15924 J. Phys. Chem.

C 2007, 111, 15924-15934

Phase Equilibria, Excess Properties, and Henrys Constants of the Water + Carbon Dioxide
Binary Mixture

Mara Carolina dos Ramos, Felipe J. Blas,*, and Amparo Galindo

Departamento de Fsica Aplicada, Facultad de Ciencias Experimentales, UniVersidad de HuelVa,
21071 HuelVa, Spain, and Department of Chemical Engineering and Chemical Technology,
Imperial College London, South Kensington Campus, London SW7 2AZ, United Kingdom
ReceiVed: May 15, 2007; In Final Form: July 9, 2007

The high-pressure phase diagram and other thermodynamic properties of the water + carbon dioxide binary
mixture are examined using the SAFT-VR approach. The carbon dioxide molecule is modeled as two spherical
segments tangentially bonded. The water molecule is modeled as a spherical segment with four associating
sites to represent the hydrogen bonding. Dispersive interactions are modeled using the square-well
intermolecular potential. The polar and quadrupolar interactions present in water and carbon dioxide are
treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters
are taken from the works of Galindo and Blas (Fluid Phase Equilib. 2002, 194-197, 502; J. Phys. Chem. B
2002, 106, 4503) and Clark et al. (Mol. Phys. 2006, 22-24, 3561) for carbon dioxide and water, respectively.
The phase diagram of the mixture exhibits a number of interesting features: type-III phase behavior according
to the classification of Scott and Konynenburg, three-phase behavior at low temperatures with its corresponding
upper critical end point, a gas-liquid critical line at high temperatures and pressures that continuously changes
from gas-liquid to liquid-liquid as the pressure is increased and gas-gas immiscibility of second kind.
Only one unlike interaction parameter is fitted to give the best possible representation of the temperature
minimum of the gas-liquid critical line of the mixture. This unlike parameter is then used in a transferable
manner to study the complete pressure-temperature-composition phase diagram. The phase diagram calculated
with SAFT-VR is in excellent agreement with the experimental data taken from the literature in a wide range
of thermodynamic conditions. The theory is also able to predict a good qualitative description of the excess
molar volume and enthalpy of the mixture as well as the most important features of the Henrys constants at
different temperatures.

