3144 Ind. Eng. Chem. Res.

1999, 38, 3144-3161

Solubility of Hydrocarbons and CO2 Mixtures in Water under

High Pressure
Aleksande1 r Dhima,†,‡ Jean-Charles de Hemptinne,*,† and Jacques Jose§
Institut Français du Pétrole, 1 à 4 avenue de Bois Préau, Rueil-Malmaison Cedex, 92852 France, and
Université Claude BernardsLyon 1, 43, Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex, France

New solubility data for methane, carbon dioxide, and their binary mixtures in pure water were
obtained at 344.25 K and from 10 to 100 MPa. A thermodynamic model that combines a cubic
equation of state (Peng-Robinson with kij given in the literature) with the Henry’s law approach
has been elaborated. It has been shown that the (P,T) functional form of Henry’s constant given
by the Krichevsky-Kasarnovsky equation is applicable. It involves two important parameters:
partial molar volume at infinite dilution and Henry’s constant at the vapor pressure of water.
Neither of these two parameters is a function of pressure or composition. The Henry’s constant
correlations of Li and Nghiem and Harvey, and the partial molar volume correlation of Lyckman
et al. have been validated using a great number of solubility data.

1. Introduction given solute i in the aqueous phase, faq i (P,T,x j) is its

Solubilities of hydrocarbons and natural-gas compo-
nents such as CO2 and H2S in water are of great interest
to petroleum engineers. Especially under high-pressure/
high-temperature conditions, hydrocarbon-water mu-
tual solubilities become important. Unfortunately, the
experimental data and therefore the theoretical knowl-
edge still present some gaps.
In a previous work,1 we have published some solubil-
ity data of methane, ethane, n-butane, and the binary
mixtures of methane and ethane or n-butane in pure
water at 71 °C (160 °F) and at high pressures. These
data have been analyzed on the basis of Henry’s law,
which seems to be a very simple and powerful approach.
Contradicting some ambiguous literature data,2,3 we
concluded that, using this approach, the ternary solubil-
ity data can be predicted by the binary ones.
This paper gives, for the same conditions, some new
data on the solubility of carbon dioxide and carbon
dioxide + methane mixtures in water. The analysis of
these data allows us to reach the same conclusion: the
binary solubility data, as well as the ternary ones, can
be predicted using the Henry’s law approach.
Henry’s law is expressed in its most general form by4,5
faq j) ) γH
i (P,T,x
aq
i (Pref,T,x)‚xi ‚H°
i,w(Pref,T)
aqueous-phase fugacity under the system pressure and
temperature conditions, and H°i,w(Pref,T) is its corre-
sponding Henry’s constant defined at the reference
pressure, Pref.
The use of eq 1 to calculate the solute aqueous-phase
fugacity requires the knowledge of three parameters:
(1) the aqueous phase activity coefficient γH j);
i (Pref,T,x
(2) Henry’s law constant of component i in water H°i,w
(Pref,T); (3) the aqueous partial molar volume of com-
ponent i vj aq
i .
The use of eq 1 for a phase equilibrium calculation
requires, in addition, an equation of state (EOS) for
evaluating the hydrocarbon (vapor or liquid)-phase
fugacity of each component in the presence of water.
This work has two objectives. First, we want to
complete the solubility data published in our previous
paper.1 Second, we will determine all three parameters
mentioned above (γH j),H°i,w(Pref,T),vj aq
i (Pref,T,x i ) for sev-
eral important hydrocarbons and CO2, using a large
number of solubility data.
2. Experimental Data and Discussion of the
Results

(∫ )
In this work we complete our previously published
P v j aq j)
i (P,T,x
solubility data1 with solubility measurements of pure
exp dP (1) carbon dioxide and its binary mixtures with methane
Pref RT
in pure water at 71 °C (160 °F). The high-pressure
with apparatus (given in Figure 1) and the experimental
procedure are described in our previous work.1 In
contrast to the previously published method, no inert
lim γH
i ) 1
xif0 gas is used during the flash (see Figure 1). The residual
solubility of gases in the trapped water at atmospheric
where xj ) xj(xaq aq aq aq
1 , ..., xi , ..., xn-1, xw ) is the vector of the
pressure is also measured by chromatography using a
aq
aqueous phase composition, xi is the mole fraction of a technique described by Benoit and Monot6 and was
nearly 800 ppm mole fraction in the case of pure carbon
dioxide and between 150 and 500 ppm mole fraction for
* Corresponding author. E-mail: J-charles.de-hemptinne@
ifp.fr. Fax: 33 (1) 47 52 70 25. Phone: 33 (1) 47 52 71 28. the methane-carbon dioxide mixtures. The results
† Institut Français du Pétrole. presented in Table 1 take into account these corrections.
‡ Present address: ENSM de Paris, 35, rue Saint-Honoré, It should be noted that, since the solubility of carbon
77305 Fontainebleau Cedex, France. dioxide in water is very high, the composition of the
§ Université Claude BernardsLyon 1. gaseous mixtures has changed with equilibrium pres-
10.1021/ie980768g CCC: $18.00 © 1999 American Chemical Society
Published on Web 07/16/1999
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3145

Figure 1. Schematic diagram of experimental apparatus.

