PETROLEUM SOCIETY

PAPER 2008-084

On Estimating the
Water Content of CO2
in Equilibrium with
Formation Brine
H. SALARI, H. HASSANZADEH, S. GERAMI
IOR Research Institute, National Iranian Oil Company

J. ABEDI
University of Calgary
This paper is accepted for the Proceedings of the Canadian International Petroleum Conference/SPE Gas Technology Symposium
2008 Joint Conference (the Petroleum Societys 59th Annual Technical Meeting), Calgary, Alberta, Canada, 17-19 June 2008. This
paper will be considered for publication in Petroleum Society journals. Publication rights are reserved. This is a pre-print and
subject to correction.

literature and other predictive models for CO2-water systems. A

CO2 water content chart is presented that can be used simply to
predict the water content of CO2 in equilibrium with formation
brine. The procedure presented may be used for generating
necessary input data for flow simulation of CO2 storage in deep
saline aquifers.

Abstract
Water content of carbon dioxide (CO2) is an important
parameter in engineering applications, such as CO2 storage in
deep saline aquifers and enhanced oil recovery processes.
Large numbers of experimental data have been reported on the
solubility of CO2 in brine. However, experimental data on the
water content of CO2 in equilibrium with formation brine are
not reported in the literature. Water content of natural gas is
traditionally calculated by general water content charts;
however, these charts are not available for CO2 in equilibrium
with formation brine. In this work, using an accurate fugacity
and activity model available in the literature, an efficient and
simple procedure is developed to estimate the water content of
CO2 in equilibrium with formation brine. To validate the
developed procedure, the predicted CO2 rich phase water
content is compared with the reported experimental data in the

Introduction
As concern about the adverse consequences of anthropogenic
climate change has grown, so has research into methods to
reduce the emissions of greenhouse gases that drive future
climatic change. Carbon dioxide (CO2) emissions arising from
use of fossil fuels are likely to be the dominant drivers of
climate change over the coming century. The use of carbon
dioxide and geologic storage (or sequestration) offers the

possibility of maintaining access to fossil energy while reducing

emissions of carbon dioxide to the atmosphere. Many attempts
have been made to mitigate this problem, and several potential
methods have been proposed. Among them, the sequestration of
CO2 into deep saline aquifers, depleted oil and gas reservoirs,
unmineable coal seams and deep oceans are promising options
(1)
. CO2 storage in saline aquifers is proposed for disposition at
depths greater than 800 meters, where the injected CO2 is in a
supercritical state (2). The in-situ dissolution of CO2 under such
conditions depends on the pressure, temperature and salinity of
the resident formation brines. The precise PVT (pressure,
volume, temperature) and composition properties of CO2 and
brine are essential for accurate evaluation and predicting the
long-term behavior of the injected fluid. Thermodynamic
modeling of these properties have been attempted by many
researchers, including Spycher et al. (3), Spycher and Pruess (4),
Portier and Rochelle (5), Duan and Sun (6), Duan et al. (7), and
Hassanzadeh et al. (8). Accurate modeling of the disposition of
CO2 injected into subsurface formations requires an accurate
thermodynamic model. However, using sophisticated
thermodynamic models are computationally expensive and are
not well suitable for CO2 storage. It is, therefore, important to
use a simple but accurate thermodynamic model for a very
specific case of geological CO2 sequestration (8).
Water (H2O) content of CO2 is an important parameter in
several engineering applications, such as sweetening of natural
gas, enhanced oil recovery, and CO2 storage in deep saline
aquifers. The experimental measurements of CO2-H2O mixtures
have been the subject of many studies; and, many researchers
have measured the various properties of the mixture, including
CO2 solubility in water, brine and other salt solutions. Detailed
reviews on this subject can be found in Spycher et al. (3), Duan
and Sun (6), and Diamond and Akinfiev (9).
Wiebe and Gaddy (10,11) and Wiebe (12) reported
measurements of the water content of CO2 rich phase for
pressures up to 71 MPa and temperatures up to 100C. Dodson
and Standing (13) presented PVT and solubility data for mixtures
of natural gas and oilfield brines and water for a pressure range
of 3.45 to 34.46 MPa and a temperature range of 37.8 to 121C.
The phase equilibrium data for the water-CO2 system was also
measured by Gillespie et al. (14), Coan and King (15), and King et
al. (16) and included water content in CO2 rich phase. The data
from Coan and King (15) covered a temperature range up to
100C and a pressure range less than 5.17 MPa. King et al. (16)
measured the vapor-liquid equilibrium near the critical region
and at a pressure a little over 20 MPa and for a temperature
range from 15 to 40C. Mller et al. (17) measured the vaporliquid equilibrium in the temperature range of 100 to 200C.
Zawisza and Malesinska (18) determined the solubility of CO2 in
water and the solubility of water in gaseous CO2 for the
pressure range of 0.207 to 5 MPa and temperatures up to 200C.
They also calculated the Henry constants for the temperature
range of 50 to 200C. The measurements done by Song and
Kobayashi (19) provided valuable data on the water content of
CO2 rich fluids for temperatures above 104C. Enick and Klara
(20,21)
have used 110 solubility data from the literature for the
CO2-water system over a temperature range of 25 to 250C and
a pressure range of 3.4 to 72 MPa to determine the reference
Henrys constant. Span and Wagner (22) reviewed the available
data on the thermodynamic properties of CO2 and presented a
new equation of state that accurately represents the
experimental data. Dubessy et al. (23) reviewed the data available
in the literature and developed a thermodynamic model for two
systems of CO2-water and sodium chloride (NaCl) and H2O,

