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Density of Aqueous Solutions of CO2


Julio E. Garcı́a
Graduate Student Research Assistant
Earth Sciences Division

Lawrence Berkeley National Laboratory
October 11, 2001

Abstract the caprock. Because the density of CO2 saturated


water is slightly higher than the density of pure wa-
In this report, we present a numerical representation ter, density driven flow will occur enhancing the dis-
for the partial molar volume of CO2 in water and solution process by convective mixing. In such flow
the calculation of the corresponding aqueous solution problems, numerical simulation capabilities that take
density. The motivation behind this work is related into account variable density brines are crucial (Old-
to the importance of having accurate representations enburg and Pruess, 1995).
for aqueous phase properties in the numerical simu- In this report we present a new correlation for the
lation of carbon dioxide disposal into aquifers as well partial molar volume of CO2 in water and the cal-
as in geothermal applications. According to reported culation of the corresponding aqueous solution den-
experimental data the density of aqueous solutions sity. This aqueous phase density correlation is then
of CO2 can be as much as 2-3 % higher than pure incorporated into the TOUGH2 Equation-of-State
water density. This density variation might produce (EOS) module for carbon dioxide ECO2 (under de-
an influence on the groundwater flow regime. For in- velopment) (Pruess and Garcı́a, 2001; Pruess et al.,
stance, in geologic sequestration of CO2 , convective 1999). Currently, the brine density correlation con-
transport mixing might occur when, several years af- siders only salinity effects with no CO2 dependency
ter injection of carbon dioxide has stopped, the CO2 - (Battistelli et al., 1997). Figure 1 shows the com-
rich gas phase is concentrated at the top of the for- puted brine density from 10 to 110 o C at various
mation, just below an overlaying caprock. In this salt mass fractions (XNaCl=0.00, 0.05, 0.10 and 0.25)
particular case the heavier CO2 saturated water will as implemented inside EWASG. The density increase
flow downward and will be replaced by water with a due to salinity is up to almost 20%.
lesser CO2 content. Experimental data for the system H2 O-CO2 show
that the carbon dioxide content produce an increase
in aqueous phase density on the order of 2 to 3 %.
1 Introduction Because the salinity effect is considerable higher, the
dependency on CO2 content is often ignored. This
Disposal of CO2 into geological formations requires,
assumption is perfectly acceptable in geothermal ap-
among other conditions, the presence of a regional
plications. Nevertheless, as discussed before, it can
caprock for confinement. In order to avoid two-phase
conceal key processes in fluid flow dynamics of carbon
conditions in the injection line, geological disposal
dioxide sequestration.
of CO2 would be made at supercritical conditions.
Under such conditions, CO2 is less dense than wa- Based on thermodynamic theory (Söhnel and
ter and would have a tendency to migrate to the top Novotný, 1985; Anderson and Crerar, 1993), the den-
of the formation (Pruess and Garcı́a, 2001). After a sity of aqueous solutions of CO2 may be expressed as:
relatively long time (decades after ending injection)
almost all gas would be stored at the top, underlying ρaq = ρ1 + M2 · c − c · ρ1 · Vφ (1)
∗ Research Advisors: Dr. Karsten Pruess, Earth Sci-
ences Division, Lawrence Berkeley National Laboratory and
Prof. Nicholas Sitar, Department of Civil and Environmental
where Vφ is the apparent molar volume of dissolved
Engineering, University of California at Berkeley CO2 ; M2 is the molecular weight of CO2 ; ρ1 is the
† email address: garcia@ce.berkeley.edu density of pure water and c is the CO2 concentration

1
Density of Aqueous Solutions of CO2

1200 Table 1: Experimental data for partial molar volume


and density of aqueous solutions for the system CO2 -
1150 H2 O.
Brine Density [kg/m ]
3

XNaCl = 0.00
1100 XNaCl = 0.05
XNaCl = 0.10
NP * T [o C] P [M P a] Reference
1050
XNaCl = 0.25
24 5-20 6.4-29.5 Teng et al. (1997)
14 25-300 20-35 Hnědkovský et al. (1996)
1000 5 274-297 19.6-29.4 Malinin (1974)
8 25-100 1.96 Ellis and McFadden (1972)
950
25 50 75 100 1 5-40 NR ** Parkinson and Nevers (1969)
Temperature [oC]
1 25 NR ** Moore et al. (1982)
* Number of points used in this study
20 ** Not reported
18
16
Density Increase [%]