Table 1. Corrected Solubility of Carbon Dioxide and Methane-Carbon Dioxide Mixtures in Pure Water at 71 °C (160 °F)

total pressure mole fraction of pure total pressure equilibrium methane mole aqueous mole fraction of
(MPa) CO2 in aqueous phase (MPa) fraction in gaseous mixturea C1 CO2 C1 + CO2
10 0.0166 10 0.5670 0.000 776 0.008 346 0.009 122
12.5 0.0182 10 0.8045 0.001 100 0.003 555 0.004 655
15 0.0197 20 0.5700 0.001 310 0.011 300 0.012 610
20 0.0213 20 0.8102 0.001 820 0.005 390 0.007 210
50 0.0256 50 0.5850 0.002 434 0.012 670 0.015 104
50 0.8205 0.003 190 0.006 265 0.009 455
75 0.0285 75 0.5870 0.003 027 0.014 347 0.017 374
75 0.8260 0.003 893 0.007 105 0.010 998
100 0.0317 100 0.5940 0.003 610 0.015 071 0.018 681
a On dry basis.

sure. Another peculiarity of the CO2 is its high density.
Under pressures higher than 800 bar the compressed
pure supercritical carbon dioxide at 71 °C is heavier
than the liquid water. In this case the flash is performed
maintaining the equilibrium cell as presented in posi-
tion 1 of Figure 1, while the equilibrium was attained
in position 2.
The fluids used in this work were all purchased from
Air Liquide and have a degree of purity of g 99.995%,
specified as N45. As in our previous work, the temper-
ature measurement is accurate within 2 °C and the
pressure is regulated and maintained constant during
the flash with a precision of (1%. Subsequently, we
estimate an overall experimental uncertainty of (2%.
Figure 2 summarizes the binary solubility data
obtained in this and previous work.1 A brief comparison
with some other literature data shows good agreement.
It should be noted that the literature data of carbon
dioxide dissolved in water correspond to 75 °C, as given
by Wiebe and Gaddy,7 Gillespie and Wilson,8 and Sako
et al.9).
We observe that the Soreide and Whitson model10
describes very well the methane and ethane water
solubility but slightly underestimates the solubility of
n-butane in water compared to the solubility data
reported by Reamer et al.11 and Sage and Lacey.12 The
solubility of CO2 in water is well described at high
pressure, but it is slightly underestimated at moderate
pressure (up to 300 bar).
Figure 3 compares our measurements on the aqueous
solubility of methane-carbon dioxide mixtures with the
Soreide and Whitson model.10 Again, the predicted
values are slightly lower than the measured values,
especially at moderate pressure.
3146 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Figure 2. Solubility of methane, ethane, butane, and carbon dioxide in pure water at 71 °C (160 °F).

Figure 3. Total solubility of methane-CO2 mixtures in water at 71 °C (160 °F).

3. Proposed Modeling Approach
In this work, the fugacity coefficients of the hydro-
carbon-phase components are described with a cubic
equation of state, while those of hydrocarbons in the
aqueous phase are calculated using a Henry’s law
approach.
3.1. Hydrocarbon-Rich Phase. The equation that
will be considered here is the Peng-Robinson13 equation
of state:
The temperature dependence of the attractive param-
eter for any component (i) other than water (w) is given
by the usual Soave relationship, with the parameters
of Robinson and Peng.14 For water (w) we develop a
specific R function of the form
Rw(Tr,w) ) 1 + R1(1 - xTr,w) + R2(1 - xTr,w)2 (2)
Knowing the vapor pressure of water given by Saul and
Wagner15 and on the basis of a very simple procedure
given by Soave,16 we easily determine the value of the
Peng-Robinson R function for each temperature. The
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3147

Figure 4. Aqueous activity coefficient ratio of methane and carbon dioxide at 71 °C (160 °F).

Table 2. Binary Interaction Parameters Used in This Work

methane ethane propane butane pentane decane toluene CO2
methane 0.0079 0.0153 0.0218 0.0268 0.0431 0.0412 0.1300
ethane 0.0079 0.0013 0.0038 0.0063 0.0161 0.0146 0.1300
propane 0.0153 0.0013 0.0007 0.0019 0.0086 0.0074 0.1268
butane 0.0218 0.0038 0.0007 0.0003 0.0045 0.0036 0.1236
pentane 0.0268 0.0063 0.0019 0.0003 0.0024 0.0017 0.1204
decane 0.0431 0.0161 0.0086 0.0045 0.0024 0.0001 0.1043
toluene 0.0412 0.0146 0.0074 0.0036 0.0017 0.0001
CO2 0.1300 0.1300 0.1268 0.1236 0.1204 0.1043
H2O 0.5000 0.5000 0.5200 0.5400 0.5000 0.4540 0.2850 0.1896

Table 3. Critical Component Parameters and Acentric other hydrocarbons. The binary interaction parameters
Factors Used in This Work between carbon dioxide and hydrocarbons are also taken
Tc (K) Pc (bar) Zc ω from Davidson et al.,18 while the CO2-water parameters
methane 190.4 46.0 0.288 0.011 are taken from Soreide and Whitson.10 The component
ethane 305.4 48.8 0.285 0.099 critical parameters are from Reid et al.20 The binary
propane 369.8 42.5 0.281 0.153
butane 425.2 38.0 0.274 0.199 interaction parameters used are summarized in Table
pentane 469.7 33.7 0.263 0.251 2, and the critical parameters in Table 3.
decane 617.7 21.2 0.249 0.489
toluene 591.8 41.0 0.263 0.263 3.2. Aqueous Phase. The fugacity of water (w) in
CO2 304.1 73.8 0.274 0.239 the aqueous phase will be calculated using the following
H2O 647.3 221.2 0.235 0.344
equation proposed in our earlier work:1