I. Introduction amount of carbon dioxide in the atmosphere by storing it in

In the last few years, the use of supercritical carbon dioxide
(CO2) has gained great chemical and industrial interest. The
supercritical CO2 is being considered as a substitute solvent for
the conventional organic solvents that generally are hazardous
and dangerous for health and for the environment.1 In this case,
the advantages that CO2 displays against other solvents are the
following: relatively nontoxic, nonflammable, relatively inert
in most of the processes, very inexpensive, economically
profitable, and nonpolluting, it has a greater solvation power,
is readily recovered and recycled, and hence the industrial
processes are more efficient. There are several areas in which
processes are using CO2 as a solvent, including the separation
in the food industry, coatings, polymer production, and dry-
cleaning.2 Other applications and uses of CO2 are of interest
within the oil and gas industries. For instance, enhanced oil
recovery uses carbon dioxide to inject it in order to extract more
crude.
Another important field in which an accurate knowledge of
the thermodynamic properties for the H2O + CO2 binary
mixtures is essential is found in geochemistry and environmental
technology because of the increasing concern to reduce the
Part of the Keith E. Gubbins Festschrift.
* Corresponding author. E-mail: felipe@uhu.es.
Universidad de Huelva.
Imperial College London.
10.1021/jp073716q CCC: $37.00 2007 American Chemical Society
Published on Web 08/24/2007
geological formations. The methods to dispose the CO2 are
under examination. The storage of carbon dioxide by means of
sequestering it into depleted hydrocarbon reservoirs, by injecting
it into saline aquifers, or using industrial fixation into inorganic
carbonate are being considered.3-5
Unfortunately, CO2 is a low-dielectric-constant fluid, and,
consequently, a relatively poor solvent of many polar and
organic compounds, including water. Experimental data from
different sources, including analysis of rocks and minerals, fluid
inclusion studies, and laboratory measurements, among others,
indicate that aqueous and carbonic fluids (such as CO2, methane,
and other components) have played a key role in the genesis of
hydrocarbon reservoirs. In addition, most of fluids in these
reservoirs contain water + carbon dioxide mixtures. The
importance of the water + carbon dioxide mixtures comes not
only from a practical point of view but also from a theoretical
point of view. Both components are particularly complex to
model. Water is one of the most important and complex
substances in life. It has a permanent electric dipole moment
and can associate with other water molecules and/or other polar
substances through hydrogen bonding. Carbon dioxide is a linear
molecule, and although it has no electric dipole moment
(because its symmetry), it has an important electric quadrupole
moment. Although several authors6,7 have suggested possible
specific interactions between carbon dioxide molecules and other
Water + Carbon Dioxide Binary Mixture
polar substances, such as water, there is no clear and definitive
evidence of such a specific interaction.
It is clear from the previous discussion that it would be
desirable to have an accurate description of the thermodynamic
behavior of the water + carbon dioxide binary mixture in a
wide range of temperatures and pressures. There has been an
important number of experimental and modeling studies to
determine its thermodynamic properties, including the phase
behavior, of the water + carbon dioxide binary mixture. See
the excellent reviews of Blencoe and co-workers8,9 for a detailed
account of the theoretical approaches undertaken over the last
50 years. From an experimental point of view, most of the
interest has been focused on the mutual solubilities, and as a
result a large number of experiments have been conducted, as
shown in the excellent reviews of Larryn and Akinfiev,10
Spycher et al.,11 and Chapoy et al.12 More recently, the vapor-
liquid equilibria has been studied by Valtz et al.6 From a
theoretical point of view, the binary mixture of carbon dioxide
and water exhibit the interesting type-III phase behavior
according to the classification of Scott and van Konynen-
burg.13,14 These types of mixtures exhibit liquid-liquid-vapor
(LLV) three-phase coexistence at low temperature, an upper
critical end point (UCEP), and two different gas-liquid critical
loci, one running from the critical point of the more volatile
component (CO2 is this case) to the UCEP of the mixture, and
a second one that departs from the other component (in our
case H2O) and continues to high pressures turning into a fluid-
fluid critical line. Some mixtures exhibit the so-called gas-gas
immisciblity of the second kind, in which the critical line that
departs from the less-volatile component has a negative slope
as the pressure increases, passing through a temperature
minimum, and then develops a positive slope at higher pressures.
Another interesting feature that this mixture presents is the
barotropic inversion, in which there is an inversion of density
due to the pressure effect.15 Most of the theoretical approaches
mainly concern the solubilities,7 hydrates,16 VLE in a small
range of temperatures,6 and excess properties.17 Despite of this,
there is a little information about the global description of the
phase behavior and other properties of such a binary system.
In this work, we use the SAFT-VR approach to examine the
high-pressure phase behavior, excess functions, and other
thermodynamic properties of the water + carbon dioxide binary
mixture. We have adjusted only one crossed interaction
parameter by fitting the temperature minimum observed in the
gas-liquid critical line. We have then used the same parameters
to the study other conditions of pressure and temperature as
well as other thermodynamic properties. In particular, we
investigate the global pressure-temperature-composition (PTx)
phase diagram of the mixture. We analyze in detail the
peculiar behavior of the mutual solubilities of CO2 and H2O.
The ability of the theoretical approach is also tested by
comparing the calculated excess volume and enthalpy and the
infinite-dilution Henrys constant of the mixture with the
corresponding experimental data. This is a very stringent test
because excess properties and Henrys constant are very
sensitive to the molecular details of the model.
The rest of the paper is organized as follows. We present the
molecular model and theory in Section II, where we also
highlight the most-relevant features of the molecular parameters
used in this work. The results and discussion are presented in
Section III; and the conclusions are made in Section IV.
II. Molecular Model and Theory
The water molecules are modeled based on the four-site
model first proposed by Bol18 and Nezbeda et al.19 The
J. Phys. Chem. C, Vol. 111, No. 43, 2007 15925
molecules are modeled as square-well segments of hard-core
diameter 11, with four off-center short-range attractive sites,
which mediate the hydrogen-bonding interactions. Two of the
sites (of type H) represent the hydrogen atoms in the water
molecule, and the other two sites (of type O) represent the lone
pairs of electrons of the oxygen atom. The sites are placed at a
distance rd/11 ) 0.25 from the center of the sphere and have
a cutoff range of rc so that an attractive energy, HB, is realized
if sites are closer than rc. Only O-H bonding is considered;
that is, no H-H or O-O interactions are allowed. The square-
well interaction is characterized by a depth 11 and a range 11.
This model has been used previously in many studies6,20-26 and
has been shown to describe the phase behavior of aqueous
mixtures accurately. Carbon dioxide is a linear symmetrical
molecule with a zero dipole moment but with a large quadrupole
moment. Following our previous works,27,28 we model carbon
dioxide with a simple united-atom approach in which m2 ) 2
square-well segments of equal hard-core diameter 22 are bonded
tangentially. The square-well segments are further characterized
by a depth 22 and range 22.
It is important to note at this point that the models proposed
correspond to an effective treatment of the polar and quadrupolar
interactions present in water and carbon dioxide via square-
well potentials of variable range. The SAFT approach has been
extended in a number of works to incorporate explicit polar in-
teractions (both dipoles and quadrupoles).29-36 These approaches
can be very successful in modeling real polar and associating
fluids, but they require the addition of polar parameters, such
as the molecular dipole or quadrupole moments. These are
usually taken from experimental data, if available, although care
should be taken to note that the value of the dipole moment is
state-dependent. A Boltzmann averaging of the dipole-dipole
interaction energy over all orientations leads to an angle-
averaged (i.e., angle-independent) free energy varying as the
sixth inverse power of intermolecular distance, usually called
the Keesom interaction,37 which can be treated as contributing
to the overall van der Waals intermolecular interaction. We take
this view, and treat orientation-independent polar interactions
effectively as dispersion forces using square-well potentials of
variable range. As we will show below, the model is perfectly
adequate to describe the phase behavior of the compounds of
interest, and we reduce the need to add polar parameters.
Related to this discussion are also the works of Ji et al.25 and
Valtz et al.6 who have considered the use of association-like
interactions between CO2 and H2O. Ji et al.25 have modeled
carbon dioxide as an associating molecule with three sites to
take into account self-association in CO2 and the association of
CO2 and H2O molecules. In particular, these authors use the
SAFT1 equation, which is directly comparable with the
SAFT-VR approach we use in this work. They find the need to
incorporate association sites in CO2 and to use temperature-
dependent parameters in order to reproduce the phase equilibria
of the mixture to the desired accuracy. Valtz et al. also
considered incorporating association sites to model CO2, but
found that the unlike water-carbon dioxide association energy
parameter takes very-small values when fitted, and hence
concluded that this was not necessary. In agreement with their
work, we find that we can predict the most-important features
of the H2O + CO2 phase behavior and other thermodynamic
properties without incorporating association sites in the CO2
model and with unlike parameters that are not temperature-
dependent.
Because the SAFT-VR theory has already been presented in
a number of works,38,39 here we give only an overview of the
15926 J. Phys. Chem. C, Vol. 111, No. 43, 2007 dos Ramos et al.