14
XNaCl=0.05
12 porting only densities and solubilities were calculated
XNaCl=0.1
XNaCl=0.25
10
using the theory presented in Appendix A.
8
6
Experimental results show that the partial molar
4 volume (approximated here as the apparent molar
2 volume) is weakly dependent on CO2 mole fraction
0
25 50 75 100 (Parkinson and Nevers, 1969) and, for temperatures
below 300o C is independent of pressure (Malinin,
o
Temprerature [ C]

1974). Salinity effects on partial molar volume of CO2


Figure 1: Computed density and density increase of in water are not considered in this study. There are
NaCl solutions for salt mass fraction (XNaCl) from 0 limited data that consider salinity. Malinin (1974)
to 0.25 using the EWASG correlation. presented several data points for solutions of 1 M
NaCl at high temperatures and pressures. His find-
ings showed that the salinity effects are weak and
expressed by the number of moles of solute in 1 m within experimental uncertainty.
3

of solution (for details see Appendix A).


2.1 Previous Work
2 Experimental Data and Pre- There are correlations available for the partial molar
volume as a function of temperature. Most of these
liminary Correlations representations consider a polynomial fit as follows:

A large number of data exist on the solubility of CO2 Vφ = a + bT + cT 2 + dT 3 + eT 4 (2)


in water (Scharlin (1996) and Drummond (1981)).
In spite of their significance, there is limited experi- Table 2 summarizes the different fits for Equation
mental data on densities of the aqueous system H2 O- 2 found in the literature as well as other types of
CO2 -NaCl. Usually, there is two sets of data, one correlations.
for the system H2 O-NaCl and another for the system
H2 O-CO2 . Because the effect of salinity on density is 2.2 Novel Correlation
considerably higher than the effect of carbon dioxide,
The fit to Equation 2 proposed in this study considers
the latter is often ignored. The most significant inves-
53 data points (See Figure 2). The following equation
tigations of partial molar volume of CO2 and density
adequately represents the data with an R2 = 0.98.
of aqueous solutions of CO2 along with experimental
conditions are listed in Table 1.
The data collected indicate that CO2 saturated wa- Vφ =37.51 − 9.585 ∗ 10−2 T
ter is heavier than pure water below 300 o C and down (3)
+ 8.740 ∗ 10−4 T 2 − 5.044 ∗ 10−7 T 3
to at least 5 o C. Some measurements were done at
CO2 saturation, while others were for very low mole Equation 3 and 1 were used to compute densities
fraction. Apparent molar volumes for data sets re- of aqueous solutions of CO2 at a pressure of 100 bar

2
Density of Aqueous Solutions of CO2

Table 2: Correlations used by other authors for partial molar volume of CO2 in water.

a b c d e Reference

37.36 −7.109 ∗ 10−2 −3.812 ∗ 10−5 +3.296 ∗ 10−6 −3.702 ∗ 10−9 Andersen et al. (1992) *
1799.36 −17.8218 0.0659297 −1.0579 ∗ 10−4 +6.200 ∗ 10−8 Enick and Klara (1990) **
35.663 −5.960 ∗ 10−2 +6.308 ∗ 10−4 Jonathan Ennis-King1 *
37.51 −9.585 ∗ 10−2 +8.740 ∗ 10−4 −5.044 ∗ 10−7 This work *
3582.452
Vφ = e154.7881− T −26.7757773log(T )+0.045234908T
Iglesias and Moya (1992) ***

* Equation 2 Vφ is in cm3 /mole and T is in degrees Celsius


** Equation 2 Vφ is in cm3 /mole and T is in degrees Kelvin
*** Vφ is in cm3 /mole and T is in degrees Kelvin
1
Personal Communication

1040
90 1030
H 2O-CO2 Density [kg/m3]
1020
80 1010
Apparent Molar Volume [cm3/mole]

1000
70 990
980
Xmole = 0.00
60 970 Xmole = 0.02
960 Xmole = 0.05

50 950
940
25 50 75 100
40 Temperature [oC]

30 (a)
(b) 3
(c)
20
(d) 2.5
Density Increase [%]

(e)
10 This Work 2
Xmole = 0.02
0 Xmole = 0.05
1.5
0 100 200 300
o
Temperature [ C]
1