[ ]
regression of R1 and R2 between 273 and 498 K yields
vlw
faq j) = xaq
w (P,T,x
sat sat sat
w ‚φw (Pw ,T)‚Pw exp (P - Psat
w )
R1 ) 1.814 852 14 RT
(3)
and Since the solubility of hydrocarbons in the aqueous
phase is generally very low, the water activity coefficient
R2 ) 0.325 217 76
in the aqueous phase is considered equal to unity.
Furthermore, for temperatures far from the water
Using this procedure, the average error on the R
critical temperature (we consider temperatures up to
parameter is 0.4%.
200 °C), the saturated molar volume of the liquid water
The conventional mixing rule has been used for the
parameters a and b of the equation of state. The use of vlw is considered independent of pressure.
binary interaction parameters coming from different The water fugacity coefficient at saturation
sources is not recommended. Nevertheless, we could not φsat sat
w (Pw ,T) has been calculated using the expression
find a single author providing all the parameters given by Li and Nghiem.21 The water vapor pressure,
needed. We used the following references. The binary Psat
w (T) and the saturated liquid water molar volume,
interaction parameters kij between all hydrocarbons vlw(T) are both calculated using the expressions given
from methane to decane are taken from Gao et al.17 The by Saul and Wagner.15
binary interaction parameters between hydrocarbons The fugacity of all hydrocarbons i dissolved in the
and water are taken from Davidson et al.18 for methane aqueous phase will be calculated using the Henry’s law
to butane and from Tsonopoulos and Heidman19 for approach. This approach may be summarized as fol-
3148 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Figure 5. Relative behavior of ternary systems with methane in water of ethane, butane, and CO2 at 71 °C and for pressures from 10
to 100 MPa.

Figure 6. Behavior of some ternary systems compared to their respective binary systems.

lows:4 The Henry’s constant, Hi,w(P,T) is always defined at

infinite dilution of the solute in the solvent. When the
faq H
j)‚xaq
i (P,T,x) ) γi (Pref,T,x i ‚Hi,w(P,T) ) system pressure reaches the solvent saturation pres-

(∫ )
sure, both phases contain nothing but solvent molecules,
P vj aq j)
i (P,T,x
γH j)‚xaq and infinite dilution is thus automatically reached. It
i (Pref,T,x i ‚H°
i,w(Pref,T) exp dP (1)
Pref RT is therefore common to define the Henry’s constant at
with the solvent vapor pressure Psat w , considered as the
reference pressure:
lim γH
i ) 1
xif0 faq j)
i (P,T,x
H°i,w(Psat
w ,T) ≡ lim (4)
We will discuss each of the factors in turn. (xaq sat
i f0),(PfPw ) xaq
i
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3149

Figure 7. Ideal behavior of the aqueous phase at 71 °C (160 °F).

Table 4. Observed and Calculated Partial Molar independent of pressure, one obtains
Volumes and Henry’s Constants at Saturated Water
Vapor Pressure at 71 °C
fhc
i vj aq
i
partial molar
volume (cm3/mol)
ln ) ln(γH
i H°
i,w) + (P - Psat
w ) (5)
Henry’s constant: xaq RT
i
calcd value H°(T) (MPa)
our
Lyckman Brelvi and measure- calcd value our The well-known Krichevsky-Kasarnovsky [K-K]
solute et al.36 O’Connell 41 ment Harvey42 measurement
equation22 is written using vj aq j ∞i and γH
i ) v i ) 1:
methane 36 41 34 6178 5930
ethane 52 52 48 6213 6073
n-butane
CO2
91
36
72
39
89
33
7980a
390
8002
374
fhc
i vj ∞i
ln ) H°
i,w + (P - Psat
w ) (6)
a Li and Nghiem.21 xaq RT
i

Table 5. References Providing Henry Constant Values of

Light Hydrocarbons in Water Generally, it is admitted that at low temperatures the
aqueous solute ref
[K-K] equation works well for the hydrocarbons dis-
solved in water under high pressure (up to 1000 bar).
methane, ethane, propane, butane, Li and Nghiem21
pentane, octane, carbon dioxide The only paper presenting some doubts is presented by
methane, ethane Fernandez-Prini and Crovetto45 O’Sullivan and Smith.23 They conclude that the change
carbon dioxide for T < 353 K Crovetto46 of the aqueous partial molar volumes of methane and
carbon dioxide for T > 353 K Crovetto46
methane, ethane, carbon dioxide, Harvey42 nitrogen with pressure is not negligible. Subsequently,
hydrogen sulfide + gases the [K-K] equation cannot be applied to model the
methane, ethane, propane Carroll and Mather47 aqueous phase. This point is mentioned more recently
butane Carroll et al.48
by Lekvam and Bishnoi,24 without any analysis. We will
further demonstrate that a constant γH i value can be
However, the true molar fraction of solute in water used.
may not be zero. A correction factor, or activity coef- However, for CO2 and at high temperatures some
ficient γH controversy remains concerning the use of the [K-K]
i , that is a function of the mole fraction must
therefore be used. Although the activity coefficient can equation: King25 and Weiss26 conclude that the [K-K]
be taken as a function of pressure, it is most convenient equation can be used to correlate the water solubility
to define it at the same reference pressure as that for data of CO2 given by Wiebe and Gaddy7,27 while Par-
kinson and De Nevers,28 Gibbs and Van Ness,29 and
the Henry’s constant, that is, the water vapor pressure.
Malinin30 conclude that the activity coefficient γHi can-
It is then only a function of temperature and mole
not be neglected. This contradiction is analyzed by
fraction and can be considered as a correction on the
Carroll and Mather in a more recent paper31 that
Henry’s constant. concludes that the [K-K] equation is valid below 100
The last factor of eq 1 provides the influence of °C, while at higher temperatures a γH i should be used.
pressure on the fugacity. When the partial molar volume Using a detailed analysis of all available data, we
of component i in the aqueous phase is considered investigate this question in a separate section.
3150 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Table 6. Application of Eq 5 and Results Obtained on the Methane-Water System

