
Chem. 40, 853-863 (1948).
Mehra, R. K., R. A. Heidemann and K. Aziz, Computation of
Multiphase Equilibrium for Compositional Simulation, SOC.
Petrol. Eng. J . 22, 61-68 (1982).
Mehra, R. K., R. A. Heidemann and K. Aziz, An Accelerated
Successive Substitution Algorithm, Can. J . Chem. Eng. 61,
590-596 (1984).
Michelsen, M. L., The Isothermal Flash Problem. I . Stability,
Fluid Phase Equilibria 9, I - 19 (1982a).
Michelsen, M. L., The Isothermal Flash Problem. 11. Phase-Split
Calculation, Fluid Phase Equilibria 9, 21 -40 (1982b).
Nghiem, L. X. and R. A. Heidemann, General Acceleration
Procedure for Multiphase Flash Calculation with Application
to Oil-Gas- Water Systems, Proceedings of the Second
European Symposium on Enhanced Oil Recovery, November
8- loth, 1982, Paris, Editions Technip, Paris, 303-316.
Nghiem, L. X. , K. Aziz and Y . K. Li, A Robust Iterative Method
for Flash Calculations Using the Soave-Redlich-Kwong or the
Peng-Robinson Equation of State, SOC. Pet. Eng. J . 23,
521 -530 (1983).
Nghiem, L. X. and Y. K. Li, Computation of Multiphase Equi-
librium Phenomena with an Equation of State, Fluid Phase
Equilibria 17, 77-95 (1984).
OConnell, J . P., Thermodynamics of Gas Solubility, Proc.
Second Int. Conf. on Phase Equilibria and Fluid Properties in
the Chemical Industry, Berlin (West), March 17-21. 1980,
Dechema, Frankfurt/Main, West Germany, 445-455.
Olds, R. H., B. H. Sage and W. N. Lacey, Phase Equilibria in
Hydrocarbon Systems-Composition of the Dew-Point Gas of
the Methane-Water Systems, lnd. Eng. Chem. 34,
OSullivan, T. D. and N. 0. Smith, The Solubility and Partial
Molar Volume of Nitrogen and Methane in Water and in Aque-
ous Sodium Chloride from 50 to 125C and 100 to 600 Atm.,
J . Phys. Chem. 74, 1460-1466 (1970).
Peng, D. Y. and D. B. Robinson, A New Two-Constant Equation
of State, Ind. Eng. Chem. Fundam. 15, 59-64 (1976a).
Peng, D. Y. and D. B. Robinson, Two- and Three-Phase Equi-
librium Calculations for Systems Containing Water, Can. J .
Chem. Eng. 54, 595-599 (1976b).
Peng, D. Y . and D. B. Robinson, Two- and Three-Phase Equi-
librium Calculations for Coal Gasification and Related
Processes, in Thermodynamics of Aqueous Systems with Indus-
trial Applications, Newman, S. A., Ed., Amer. Chem. SOC.
Symp. Ser. 133, 393-414 (1980).
Pierotti, R. A., The Solubility of Gases in Liquids, J . Phys.
Chem. 67, 1840- I845 (1963).
Pierotti, R. A., On the Scaled-Particle Theory of Dilute Aqueous
Solutions, J . Phys. Chem. 71, 2366-2367 (1967).
Pierotti, R. A., A Scaled-Particle Theory of Aqueous and
Nonaqueous Solutions, Chem. Rev. 76, 717-726 (1976).
Prausnitz, J . M., Molecular Thermodynamics of Fluid- Phase
Equilibria, Prentice-Hall, Inc., Englewood Cliffs, N.J ., 1969,
170.
Rachford, H. H., J r. and J . D. Rice, Procedure for Use of
1223-1227 (1942).
Electronic Digital Computers in Calculating Flash Vaporization
Hydrocarbon Equilibrium, Trans. SOC. Petrol. Eng. 195,
327-328 (1952).