0.5
Figure 2: Fit of Partial Molar Volume Vs. Tempera-
0
ture. (a) Teng et al Teng et al. (1997), (b) Hnedkosky 25 50 75 100
o
Temperature [ C]
et al Hnědkovský et al. (1996), (c)Malinin Malinin
(1974), (d) Ellis and McFadden Ellis and McFadden Figure 3: Computed density of aqueous solutions of
(1972), (e)Moore et al Moore et al. (1982) CO2 (P=100 bar)

for mole fractions (Xmole) of 0.02 and 0.05 (Figure measured and predicted values of the partial molar
3). A maximum density increase of 2.5 % is obtained volume of CO2 in water and the density of aqueous
for a solution with a CO2 mole fraction of 0.05. solutions of CO2 , respectively. Predicted values using
As expected according Equation 1, the density vari- Equation 3 agree very well with the measured data.
ation of the aqueous solutions of CO2 is nearly lin-
ear with respect to CO2 mole fraction (See Figure
4). Figure 5 and 6 show a comparison between the

3
Density of Aqueous Solutions of CO2

1030

1025

1000
H 2O-CO2 Density [kg/m ]

1020
3

Calculated Density [kg/m3]


1015

1010 950
a)
1005 b)
P=100 [bar]
P=200 [bar] c)
1000 P=300 [bar] d)
900 1-1

995

990
0 0.01 0.02 0.03 0.04 0.05 850
CO2 mole fraction 850 900 950 1000
Measured Density

Figure 4: Computed density of aqueous solutions of a)


0.01
CO2 (P=100 bar) b)
c)
0.0075 d)
Zero
0.005

Relative Error
0.0025
90 0

-0.0025
80
-0.005
Calculated Molar Volume

70 -0.0075

-0.01
60 850 900 950 1000
Measured Density
a)
b)
50 c)
d) Figure 6: Comparison between measured and pre-
1-1
40 dicted density of aqueous solution of CO2

30
30 40 50 60 70 80 90
Measured Molar Volume
3 TOUGH2-ECO2 Implemen-
tation
1 a)
b)
c)
0.75 d) The proposed new formulation for the partial molar
Zero
0.5 volume of CO2 in water and the corresponding
aqueous solution density is incorporated into the
Relative Error

0.25

0 TOUGH2 Equation-of-State module ECO2 through


-0.25
the new subroutine COCO2. Only few changes
are required in the rest of the module. Calls to
-0.5
subroutine COCO2 require the following arguments:
-0.75
aqueous phase temperature and pressure, CO2 and
-1
30 40 50 60 70 80 90 Salt mass fractions, and brine density:
Measured Molar Volume

CALL COCO2(TX,PL,XG,XSA,DB)
Figure 5: Comparison between measured and pre-
dicted partial molar volume of CO2 in water The CO2 dependency on brine density can be
turned on through parameter specification in data
block SELEC. A description of additional SELECtion
options is provided in Pruess et al. (1999).

4
Density of Aqueous Solutions of CO2

IE(9) Allows to select brine density as a function References


of CO2 content
0: Brine density independent of CO2 content Andersen, G., Probst, A., Murray, L., and Butler, S.
1: Full dependence (1992). An accurate PVT model for geothermal
fluis as represented by H2 O-CO2 -NaCl mixtures.
Proceedings, Seventeenth Workshop on Geothermal
Reservoir Engineering, 17:239–248. Stanford Uni-
versity, Stanford, California, January 29-31, 1992.
The beta version of subroutine COCO2 is pre-
sented in Appendix B. Anderson, G. M. and Crerar, D. A. (1993). Ther-
modynamics in Geochemistry: The Equilibrium
Model. Oxford University Press.

Battistelli, A., Calore, C., and Pruess, K. (1997).