T (K) H°γH (MPa) vaq 3
i (cm /mol) σ (%) Adev (%) MaxDev (%) N P (MPa) ref
323 5851 36 1.0 0.9 1.6 6 5-21 Michels et al.49
298 3864 35 2.0 1.5 4.3 11 3-64 Culberson and McKetta50
311 4767 32 1.0 0.8 2.1 12 2-68
344 6271 34 1.9 1.6 4.1 12 2-68
378 6409 37 1.9 1.4 4.5 13 2-68
411 5748 36 1.8 1.5 3.7 12 2-68
444 4405 41 1.9 1.5 3.4 12 2-68
298 3889 2.8 2.4 4.9 7 2-5 Duffy et al.51 a
325 5418 34 0.3 0.3 0.4 6 10-61 O’Sullivan and Smith23
376 6167 40 1.5 1.3 2.2 6 10-61
398 5957 46b 2.1 2.0 2.9 6 10-61
311 4798 31 0.1 0.1 0.1 4 4-34 Amirijafari and Campbell3
344 6086 39 0.9 0.8 1.6 4 4-34
423 5092 38 2.5 1.9 5.9 12 5-108 Sulltanov et al.52
473 3135 43 2.4 1.8 5.5 12 5-108
523 1853 47 0.9 0.7 1.9 8 25-108
473 3610 46 2.1 1.8 3.0 6 9-98 Sulltanov et al.53
523 1935 63 4.2 3.7 6.7 6 9-98
423 5873 50 16.6 14.1 24.0 9 30-250 Sanchez54
473 3445 43 7.4 5.7 16.3 10 20-250
523 2608 44 12.8 10.5 27.9 10 20-250
427 4394 43 10.6 9.1 18.0 9 3-164 Price55
479 2994 43 8.0 6.8 14.0 8 5-192
423 5139 41 0.4 0.4 0.6 3 1-14 Gillespie and Wilson8
478 3362 28 0.0 0.0 0.0 3 6-14
298 3889 28 2.2 1.6 4.0 5 3-12 Yarym-Agaev et al.56
313 4715 29 1.2 1.0 2.0 5 3-12
338 5748 32 0.9 0.8 1.4 5 3-12
298 4074 0.2 0.2 0.3 3 3-5 Yokoyama et al.57 a
323 5490 1.2 1.1 1.7 3 3-5
283 2914 1.0 0.8 1.4 4 1-5 Wang et al.58 a
288 3267 1.0 0.9 1.5 5 1-5
293 3798 8.5 8.0 10.5 5 1-5
298 3757 1.1 0.9 2.1 6 1-5
283 1400 2 0.18-0.2 Reichl59 a
303 4458 2 0.19-0.22
323 2392 2 0.21-0.24
343 6148 2 0.23-0.26
274 2273 4.0 3.5 6.0 8 1-3 Lekvam and Bishnoi24 a
283 3039 6.8 5.7 11.8 4 2-7
286 3213 1.3 1.0 2.1 5 2-9
324 5391 34 3.0 2.5 5.2 7 10-58 Gao et al.60
344 5930 34 1.4 1.2 2.3 4 20-100 Dhima et al.1
a Considered as low-pressure solubility data. b Unreasonable value.

Table 7. Application of Eq 5 and Results Obtained on the Ethane-Water System

T (K) H°γH (MPa) vaq 3
i (cm /mol) σ (%) Adev (%) MaxDev (%) N P (MPa) ref
311 4165 48 2.9 2.8 4.6 10 4-65 Culberson and McKetta61
344 6303 49 2.6 2.0 6.3 11 2-66
378 7011 50 3.9 3.3 7.5 12 2-68
411 5958 59 3.0 2.4 5.5 12 2-67
444 4603 61 2.1 1.5 4.4 13 5-68
473 3037 61 19.0 16.4 32.7 8 20-350 Danneil et al.62
523 2072 51 15.0 12.7 26.3 8 20-350
573 1144 57 15.0 13.4 22.7 8 20-350
344 6766 38 4.4 4.0 6.2 3 3-27 Anthony and McKetta63
344 6073 48 0.9 0.8 1.2 4 20-100 Dhima et al.1
4. Can the Krichevsky-Kasarnovsky Equation Each flash calculation requires, in addition to pres-
Be Applied? sure and temperature, the input of a global composition
zj(z1, ...., zi, ..., zn-1, zw). When binary water-hydrocarbon
An answer to this question requires a realistic analy-
mixtures are considered, the use of z1 ) z2 ) 0.5 is a
sis of all available experimental solubility data. How- aq aq
ever, the accuracy of this answer depends not only on safe choice. By forcing xi,cal ) xi,exp , a unique value of
hc aq
the precision of the measurements but also on the way γiHi(P,T) ≡ fi (P,T)/xi is found for the hydrocarbon.
the hydrocarbon-phase fugacities are calculated. Gener- When two or more hydrocarbons are used, two cases
ally, only the aqueous-phase composition is available. can be distinguished. Either the composition of the
A flash calculation is therefore needed to estimate the hydrocarbon mixtures is known before it is brought in
hydrocarbon phase composition (in particular its water contact with water, in which case the zj vector is
content) and hence the fugacity of each component. composed of 50% water and 50% of this mixture, or the
4.1. Flash Calculation. The three-phase flash cal- composition of the vapor in equilibrium with water is
culations are performed using a Rachford-Rice ap- known. In the latter case, we assume that the solubility
proach. is small enough and does not change the ratio of their
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3151