NaCl and hydrogen sulfide (H2S) below the temperatures of 270

and 250C for both mixtures, respectively.
Thermodynamic models have recently appeared in the
literature, including those investigated by Spycher et al. (3),
Spycher and Pruess (4), Portier and Rochelle (5), Duan and Sun
(6)
, and Duan et al. (7). Hassanzadeh et al. (8) used a combination
of the Spycher et al.(3) fugacity model and the Duan and Sun (6)
activity model to predict PVT data for black-oil simulation of
CO2 storage in a saline aquifer.
Since the water content of CO2 is essential in various
engineering applications, large numbers of experimental data
have been reported on the solubility of CO2 in brine. However,
experimental data on the water content of CO2 in equilibrium
with formation brine are not reported in the literature (4,23), or at
least we were not able to locate them. The water salinity affects
the water content of CO2 rich phase and needs to be accounted
for in engineering calculations. Water content of natural gas is
traditionally calculated by general water content charts. These
charts, however, are not available for CO2 in equilibrium with
formation brine. In this work, such a general chart is presented
by estimation of the water content of CO2 in equilibrium with
formation brine, using an accurate fugacity and activity model.
In order to validate the developed procedure, the predicted
water content is compared with the reported experimental data
for pure water CO2 systems.
This paper is organized as follows. First, predictive models
for water content are reviewed briefly. The CO2-brine
thermodynamic equilibrium used in this work is described. The
predicted water content of CO2 are then compared with the
experimental data and those predicted by other models. The
summary and conclusion follow.

Predictive Models for Water Content

There are several predictive models for estimating the water
content of a gaseous phase. Some of these models take the
vapor pressure of pure water as input data; however, the poorer
the estimates of vapor pressure, the poorer the estimates of the
water content. The following subsections present brief
descriptions of the current water content prediction models (24).

Ideal Model
The simplest model is the ideal model, where the water
content is calculated by assuming an ideal mixture and by
representing the equilibrium ratio of water equal to the ratio of
water vapor pressure to the total system pressure as given by
(24)
:
= 760627.3

psat
................................................................................ (1)
pt

where is the water content in kg/MMSm3, p sat is the water

vapor pressure, p t is the total system pressure, and 760627.3 is
a unit conversion factor. The pressures can be in any unit but
need to be in a consistent set of units. This simple method
inherently provides results that are not highly accurate, but good
accuracy can be expected at low pressures.
In order to make this model more realistic from a
thermodynamic point of view, the effect of gases dissolved in
the water should be included. Therefore, Equation (1) becomes:

 = 760627.3

(1 xgas ) psat
pt

p
= sat
pt

................................................................ (2)

where x is the mole fraction of gas dissolved in the water. For

hydrocarbons, solubility is negligible and can be set to zero
without producing considerable error; however, for acid gases,
the value of x can be very determining and significant.

f sat
= 47484 w
f gas

To estimate the water content of sweet natural gas for the

purpose of gas dehydration, McKetta and Wehe (25) produced a
chart, which has been modified over the years and is being used
widely in industrial applications. The application of this chart is
limited to sweet gases. In order to make the chart applicable for
sour gases, some corrections have been developed, such as the
Maddox correction (26,27) and the Wichert and Wichert
correction (28). The former correction considers the water
content of sour gas as a combination of the water content of
three parts, namely a) sweet gas, b) CO2 and c) H2S. The water
content of the sweet gas is obtained from the McKetta-Wehe
chart, and the water contents of CO2 and H2S are determined
using charts provided by Maddox. The later charts cover a
pressure range of 0.689 to 20.68 MPa and temperature ranges of
27 to 71C for CO2 and 27 to 138C for H2S. The water content
of sour gas is thus calculated using the following equation:
2

............................................................................ (6)

Bukacek(32) proposed a simple method to calculate the water

content of sweet gas using an ideal approach and a factor to
account for deviation from the ideal system. This method can
accurately predict the water content in the temperature range of
15.6 to 278C and the pressure range of 0.103 to 68.929 MPa.
Although the relations proposed by Bukacek (32) seem simple,
they need a precise estimate of the vapor pressure of pure water
to find accurate results.
The relations of Bukacek (32) are as follows:

= 47484

log B =

yHeq S = y H S +0.75 yCO ............................................................................ (4)

2

..................................................... (5)

Bukacek Method

where y is the contribution of each part in the gaseous phase in

the form of mole fraction.
Wichert and Wichert (28) developed a single chart to correct
water content for the effect of the equivalent H2S content of gas,
which includes the effects of both CO2 and H2S. Their method
is easy to use, but limited to a concentration of H2S equivalent
no greater than 55 mole percent, a temperature range of 10 to
177C, and a pressure range of 1.379 to 68.93 MPa.
The equivalent mole fraction of H2S is calculated using the
relation below:

0.0049

where f gas and Z are the fugacity and compressibility factor of

gas at the system conditions, respectively. Although a chart for
determining water fugacity at system conditions has been
provided, it is only valid for a temperature range of 27 to 71C
and pressures below 13.786 MPa. These drawbacks along with
determination of the compressibility factor of the gas mixture
make this method less attractive than other methods.

= ysweet gassweet gas + yCO CO + yH SH S ......................................... (3)

2

pt

p
sat

where f wsat and f w are the fugacity of water at saturation and

system conditions, respectively, and is the correlation factor
and is dimensionless if a consistent set of units is used. The
water content is then calculated by the following equation:

McKetta-Wehe Chart

f wsat pt

f p
sat
w

p sat
+ B ............................................................................ (7)
pt

3083.87
+ 6.69449 ......................................................... (8)
459.6 + T

where p sat is the water vapor pressure, p t is the total system

pressure, T is in F and is in lb/MMCF, and B is a
parameter for deviation from the ideal state.

Furthermore, Robinson et al. (29,30) developed a relationship

to determine the water content of sour gases. They presented a
series of charts for different pressures up to 68.929 MPa and
temperatures from 10 to 177C. Their charts need the H2S
equivalent defined by Equation (4) as an input parameter. These
charts can be used up to 40 mole percent of H2S equivalent, but
multiple interpolations are required to determine the water
content, which consequently reduces the accuracy of the
method.

Ning et al. Method

Ning et al. (33) developed a method to calculate the water
content of natural gas based on the McKetta-Wehe (25) chart.
They derived a linear equation as a function of temperature and
pressure, which cover pressures up to 100 MPa. The
coefficients of correlation are not smooth functions of pressure,
and it is necessary to interpolate between the tabular values to
obtain the water content.
In the next section, the thermodynamic model used for
calculating the water content of the CO2 rich phase in
equilibrium with brine is described.