Reamer, H. H., R. H. Olds, B. H. Sage and W. N. Lacey,
Composition of Dew-Point Gas in Ethane- Water System,
Ind. Eng. Chem. 35, 790-793 (1943).
Reamer, H. H., R. H. Olds, B. H. Sage and W. N. Lacey,
Composition of Coexisting Phases of n-Butane- Water in the
Three-Phase Region Ind. Eng. Chem. 36, 381-383 (1944).
Reamer, H. H., B. H. Sage and W. N. Lacey, Phase Equilibria
in Hydrocarbon Systems: n-Butane- Water System in the Two-
Phase Region, Ind. & Eng. Chem. 44, 609-614 (1952).
Reid, R. C., J . M. Prausnitz and T. K. Sherwood, The Properties
of Gases and Liquids, 3rd Ed., McGraw-Hill Book Co., New
York, N.Y., 1977, pp. 133-115, 188.
Reiss, H., H. L. Frisch, E. Helfand and J . L. Lebowitz, Aspects
of the Statical Thermodynamics of Real Fluids, J . Chem. Phys.
Rigby, M. and J . M. Prausnitz, Solubility of Water in Com-
pressed Nitrogen, Argon and Methane, J . Phys. Chem. 72, I
(1968).
Risnes, R. and V. Dalen, Equilibrium Calculations for Coexisting
Liquid Phases, SOC. Petrol. Eng. J . 24, 87-96 (1984).
Rowe, A. M. and J . C. S. Chou, Pressure-Volume-Tern-
perature-Concentration Relation of Aqueous NaCl Solutions,
J . Chem. Eng. Data 15, 61-66 (1970).
Saddington, A. W. and N. W. Krase, Vapor-Liquid Equilibria
in the System Nitrogen-Water, J . Am. Chem. SOC. 56,
353-361 (1934).
Water at High Temperatures, Ind. Eng. Chem. Fundam. 20,
175-177 (1981).
Selleck, F. T., L. T. Carmichael and B. H. Sage, Phase Behavior
in the Hydrogen Sulfide - Water System, Ind. & Eng. Chem.
Shoor, S. K. and K. E. Gubbins, Solubility of Nonpolar Gases in
Concentrated Electrolyte Solutions, J . Phys. Chem. 73,
Smith, J . M. and H. C. Van Ness, introduction to Chemical
Thermodynamics, Third Edition, McGraw-Hill, New York,
N.Y., 1975, pp. 241-244, 614.
Takenouchi, S. and G. C. Kennedy, The Binary System
H20-C02 at High Temperatures and Pressures, Am. J our. Sci.
262, 1055- I074 (1964).
Takenouchi, S. and G. C. Kennedy, The Solubility of Carbon
Dioxide in NaCl Solutions at High Temperatures and
Pressures, Am. J our. Sci. 263, 445-454 (1965).
Todheide, K. and E. U. Franck, Das Zweiphasengebiet und
die Kritische Kurve imSystem Kohlendioxid-Wasser bis au
Drucken von 3500 bar, Z. Physik Chem. (Frankfurt) 37,
387-401 (1963).
Weast, R. C. and M. J . Astle, Eds., CRC Handbook of Chemistry
and Physics, 60th Ed.. CRC Press, 1979.
Wiebe, R., The Binary System Carbon Dioxide - Water Under
Pressure, Chem. Rev. 29, 475-481 (1942).
Wiebe, R. and V. L. Gaddy, The Solubility in Water of Carbon
Dioxide at 50, 75 and IOOC, at Pressures to 700 Atmospheres,
J . Am. Chem. SOC. 61, 315-318 (1939).
32, 119-124 (1960).
Schulze, G. and J . M. Prausnitz, Solub
44, 2219-2226 (1952).
498 - 505 ( 1969).
Manuscript received J une 7, 1985; revised manuscript received
December 5, 1985; accepted for publication J anuary 3, 1986.
496 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 64, JUNE 1986