Table 8. Application of Eq 5 and Results Obtained on the Propane-Water System

T (K) H°γH (MPa) vaq 3
i (cm /mol) σ (%) Adev (%) MaxDev (%) N P (MPa) ref
285 1940 83 1.3 1.2 1.9 4 4-14 Kobayashi and Katz64
311 4990 68 1.9 1.6 3.1 5 3-18
329 6901 68 1.2 1.0 2.0 4 1-19
361 9013 75 0.5 0.5 0.9 5 2-19
370 8789 84 0.6 0.6 1.0 5 3-19
383 8810 79 1.8 1.5 3.2 6 2-19
400 8234 82 1.6 1.4 2.3 7 1-19
422 7195 80 1.6 1.5 2.6 7 2-19
273 1427 7.1 5.9 11.6 4 0.03-0.1 Umano et al.65 a
344 7326 3.9 3.2 8.0 8 0.51-1.25 Wehe and McKetta66 a
289 1534 5.9 5.3 7.9 6 0.1-0.69 Azarnoosh and McKetta67 a
311 5428 3.3 2.8 6.5 16 0.23-1.1
344 9034 3.1 2.6 6.1 20 0.28-2.66
378 9357 3.1 2.4 8.2 20 0.52-3.53
411 8107 2.3 2.1 3.4 6 0.86-3.44
a Considered as low-pressure solubility data.

Table 9. Application of Eq 5 and Results Obtained on the Butane-Water System

T (K) H°γH (MPa) vaq 3
i (cm /mol) σ (%) Adev (%) MaxDev (%) N P (MPa) ref
311 5754 65 7.5 6.0 13.8 10 7-68 Brooks et al.68
378 8693 91 4.2 3.3 7.8 5 8-69
311 5195 80 0.9 0.7 1.7 20 1-69 Reamer et al.11
344 8006 88 1.8 1.1 6.8 20 1-69
378 9014 94 2.2 2.0 3.9 24 1-69
411 9424 90 0.9 0.8 1.8 12 10-69
444 7139 97 1.6 1.4 2.7 13 8-69
478 5266 99 0.9 0.8 1.6 12 10-69
311 5315 78 4.4 3.8 8.9 17 1-69 Sage and Lacey12
344 7872 90 2.4 1.8 6.3 15 1-69
378 9157 92 2.9 2.3 5.5 19 2-69
411 9140 93 2.3 1.9 5.3 16 4-69
444 6901 100 2.8 2.4 4.9 19 2-69
478 5169 101 1.6 1.3 3.5 15 5-69
511 3536 114 4.7 4.1 9.0 13 7-69
298 4596 0.6 0.6 0.9 3 0.1-0.25 Carroll et al.48 a
313 6016 2.6 2.6 3.2 4 0.11-0.38
343 8359 0.3 0.3 0.5 3 0.27-0.84
373 9793 7.1 7.0 8.7 5 0.2-1.61
398 9722 0.0 0.0 0.0 2 1.23-2.65
423 7836 0.0 0.0 0.0 2 2.2-4.13
344 8002 89 4.4 3.7 7.9 5 10-100 Dhima et al.1
a Considered as low-pressure solubility data.

compositions. The hydrocarbon part of the zj vector is
then defined using the known hydrocarbon composition
ratio in the vapor phase. Again, forcing the calculated
aqueous mole fraction of each hydrocarbon to be equal
to its experimental value allows the determination of a
unique value of γiHi(P,T) ≡ fhc aq
i (P,T)/xi for each hydro-
carbon.
4.2. Analysis of Solubility Data. To evaluate
whether the use of the [K-K] equation is justified, three
arguments will be investigated: (i) the effect of mixture,
(ii) the ln(f/x) versus P diagram, and (iii) comparison of
the values of γH i H° j aq
i,w and v i with literature data.
4.2.1. Effect of Mixture. Equation 1 indicates that
at a given pressure and temperature, and for two
different hydrocarbon compositions, the activity coef-
ficients behave as follows
above, both for binary and ternary mixtures. Figure 4
thus shows the activity coefficient ratio for methane and
carbon dioxide in the case of their corresponding binary
and ternary systems. Two different ternary systems
have been considered at four different pressures at 71
°C.
Figure 5 gives this ratio as a function of aqueous-
phase mole fraction for all solutes considered in this
work as well as in our previous work.1
We observe that for all our ternary systems (except
the n-butane) this activity coefficient ratio (γ(1)/γ(2)) is
close to unity within the experimental uncertainty.
Hence, no interaction between solutes is observed in the
aqueous phase. Furthermore, the activity coefficient is
constant with composition. Since at infinite dilution its
value must be 1, we conclude that it is 1 within the full

()
concentration range of interest.
γ(1) [fhc,(1)(P,T,yj(1))]/x(1) The experimental uncertainty for the n-butane solu-
i i i
) (7) bility is too large to draw any conclusion from the small
γ(2)
i [fhc,(2)
i (P,T,yj(2))]/x(2)
i activity coefficient ratio. This has been discussed in
detail by Dhima et al.1
This approach has been proposed by Dhima et al.,1 Figure 6 extends this analysis to the most important
where exponent (1) referred to the binary system and ternary systems for which data have been found for all
(2) to a ternary system. This ratio can also be inter- temperatures.
preted as the ratio of the actual, measured solubility It can be observed that the evolution of the experi-
and its “theoretical” value. mental values of the activity coefficient ratio with the
The ratio of hydrocarbon-phase fugacities and the solute aqueous-phase molar fraction is not very clear.
aqueous mole fraction can be determined as explained Especially in the case of hydrocarbons such as n-butane
3152 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Table 10. Application of Eq 5 and Results Obtained on the CO2-Water System