Sharma-Campbell Method
Sharma and Campbell (31) developed an approach for
determining the water content of natural gas, regardless of being
sweet or sour. In their method, the fugacity of water at
saturation and system conditions, and the fugacity and
compressibility of gas at system conditions need to be
calculated. Their method is formulated as follows:

CO2-Brine Thermodynamic Equilibrium

The thermodynamic model used in this work is based on a
combination of the methods of Duan and Sun (6) and Spycher et

al. (3), where the Spycher et al. (3) approach is employed to

calculate component fugacities in the CO2 rich phase by using
the Redlich-Kwong (34) equation of state (EOS), and the Duan
and Sun (6) activity model is utilized to calculate the activity
coefficient of CO2. This model was recently used by
Hassanzadeh et al. (8) to generate PVT data for black-oil
simulation of CO2 storage in deep saline aquifers, and they
presented detailed comparisons with experimental data and
other predictive models. Appendix A describes the RedlichKwong (34) EOS used in this study. In this section, an algorithm
is presented to estimate the water content of CO2 in equilibrium
with formation brine. The procedure for calculation of CO2
water content is as follows:

can be neglected in the calculation of the mixing rules, as

suggested by Spycher et al. (3), which in turn avoids iteration.

1.
2.
3.

Par (T , p ) = c1 + c 2 T + c3 / T + c4 p / T +

5.

ln CO = 2mC CO C + 2m A CO A
2

......................................... (16)

+ mC m A CO AC
C

The following parametric equation is used to calculate

and , after Duan and Sun (6):

Calculate gas molar volume by Equation (A5)

Calculate gas compressibility factor by PV / RT
Calculate fugacity coefficient for each component by using
Equation (A4)
0
Calculate CO2 molality in pure water ( mCO
) as outlined
(3)
below :

4.

Calculate CO2 molality in pure water ( mCO ) as outlined

below:

c5 p /(630 T ) + c6 T ln p

...................................... (17)

where Par (T , p ) can be either or , T is the temperature in

Kelvin, and p is the pressure in bar. Table 1 gives the constants
needed to calculate the interaction parameters.

0
2
5 2
4.1 logkCO
( g ) = 1.189+ 1.30410 5.44610 .............................. (9)
2

6.

Calculate molality in saline water using:

0
mCO = mCO
/ CO ............................................................................... (18)

0
2
4.2 log kH O = 2.209 + 3.097 10 1.098 ......................................... (10)

10 4 2 + 2.048 107 3

0
0
with CO = mCO
/ mCO , where mCO
and mCO are the CO2
molality in pure and saline water, respectively, as identified by
Spycher and Pruess (4).
2

p p0 V H O
exp
............................................ (11)
RT
H O p

k H0 O ( g )

4.3 A =

7.

4.4 B =

55.508k

4.5 y H O =
2

0
CO 2 ( g )

m CO

(m CO + 55.508 + m s )

........................................................ (19)

where m s is the salt molality, and is the stoichiometric

number of ions in the dissolved salt. For the NaCl solution
=2.
8.

where V H O = 18.1 cm3/mol; V CO ( g ) = 32.6 cm3/mol;

V CO (l ) = 32 cm3/mol; k is the equilibrium constant; is the
temperature in C; p is pressure in bar; p 0 is a reference
pressure (1 bar); T is the temperature in Kelvin; R is the
universal gas constant; and, V i is the average partial molar
volume of the pure condensed component i over the pressure
interval p 0 to p , which is assumed constant in the pressure
interval of interest (3).