4 Nomenclature The simulator TOUGH2/EWASG for modelling
geothermal reservoirs with brines and non-
c molarity of solution (moles/m3 ) condensible gas. Geothermics, 26(4):437–464.
M molecular weight (kg/mol)
m molality of the solution expressed in Drummond, S. E. (1981). Boiling and Mixing of Hy-
moles of solute in 1 kg of solvent drothermal Fluids: Chemical Effects on Mineral
(mol/kg) Precipitation. PhD thesis, Pennsylvania State Uni-
ni number of moles of the i-th component versity.
in the mixture (mol)
P pressure (Pa) Ellis, A. and McFadden, I. (1972). Partial molal vol-
T temperature (o C) umes of ions in hydrothermal solutions. Geochimica
V volume (m3 ) et Cosmochimica Acta, 36:413–426.
Vi partial molar volume of the i-th compo-
Enick, R. M. and Klara, S. M. (1990). CO2 solubil-
nent (m3 /mol)
ity in water and brine under reservoir conditions.
Vm molar volume (m3 /mol)
Chem. Eng. Comm., 90:23–33.
Vφ apparent molar volume of dissolved
CO2 (m3 /mol) Hnědkovský, L., Wood, R. H., and Majer, V. (1996).
xi molar fraction Volumes of aqueous solutions of CH4 , CO2 , H2 S,
ρ density of the solution (kg/m3 ) and NH3 at temperatures from 298.15 K to 705 K
ρ1 density of water (kg/m3 ) and pressures to 35 Mpa. J. chem. Thermodynam-
ics, 28:125–142.
Subscripts
Iglesias, E. R. and Moya, S. L. (1992). An accurate
aq aqueous phase formulation of the solubility of CO2 in water for
s mixture geothermal applications. Proceedings, Seventeenth
1 solvent (H2 O) Workshop on Geothermal Reservoir Engineering,
2 solute (CO2 ) 17:231–238. Stanford University, Stanford, Cali-
fornia, January 29-31, 1992.
Superscripts
Malinin, S. (1974). Thermodynamics of the H2 O-CO2
o at infinite dilution system. Geochemistry International, 11:1060–1085.

Moore, J. C., Battino, R., Retitic, T. R., Handa, P.,


Acknowledgement and Wilhelm, E. (1982). Partial molar volumes of
”gases” at infinite dilution in water at 298.15 k. J.
For a review of the manuscript and suggestions Chem. Eng. Data, 27:22–24.
of improvements, thanks are due to Karsten Pruess
and Tianfu Xu. This work was supported by Oldenburg, C. M. and Pruess, K. (1995). Dis-
the U.S. Department of Energy through the Of- persive transport dynamics in a strongly coupled
fice of Basic Energy Sciences under Contract No. groundwater-brine flow system. Water Resources
DE-AC03-76SF00098. Research, 31(2):289–302.

5
Density of Aqueous Solutions of CO2

Parkinson, W. and Nevers, N. D. (1969). Partial mo- constant temperature and pressure. The total vol-
lal volume of carbon dioxide in water solutions. In- ume of a system with j-components can be expressed
dustrial and Engineering Chemistry Fundamentals, by the relation:
8(4):709–713.
Xj

Prausnitz, J. M., Lichtenthaler, R. N., and V = ni Vi (4)


de Azevedo, E. G. (1986). Molecular Thermody- i=1

namics of Fluid-Phase Equilibria. Prentice-Hall, where


second edition.
µ ¶
∂V
Pruess, K. and Garcı́a, J. E. (2001). Multiphase flow V i = (5)
∂ni T,P,nj6=i
dynamics during CO2 disposal into saline aquifers.
Environmental Geology, Submitted(Submitted). is the partial molar volume of the i-th component.
Pruess, K., Oldenburg, C., and Moridis, G. (1999). In practice, the apparent molar quantities are more
TOUGH2 User’s Guide Version 2.0. Technical Re- easy to be determined, and the partial molar quan-
port LBL-43134, Lawrence Berkeley National Lab- tities are calculated from these. For binary solutions
oratory. the apparent molar volume, Vφ , is defined as:
Scharlin, P. (1996). Carbon Dioxide in Water and V − n1 Vm,1
Aqueous Electrolyte Solutions, volume 62 of Sol- Vφ = (6)
n2
ubility Data Series. Oxford University Press, In-
As illustrated in Figure 7, the apparent molar vol-
ternational Union of Pure and Applied Chemestry,
ume is the volume that should be attributed to the
Oxford, UK.
solute in the solution if one assumes that the solvent
contributes the same volume it has in its pure state.
Söhnel, O. and Novotný, P. (1985). Densities of
Alternatively,
Aqueous Solutions of Inorganic Substances. Else-
vier: New York.
V = n1 Vm,1 + n2 Vφ (7)
Teng, H., Yamasaki, A., Chum, M.-K., and Lee, H.
(1997). Solubility of liquid CO2 in water at temper-
atures from 278 K to 293 K and pressures from 6.44 6
MPa to 29.49 MPa and densities of the correspond- ´
ing aqueous solutions. J. Chem. Thermodynamics, ´
´ V2
29:1301–1310. ´
Volume ´
´
V (m3 ) ´
´n 6 Volume attributed
´ 2 Vφ to solute
´ ?
A Density of Binary Aqueous 6
Solutions Volume attributed
n1 Vm,1
to solvent
The partial molar volume is an important thermo-
dynamic quantity since: (1) its value may be used ? -
to correct Henry’s constant when the gas pressure is
large (Prausnitz et al., 1986) and; (2) the knowledge Moles of solute, n2
of its value can be used to estimate the density of the
solution. In this appendix we present an overview of
theory related to partial molar volumes and estima- Figure 7: Total volume of a solution as a function of
tion of the corresponding binary aqueous solutions solute concentration showing the difference between
density. For additional details the reader is referred partial molar volume and apparent molar volume.
to Prausnitz et al. (1986) and Anderson and Crerar Adapted from Anderson and Crerar (1993).
(1993).
The definition of a partial molar property is ap-
plicable only to extensive properties differentiated at Dividing Equation 7 by (n1 + n2 ) we obtain:

6
Density of Aqueous Solutions of CO2

Vm = x1 Vm,1 + x2 Vφ (8) ρ1 − ρ M2
Vφ = + (12)
mρρ1 ρ
The apparent molar volume Vφ can be seen (Figure
Or, if the composition is expressed by the number
8) to be the intercept on the solute axis.
of moles of solute in 1 m3 of solution (i.e. n2 = c n1 =
(ρ − cM2 )/M1 ):
ρ1 − ρ M2
Vφ = + (13)
cρ1 ρ1
V1 Either Equation 12 or 13 can be used to obtain an
HH
V1 XXH
expression for aqueous density. From equation 13
V XH
XHXH
XHXXX
HHXX V2 ρaq = ρ1 + M2 · c − c · ρ1 · Vφ (14)
H XXXX
HH V2 Or from equation 12:
HH
H 1 + mM2
Vφ ρ= (15)
mVφ + ρ11
where m can be expressed in terms of mol fractions
0 A 1 (x1 , x2 ) as:
Moles fraction, x2
1 x2
m= ³ ´= (16)
1 M1 x1
M1 x2 −1
Figure 8: Molar volume of a binary solution versus mM1
mole fraction showing the difference between partial x2 = (17)
1 + mM1
molar volume and apparent molar volume for solu-
tion at composition A. Adapted from Anderson and Replacing equation 16 into equation 15
Crerar (1993) x2 M2
1+ M1 x1
ρ= x2 Vφ 1
(18)
M1 x1 + ρ1
The partial molar volume of solute and solvent in
After further simplification we obtain an alterna-
a binary solution can be obtained from Vφ as:
tive equation for the aqueous phase density
µ ¶ µ ¶ 1 x2 V φ M1 x1
∂V ∂Vφ = + (19)
V2 = = Vφ + n2 (9) ρ MT ρ1 MT
∂n2 T,P,n1 ∂n2 T,P,n1
where MT = M1 x1 + M2 x2
at infinite dilution (i.e. n2 → 0) the following rela-
tion holds
A.1 Ideal Solutions
o
V =
2 Vφo (10) For an ideal solution, the partial molar volumes of the
i.e. the partial molar volume of a solute at infi- species in solution are equal to the molar volumes of
nite dilution is equal to its apparent molar volume at pure species at the same temperature and pressure.
infinite dilution. In this event, the total volume becomes:
The apparent partial molar volume can be ex-
pressed in terms of densities and molecular weights V = n1 Vm,1 + n2 Vm,2 (20)
(Teng et al., 1997). Expressing the molar volumes in terms of densities
µ ¶ (Vm,i = M i
ρi ):
1 n1 M1 + n2 M2 M1
Vφ = − n1 (11)
n2 ρ ρ1 M1 M2
V = n1 + n2 (21)
If the composition is expressed by the number of ρ1 ρ2
moles of solute in 1 kg of solvent (i.e. n2 = m n1 = n1 M1 + n2 M2 M1 M2
1/M1 ), we obtain: = n1 + n2 (22)
ρ ρ1 ρ2

7
Density of Aqueous Solutions of CO2

Dividing Equation 22 by the total mass:


1 X1 X2
= + (23)
ρ ρ1 ρ2
n1 Mi
Where Xi = n1 M1 +n2 M2 is the mass fraction of
specie i.

B Subroutine COCO2

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