T (K) H°γH (MPa) vaq 3
i (cm /mol) σ (%) Adev (%) MaxDev (%) N P (MPa) ref
285 114 32 0.5 0.4 0.9 6 5.07-30.40 Wiebe and Gaddy27
291 135 32 0.9 0.7 1.8 7 2.53-30.40
298 163 32 0.5 0.4 0.8 4 5.07-40.53
304 188 32 0.5 0.5 0.7 8 2.53-50.66
308 206 32 0.7 0.7 1.1 8 2.53-50.66
313 228 32 1.1 0.8 2.3 9 2.53-50.66
323 275 32 1.0 0.7 2.1 9 2.53-70.93 Wiebe and Gaddy7
348 393 32 1.4 1.1 3.0 9 2.53-70.93
373 492 32 1.9 1.5 3.6 9 2.53-70.93
374 476 37 1.6 1.4 2.8 13 10.84-62.31 Prutton and Savage69
393 510 40 1.8 1.4 4.2 12 2.33-70.32
323 285 30 2.3 1.9 3.9 8 20-350 Tödheide and Franck70
373 498 31 1.5 1.3 2.5 8 20-350
423 583 32 3.5 3.2 5.0 8 20-350
473 518 35 2.0 1.6 3.3 8 20-350
383 502 34 1.3 1.0 3.1 15 10-150 Takenouchi and Kennedy71
423 556 36 1.7 1.3 3.8 15 10-150
473 478 37 2.7 1.9 8.3 15 10-150
523 416 26# 2.9 2.1 5.9 15 10-150
533 391 23# 4.8 4.2 8.7 15 20-150
543 375 10# 5.9 4.7 12.5 12 20-120
289 131 45# 3.7 3.4 5.3 3 5.07-20.28 Gillespie and Wilson8
298 163 39# 1.0 0.9 1.4 3 5.07-20.28
303 185 29 0.0 0.0 0.0 3 5.52-20.28
304 200 22# 1.9 1.6 3.2 5 0.69-20.28
348 412 23# 2.0 1.8 2.8 5 0.69-20.28
366 531 10# 7.8 5.8 15.2 5 0.69-20.28
394 561 25# 3.8 2.8 5.9 5 0.69-20.28
373 496 0.8 0.7 1.5 7 0.33-2.31 Müller et al.72 a
393 558 0.7 0.6 1.3 7 0.60-2.85
413 617 4.6 3.1 11.1 7 0.65-3.25
433 609 4.8 3.4 10.6 7 1.14-3.48
453 549 0.6 0.6 0.9 7 2.10-6.27
473 528 1.8 1.3 3.7 8 3.76-8.11
323 260 0.0 0.0 0.0 2 10-15 D’Souza et al.73
348 415 0.0 0.0 0.0 2 10-15
353 427 1.2 1.1 2.1 7 2.33-10.18 Nighswander et al.74 a
393 526 1.6 1.3 3.1 10 2.11-9.98
433 535 1.9 1.6 3.5 5 3.91-8.07
471 535 2.8 2.3 5.1 6 4.6-10.21
348 239 0.0 0.0 0.0 2 10-15 Sako et al.9
421 408 95b 1.3 0.9 2.4 5 10-20
288 127 29 0.4 0.4 0.7 11 6.08-24.32 King et al.35
293 147 29 0.3 0.3 0.7 9 6.59-20.27
298 165 31 0.4 0.3 0.7 6 7.6-20.27
323 261 36 0.3 0.3 0.4 3 10.1-30.1 Dohrn et al.75
313 224 0.9 0.8 1.5 10 0.11-1.01 Fischer et al.76 a
323 293 1.2 1.0 2.5 16 0.1-1.57
333 304 1.2 1.0 2.5 15 0.06-1.53
278 77 0.0 0.0 0.0 2 0.049-0.051 Zheng et al.77 a
303 148 0.0 0.0 0.0 2 0.064-0.066
308 161 0.0 0.0 0.0 2 0.068-0.070
333 328 0.0 0.0 0.0 2 0.078-0.079
338 355 0.0 0.0 0.0 2 0.083-0.084
344 374 33 1.8 1.6 2.6 7 10-100 this work
a b
Considered as low-pressure solubility data. Unreasonable data.

and heavier, this evolution becomes more irregular. This
coincides with very low solubility values (lower than 100
ppm) where the experimental uncertainties are very
large. For example in the case of n-pentane (solid
triangle symbols) one observes that the experimental
activity corresponding to the same amount of aqueous
molar fraction may be greater or lower than unity. The
butane data of McKetta and Katz2 also show very large
activity coefficient ratios. Concerning the behavior of
methane (open symbols) it can be observed that activity
coefficient ratios are closer to unity. We believe that this
distribution is probably the consequence of very large
experimental uncertainties (Dhima et al.1).
4.2.2. ln(f/x) versus P Diagram. Equation 5 sug-
gests that if ln(fi/xi) ) ln(γiHi(P,T)) is plotted as a
function of (P - Psatw ), a straight line is obtained, on the
condition that vj aq
i is a constant with pressure and
composition (and therefore equal to the aqueous partial
molar volume at infinite dilution vj ∞i ), and γH i H°
i,w is
constant with composition (i.e.γH i H°i,w ) H°
i,w). Figure 7
presents the values of ln(fi/xi) as calculated using the
above procedure, for all components investigated ex-
perimentally in this and previous work. Except for the
case of n-butane, for which the experimental uncertainty
is large, all data follow straight lines.
The intercepts of these lines with P - Psat w ) 0
provide values for γHi H°i,w, and the slope vj aq . The
i
straight line is a necessary condition for the [K-K]
equation to be valid, but is not sufficient. The last and
perhaps most important argument is the comparison of
the values for γH i H°i,w and vj aq j ∞i obtained in this
i ) v
work with other literature data.
4.2.3. Comparison of the Values of γHi H°i,w and
aq
j i with Literature Data. The infinite dilution par-
v
tial molar volume of hydrocarbons in water vj ∞i has
been measured by a number of authors using techniques
such as dilatometry (Krichevsky and Iliinskaya;32 Tiepel
and Gubbins33) or densitometry (Masterton;34 King et
al.35). Lyckman et al.36 developed a general correlation
for vj ∞i based on Hildebrand theory and have shown
good agreement between their correlation and experi-
mental data of some gases in a certain number of
organic solvents as well as in water given by Hildebrand
and Scott,37 Horiuti,38 Schumm and Brown,39 and Walk-
ley and Hildebrand.40 More recently, Brelvi and
O’Connell41 developed another correlation. Although
these correlations are not specific to aqueous solutes,
as can be seen in Table 4, the agreement between the
partial molar volumes obtained from our solubility data
analysis and the results of two correlations is good.
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3153