Calculate the component mole fractions by the following

equations:

8.1 xH O = 1 xCO xsalt ....................................................................... (20)

8.2

9.

k Ho

(1 x

CO2

xsalt

H O p

) exp ( p p )V
o

k Ho O 1 x CO x salt
2

H O p
2

It is noted that the fugacity of each component in the CO2

rich phase depends on the phase composition. Therefore, the
above computations should be performed iteratively. However,
the water mole fraction in the CO2 rich phase is very small and

H 2O

RT

.................................. (21)

Calculate the CO2 water content in lb/MMSm3 using the

following equation:

= 760627.3

0
4.7 mCO
= 55.508xCO / x H O ......................................................... (15)
2

yH

4.6 xCO 2 = B(1 y H O ) .................................................................... (14)

(1 B ) ......................................................................... (13)
1/ A B
2

Calculate water and CO2 mole fractions as outlined

below(4):

xCO =

p p 0 V CO
exp
............................ (12)
RT

CO p

) exp ( p p )V

RT

H 2O

.......... (22)

In the following section, we compare the predicted water

content of CO2 with the experimental data and those obtained
by other predictive models.

water content of CO2 in equilibrium with water with zero

salinity.
The common approach to report the salinity of formation
brine in the petroleum industry is to report a constant in terms of
total dissolved solids (water-NaCl solution of equivalent total
dissolved solid) (21,46-48). In other words, the salinity equivalent
represents the effect of all different salts existing in the
formation brines.
To find the salinity correction factor, calculations are
performed at different combinations of pressure, temperature
and salinity. In particular, computations are performed for the
three different temperatures of 30, 50 and 100C and for the
pressure range of interest in the geological storage of CO2.
Results presented in Figure 5 show the correction factor as a
function of formation water salinity. These results reveal that
the calculated salinity correction factor is not sensitive to
temperature and pressure up to two significant figures. This
accuracy may be appropriate in reading the salinity correction
factor from a chart. Therefore, to calculate the CO2 water
content in equilibrium with formation brine, one needs to
calculate the water content of CO2 in equilibrium with pure
water from Figure 4 and then apply the correction factor given
in Figure 5.

Comparison with Experimental Data and

other Predictive Models
Experimental Data
The CO2-brine mixture data available in the literature have
been reviewed and used by many authors (3,4,5,6,7,9,35) to validate
their different solubility models. The calculated water content is
also compared with such experimental data from the literature
in this section. These experimental data are taken from works
done by King et al. (16), Wiebe and Gaddy (10,11), Wiebe (12),
Malinin and Savelyeva (36), Malinin and Kurovskaya (37), Song
and Kobayashi (38), Tdheide and Frank (39), Mller et al. (17),
Gillespie and Wilson (14), Sako et al. (40), Dohrn et al. (41),
Briones et al. (42), DSouza et al. (43), and Bamberger et al. (44).
The procedure presented earlier (in the CO2-Brine
Thermodynamic Equilibrium section) is used to calculate the
water content of CO2 in equilibrium with formation brine.
Tables 2 to 4 show a comparison between the predicted
equilibrium ratios and those from the experimental data
available in the literature at 25, 50 and 80C. The comparison
reveals an acceptable match in the temperature and pressure
range of interest for the geological storage of CO2 in deep saline
aquifers in the Alberta basin acid gas injection sites (10 <p<35
MPa and 38<T<80C) (45). The calculated absolute error for
the pressure range typically encountered in geological CO2
storage is within the common experimental error. Figure 1
shows a comparison between the predicted water content of the
CO2 rich phase and the experimental data reported in the
literature (10-12,14,15,16,36-44). Results presented in Figure 1
demonstrate a good agreement between the calculations and the
experimental data within the range of interest in geological
storage.

Discussion
In our investigation, we were not able to locate experimental
data of CO2 rich phase composition in equilibrium with brine.
Therefore, to validate the developed procedure, the predicted
CO2 rich phase water content was compared with the reported
experimental data available in the literature for CO2 and pure
water systems. This problem highlights the necessity of
performing experimental measurements of CO2 rich phase
composition in equilibrium with formation brines. Such
experimental measurements would facilitate further validation
of the developed chart and procedure against experimental data.
An important application for the algorithm and the developed
CO2 water content calculation procedure is in generating blackoil PVT data for flow simulation of geological CO2 storage in
deep saline aquifers and material balance calculations involved
in CO2 storage scenarios. However, it should be pointed out that
application of the presented algorithm along with black-oil
representation of PVT data is appropriate only for cases where
CO2 rich phase and formation brine exist in a reservoir or an
aquifer. This is suitable for most circumstances of geological
storage of CO2 in deep saline aquifers, where the aquifer depth
is more than 800-1000 meters and the pressure and temperature
conditions are above the CO2 critical point. However, if
conditions exist that cause CO2 to cross a phase boundary
leading to development of a new phase, or if CO2 is in close
vicinity of critical conditions, the application of the black-oil
simulation approach and/or the algorithm and chart suggested
here would be inappropriate. Among other cases, such
conditions may occur if the stored CO2 migrates to shallow
depths, as a consequence of CO2 leakage from the storage
formations.

