1
Density of Aqueous Solutions of CO2
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]
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) ***
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
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
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
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
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
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
B Subroutine COCO2