Figure 8. Methane aqueous Henry’s constant.

Figure 9. Ethane aqueous Henry’s constant.

In addition, Table 4 compares the values of the defined as

intercept with the y-axis, γH o

x ( )
i Hi,w, to the values of
Henry’s constant as correlated by Li and Nghiem21 or aq aq 2
1 N (xi,cal - xi,exp )
by Harvey.42 Other correlations, summarized in Table
5, give similar results.
σ)
N
∑1 aq
× 100 (8)
xi,exp
The same procedure can be extended to a much larger
database. For this purpose, the flash procedure pre- aq
where N is the number of experimental points and xi,cal
sented above has been adopted to analyze any isother- aq
and xi,exp are respectively the calculated and experi-
mal data set at once. A single value for γHi H°
i,w and for mental values of the solute aqueous phase molar frac-
vj aq
i is obtained by minimizing the standard deviation, tions.
3154 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Figure 10. Propane aqueous Henry’s constant.

Figure 11. n-Butane aqueous Henry’s constant.

According to eq 5, the product γH i H°

i,w is not a
defined as
function of pressure but may be a function of the
aq aq
hydrocarbon content of water, which is higher at high 1 N (xi,cal - xi,exp )
pressure. Therefore, if we consider separately the high- Adev )
N
∑1 aq
× 100 (9)
pressure and low-pressure solubility data, different xi,exp
values of γH i H°
i,w would be obtained if the activity
coefficient were not negligible. and maximum absolute deviation (in %) defined as
The results of this analysis are presented in Table aq aq
6-10, along with other statistical data. (xi,cal - xi,exp )
MaxDev ) Max| aq
|N × 100 (10)
average deviation or mean absolute deviation (in %) xi,exp

Figure 12. Carbon dioxide aqueous Henry’s constant.
Figure 13. Methane aqueous partial molar volume.
The references containing only low-pressure data
(below 10 MPa) are identified with the symbol ‘a’.
When an isotherm contains only low-pressure data,
or only two points, the effect of pressure that is
expressed by vj aq
i is much more sensitive to the experi-
mental uncertainties. In this case the values of volumes
are not taken into consideration. Furthermore, when the
volumes appeared unreasonable in view of the other
data, they have been marked by a # (e.g. volumes
corresponding to measurements of aqueous carbon
dioxide solubility by Gillespie and Wilson8).
We observe that, using the [K-K] equation (i.e.
Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3155
assuming constant γH j aq
i and v i ), the experimental solu-
aq
bility data, xi,exp , can be reproduced within a standard
deviation less than 5%, which is comparable to the
experimental uncertainties. When only two data points
are available on a given isotherm, the deviation is
obviously zero. Table 10 shows that, even in the case of
the carbon dioxide-water system, the [K-K] equation
is applicable at least up to 200 °C, for pressures up to
100-120 MPa.
4.2.3.1. Henry’s Constants. Figures 8-12 present
the results of the product of Henry’s constant with the
3156 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999

Table 11. Henry’s Constant Values as Given by the Literature

H° H° H°
T (K) methane ref T (K) ethane ref T (K) carbon dioxide ref
275 2329 Rettich et al. 78 275 1396 Rettich et al. 78 278 87 Zheng et al.77
278 2521 275 1396 278 88
284 2938 278 1559 303 183
288 3241 283 1876 303 184
288 3243 283 1876 308 205
293 3609 284 1917 308 207
298 3969 288 2225 333 329
298 3973 293 2595 333 328
298 3970 298 2974 338 354
303 4315 298 2978 338 355
308 4648 298 2977
313 4965 298 2982 283 107 Tokunaga et al.84
318 5238 303 3370 293 145
318 5236 308 3771 303 187
323 5487 313 4176 313 231
328 5724 318 4543
318 4545 288 123 King et al.35
298 4133 Crovetto et al.79 318 4539 293 144
334 6056 318 4550 298 165
385 6392 318 4548 308 211
388 6334 318 4542 313 236
431 5058 323 4883
473 3904 323 4887 288 124 Postigo and Katz85
518 2609 293 143
295 2815 Crovetto et al.82 298 166
277 2580 Cramer80 301 3245 303 189
286 3430 301 3241 308 212
315 5800 301 3121
334 6260 314 4411 303 181 Carvantes et al.86
364 6610 315 4345
384 6310 315 4341
432 4890 318 4674 303 187 Hagewiesche et al.87
457 4050 322 4730 313 234
461 3990 330 5191 323 284
466 3120 336 5960
484 3080 342 5954 303 192 Matous et al.88
513 2580 349 6240 323 288
538 2040 351 6593 353 443
542 2240 352 6462
554 1780 364 6713 623 198 Crovetto and Wood89
573 1130 369 6719 632 169
396 6534 643 139
298 3731 Tokunaga and Kawai81 404 6240
429 5223
274 2276 Lekvam and Bishnoi24 442 4513
283 3042 474 3102
286 3214