Other Predictive Models

AQUAlibrium(24) is a software package based on a rigorous
thermodynamic model specifically developed for phase
equilibrium calculations in systems containing acid gas or sour
gas and water. Comparisons between the CO2 water content of
CO2 in equilibrium with pure water predicted in this work with
those predicted by AQUAlibrium at 50 and 75C are presented
here. Results given in Figure 2 show a reasonable agreement
between the predictions. In addition, comparisons were made
between the predicted water content of CO2 in equilibrium with
formation brine and those calculated by Spycher and Pruess (4).
Outcomes at three different temperatures (30, 60 and 90C) and
for two molalities (m = 0 and 4) are presented in Figure 3.
These results demonstrate excellent agreement. It should be
noted that, since this work is based on a combination of the
Duan and Sun (6) activity model and Spycher et al. (3) fugacity
model, it is expected that both cases lead to similar predictions.

Generation of CO2 Water Content Chart

The developed procedure can be used to calculate the water
content of CO2 in equilibrium with formation brine. To develop
a generalized chart for water content calculations, we first need
to establish a chart for the water content of CO2 in equilibrium
with pure water (zero salinity). This is achieved by setting
xsalt = 0 in Equation (22). Then, a correction needs to be applied
to account for the formation water salinity. Figure 4 shows the

Summary and Conclusion

Water content of natural gas is traditionally calculated by
general water content charts. Such general water content charts,
however, are not available for CO2 in equilibrium with
formation brine. This paper presents a simple algorithm and

REFERENCES

develops a chart for computing the water content of CO2 in

equilibrium with formation brine. The presented chart is very
simple to apply and can be used for practical applications
involving CO2 water content calculations. The developed
algorithm is also straightforward to code and may be used to
generate required black-oil PVT data for flow simulation of
CO2 storage in deep saline aquifers. In addition, the algorithm
can be easily implemented in current black-oil reservoir
simulators for flow simulation purposes.

1.

2.

3.

Acknowledgements
The authors would like to acknowledge the financial
support provided by IOR Research Institute of the National
Iranian Oil Company and University of Calgary.

4.

NOMENCLATURE
a
a
b
B
f
k
m
p
Par
R
T
T'
V
x
y
Z

=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=

activity
equation of state parameter
equation of state parameter
deviation parameter
fugacity
equilibrium constant
molality
pressure
parameter, it can be either or
universal gas constant
temperature in K
temperature in F
molar volume
mole fraction of gas in aqueous phase
mole fraction of liquid in gaseous phase
compressibility factor

=
=
=
=
=
=
=
=

correlation factor
fugacity coefficient
activity coefficient
second-order interaction parameters
water content [kg/MMSm3]
temperature in C
third-order interaction parameters
stoichiometric number of ions in the
dissolved salt

5.

6.

7.

8.

9.

10.

11.

Superscript
sat

saturation conditions

=
=
=
=
=
=
=
=

anion
cation
component index
component index
component index
saturation conditions
total
water

Subscript
A
C
k
i
j
sat
t
w

12.
13.

14.

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 RT
RTb
a b
a
V
V 3 V 2
m0.5 + bm2 m 0m.5
p
p
pT

pT

Proceedings of the 2nd Annual Conference on Carbon

Dioxide Sequestration, Alexandria, VA, 2003.
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Applied petroleum reservoir engineering, 2nd ed.,
Prentice Hall, Englewood Cliffs, NJ, 1991.
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to Primary Hydrocarbon Recovery,
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DE
AZEVEDO,
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Prentice-Hall, NJ 1986.

46.

47.

48.