H° H°
T (K) n-butane ref T (K) propane ref
283 1700 Kazaryan and Ryabtsev83 311 4909 Kobayashi and Katz64
298 2700 328 6646
303 4300 344 7922
313 6300 361 8845
378 9068
394 8837
411 8273
428 7590

activity coefficient as a function of temperature for all
components. The values of the product [γH i H°i,w] ob-
tained from the high-pressure solubility data (Tables
6-10) are compared to the values corresponding to low-
pressure solubility data (Tables 6-10). Both these
values are compared to the values of Henry’s constant
given by the literature (Table 11), as well as to the
values of Henry’s constant calculated using some exist-
ment (when available) as well as with the correlations
proposed by Lyckman et al.36 and Brelvi and O’Connell.41
Note that King et al.35 and Teng et al.43 measure the
density of the water-rich phase dsolution (kg/m3) and do
not give the values for the partial molar volumes. The
following equation is used for converting their data to
the apparent partial molar volume.

[ ]
aq
ing literature correlations (Table 5). 44.10 1 - xi 18.015 18.015
The values obtained from the low-pressure data and vj aq
i ) 1000‚ + 1000‚ aq ‚ -
dsolution x dsolution dwater
from the high-pressure data are very close, indicating i
that the activity coefficient has no effect. Furthermore,
excellent agreement exists between the Henry’s con- (11)
stant values fitted here and the literature data or Note that this equation only holds for CO2. A more
correlations presented. general equation would have been
4.2.3.2. Partial Molar Volume. The second condition

[ ]
necessary for evaluating the validity of the [K-K] Mi 1 - xaq
i 1 1
equation is the independence of aqueous partial molar vj aqi ) + ‚Mw‚ - (12)
volume from pressure and composition. If this hypoth- dsolution xaq dsolution dwater
i
esis is satisfied, the aqueous partial molar volume is
equal to its value at infinite dilution. Figures 13-17 One observes that the agreement between the values
compare our fits for the aqueous-phase partial molar obtained using the above equation (Table 12) and the
volume (Tables 6-10) with the values given in the values resulting from our flash calculation given in
literature (Table 12) that result from a direct measure- Table 10 is surprising.

Figure 14. Ethane aqueous partial molar volume.
Figure 15. Propane aqueous partial molar volume.
Figure 16 shows, in addition, the saturated liquid
molar volume as calculated by the Peng-Robinson
equation. One observes that although at very low
temperature its value is similar to that of the aqueous
partial molar volume, at high temperatures no com-
parison can be made.
From the above discussion we conclude that the
[K-K] equation can be used for calculating water-
hydrocarbon equilibria. If it is to be used for complex
mixtures, however, the Henry constant and the partial
molar volume at infinite dilution of each hydrocarbon
component must be known. As we have seen, correla-
Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3157
tions exist but they are limited to a few components,
most often light hydrocarbons. Natural gases, however,
also contain heavier components. It will be the purpose
of another paper to propose a unified correlation for a
great number of components.
Conclusions
New solubility data of carbon dioxide and its ternary
mixtures with methane in water have been obtained at
71 °C and at pressures from 10 to 100 MPa. To get a
thermodynamic model, these data as well as our previ-
3158 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999
Figure 16. n-Butane aqueous partial molar volume and its comparison to the saturated liquid volume.
Figure 17. Carbon dioxide aqueous partial molar volume.
ously published solubility data (Dhima et al.1) have been
considered together with a large number of the pub-
lished solubility data.
From this analysis, we conclude the following:
Our binary solubility data are in good agreement with
the existing literature data.
The ternary solubility data can be predicted by the
binary ones within the experimental accuracy.
As a direct consequence of this analysis, a very simple
thermodynamic model can be proposed. The hydrocarbon-
rich phase is modeled using the Peng-Robinson equa-
tion of state where the binary interaction parameters
are taken from the literature. The aqueous phase is
described by Henry’s law extrapolated by the Krichev-
sky-Kasarnovsky equation. The necessary parameters
of this equation are the Henry’s constant at the water
vapor pressure and the aqueous partial molar volume
at infinite dilution. It is demonstrated that both of these
parameters are only functions of temperature and are
independent of pressure and composition. The hydro-
carbon species dissolved in water do not interact.
The values of Henry’s constant can be calculated
using the literature expressions such as those given by
Li and Nghiem21 or Harvey.42 These correlations are
 Ind. Eng. Chem. Res., Vol. 38, No. 8, 1999 3159

Table 12. Values of the Directly Measured Apparent Partial Molar Volumes
T (K) methane ethane propane carbon dioxide benzene ref comments
290 33 48 64 Masterton34 densimetry
296 36 50 67
298 38 51 83
302 37 52 68 83
308 38 84
273 36 32 Krichevsky and Iliinskaya32 dilatometry
298 37 33
323 38 33
273 37 53 Tiepel and Gubbins35 dilatometry
288 29 King et al.43 densimetry
293 30
298 30
278 32 Teng et al. (1997) densimetry
283 32
288 32
293 32

given only for a limited number of solutes. Subse- (2+) ) multiple hydrocarbons-water system
quently, a unique and general expression is desirable. - ) composition vector (xj and yj)
The aqueous partial molar volumes at infinite dilution - ) related to partial properties (vj aq
i : aqueous solute
can be estimated by the correlation proposed by Lyck- partial molar volume)
man et al.36
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Received for review December 7, 1998
Revised manuscript received May 26, 1999
Accepted May 28, 1999
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