49.

where R= 83.1447 bar cm3 mole-1 K-1, V is in cm3/mole, p is in

bar, T is in Kelvin, b is in cm3/mole, and a is in bar cm6 K0.5
mol-2.

Appendix A
The Redlich and Kwong EOS (34) is given by
RT
am
................................................................. (A1)

V bm T 0.5V (V + bm )

p=

where V is the molar volume of the CO2 rich phase, p is

pressure, T is temperature, R is gas constant, and parameters a
and b characterize intermolecular attraction and repulsion,
respectively. Conventionally, a and b are obtained based on the
critical properties of the components. The following CO2 and
water interaction parameters are used in the proposed module
after Spycher et al. (3):
aCO = 7.54 107 4.13 104 T (bar cm6 K0.5 mol-2), and
bCO = 27.8 (cm3/mol), aH OCO = 7.89 107 (bar cm6 K0.5 mol2
), and bH O = 18.18 (cm3/mol).
The mixture constants, a and b, are calculated using
Prausnitz et al.(49) mixing rules:
2

N N

a m = y i y j aij ................................................................................. (A2)

i =1 j =1

bm = y j bij ......................................................................................... (A3)

i =1

The fugacity coefficient k of a component can be obtained

by the Prausnitz et al.(49) formulation as:

V +b
k

ln
V
.. (A4)

a b V + bk bm
PV
ln
+ m1.5 k 2 ln

RT
b
V
V
+
b
RT

m
m

V
ln k = ln
V bm

bk
+
V b
m

= 0 ..............(A5)

N ya
i ik
2
i =1 1.5

RT bm

The volume of the gas can be calculated from the following

cubic equation

106

T=
10
0

Water content (kg/MMSm3)

5000

T=

80

T=

105
T=

60

50

C
T=

4000

m=0
m=4

3000

2000

1000

31

0
0

10

15

104

T=

20

10000

Water content (kg/MMSm3)

103

102
10 -1

30

40

50

60

Pressure (MPa)

Wter content (kg/MMSm 3)

Temperature= 30 o C
(a)

10 0

101

102

Pressure (MPa)

FIGURE 1: Comparison between CO2 water content from

experimental data(10,-14, 16-17,36-44 ) and calculated water content
for various temperatures.

Temperature= 60 o C

(b)

m=0

8000

m=4

6000

4000

2000
0

10

20

30

40

50

60

Pressure (MPa)

106
18000

Water content (kg/MMSm3)

AQUAlibrium

Water content (kg/MMSm )

This work

105

Temperature= 90 C
(c)

15000

m=0

12000

m=4

9000

6000

75 oC
0

104

10

20

30

40

50

60

Pressure (MPa)

FIGURE 3: Calculated (-) water content of CO2 in equilibrium

with pure water m=0 and with brine m=4 at three different
temperatures as compared by Spycher and Pruess(4) results().

50 oC

103
10-1

100

101

102

Pressure (MPa)

FIGURE 2: Equilibrium water content of CO2 calculated as

compared by AQUAlibrium results.

TABLE 1: Constant needed to calculate the interaction

parameters in equation from Duan and Sun (6)
CO Na
CO NaCl
Coefficient

106

11
0 o
10 C
0 o
90 o C
80 o C
C
70 o
60 o C
C
105

Water content (kg/MMSm3)

50
40
30

25

104

15

c1

-0.411370585

3.3638972310-4

c2

6.0763201310-2

-1.9829898010-2

c3

97.5347708

c4

-0.0237622469

2.12222083010-3

c5

0.0170656236

-5.2487330310-3

c6

1.4133583410-5

TABLE 2: Equilibrium phase composition of CO2 - water

system and comparison of experimental and predicted k values
at 25 C.
Pressure
(MPa)

103

102
10-1

100

101

kCO2
Exp.

kCO2
Predicted

yH2O

xCO2

0.69

0.00694

0.00331

300.018

322.766

2.53

0.00239

0.01056

94.471

89.576

5.07

0.00161

0.01904

52.436

53.350

5.07

0.00163

0.01817

52.436

53.350

10.12

0.00365

0.02368

42.076

42.299

10.13

0.00408

0.02410

41.324

42.295

20.26

0.00421

0.02567

38.792

38.678

20.26

0.00450

0.02620

37.996

38.678

40.51

0.00477

0.02871

34.665

33.937

50.63

0.00480

0.03014

33.019

32.266

102

Pressure (MPa)

FIGURE 4: CO2 water content in equilibrium with pure water

as a function of pressure and temperature.

1.00

Abs.
error

0.076
0.052
0.017
0.017
0.005
0.023
0.003
0.018
0.021
0.023

Salinity correction factor

0.95

TABLE 3 Equilibrium phase composition of CO2 - water

system and comparison of experimental and predicted k values
at 60 C.

0.90

Pressure
(MPa)

0.85

0.80

0.75

0.70
0

100

200

300

400

-3

Salinity (ppmx10 )

FIGURE 5: Salinity correction factor as a function of formation

brine salinity in ppm for three temperatures of 30, 50, and 100
C.

10

kCO2
Exp.

kCO2
Predicted

Abs.
error

yH2O

xCO2

4.05

0.00660

0.00960

103.479

98.538

0.048

5.06

0.00550

0.01210

82.190

83.084

0.011

6.06

0.00550

0.01380

72.065

73.096

0.014

7.08

0.00510

0.01570

63.369

66.076

0.043

8.08

0.00500

0.01660

59.940

61.129

0.020

9.09

0.00470

0.01790

55.603

57.473

0.034

10.08

0.00490

0.01860

53.500

54.800

0.024

11.09

0.00530

0.01950

51.010

52.822

0.036

12.09

0.00580

0.02010

49.463

51.391

0.039

14.10

0.00780

0.02080

47.702

49.449

0.037

TABLE 4: Equilibrium phase composition of CO2 - water

system and comparison of experimental and predicted k values
at 50 C.
Pressure
(MPa)

yH2O

xCO2

kCO2
Exp.

kCO2
Predicted

Abs.
error

2.529

0.00620

0.00774

128.398

135.999

0.059

4.048

0.00460

0.01090

91.321

87.347

0.044

5.057

0.00360

0.01370

72.730

75.559

0.039

5.067

0.00383

0.01367

72.873

75.454

0.035

6.057

0.00370

0.01610

61.882

65.026

0.051

6.816

0.00339

0.01650

60.401

61.113

0.012

7.076

0.00340

0.01760

56.625

59.861

0.057

7.526

0.00345

0.01750

56.946

57.695

0.013

7.596

0.00350

0.01779

56.015

57.358

0.024

8.076

0.00340

0.01900

52.453

55.047

0.049

8.715

0.00364

0.01768

56.355

53.564

0.050

9.085

0.00410

0.02000

49.795

52.744

0.059

10.055

0.00450

0.02050

48.561

50.596

0.042

10.095

0.00547

0.02075

47.929

50.508

0.054

10.125

0.00436

0.02081

47.844

50.471

0.055

10.125

0.00449

0.02018

49.332

50.471

0.023

10.128

0.00550

0.01980

50.227

50.468

0.005

11.094

0.00500

0.02100

47.381

49.549

0.046

12.094

0.00550

0.02140

46.472

48.598

0.046

12.213

0.00543

0.02096

47.451

48.516

0.022

14.102

0.00610

0.02170

45.802

47.256

0.032

14.742

0.00608

0.02215

44.872

46.905

0.045

15.192

0.00610

0.02174

45.718

46.658

0.021

15.192

0.00790

0.02100

47.243

46.658

0.012

17.671

0.00643

0.02262

43.924

45.412

0.034

19.989

0.01000

0.02300

43.043

44.408

0.032

20.089

0.00682

0.02347

42.317

44.366

0.048

20.259

0.00677

0.02289

43.391

44.300

0.021

30.084

0.00782

0.02514

39.466

41.080

0.041

40.508

0.00759

0.02606

38.082

38.614

0.014

49.973

0.01000

0.02800

35.357

36.854

0.042

60.767

0.00793

0.02868

34.591

35.219

0.018

70.892

0.00801

0.02989

33.188

33.942

0.023

11