main expressions. The equation is written in terms of the equivalent and the subscripts can be dropped; that is, Xa,i ) X.
Helmholtz free energy. In the case of mixtures containing both This, together with the absence of water-carbon dioxide
chain-like and hydrogen-bonding molecules, the free energy can association, greatly simplifies the analysis, and the contribution
be expressed as a sum of four microscopic contributions: an to the free energy due to the water-water association is obtained
ideal contribution AIDEAL, a monomer term AMONO, which takes as
into account the attractive and repulsive forces between the
AASSOC X
segments that form the molecules, a chain contribution ACHAIN,
which accounts for the connectivity of the molecules, and an NkBT [(
) x1 4 ln X - + 2
2 ) ] (6)
association term AASSOC, which takes into account the contribu-
tion to the free energy due to hydrogen-bonding interactions. where the fraction of water molecules not bound is given by
The Helmholtz free energy is then written as the mass action equation.51,52 For a general site a in molecule
i it can be written as
A AIDEAL AMONO ACHAIN AASSOC
) + + + (1) 1
NkBT NkBT NkBT NkBT NkBT Xa,i ) (7)
n sj
where N is the total number of molecules, T is the temperature, 1+ Fxj Xb,j a,b,i,j
and kB is the Boltzmann constant. j)1 b)1
The free energy of the ideal mixture is given by40
and in the case of only water-water bonding the mass action
A IDEAL n equation is simply given by
) xi ln(Fii3) - 1 (2)
1
NkBT i)1 X) (8)
1 + 2Fx1
where Fi ) Ni/V is the number density, xi is the molar fraction,
and i is the thermal de Broglie wavelength of species i. The function a,b,i,j characterizes the association between the
The contribution to the free energy due to the monomer- site a on a molecule i and the site b on a molecule j. This can
monomer interactions is obtained as a high-temperature per- be written in general as38,39
turbation expansion up to second order41-43
a,b,i,j ) Ka,b,i,j Fa,b,i,jgSW
ij (ij) (9)
mono
A A A1 A2
HS
) + + (3) or specifically here as
NkBT NkBT NkBT NkBT
) K11F11gSW
11 (11) (10)
where the residual free energy of the reference hard sphere fluid
AHS/NkT is calculated using the expression of Boublk and Here, the Mayer f-function of the a-b site-site interaction a,b,i,j
Mansoori et al.44,45 A1/NkT corresponds to the mean attractive is given by Fa,b,i,j ) exp(-a,b,i,j/kBT) - 1, and Ka,b,i,j is the
energy of the mixture and is obtained in the context of the M1Xb available volume for bonding.53 Because in the mixture there
mixing rules.38,39 The second-order fluctuation term A2/NkT is is only one type of water-water hydrogen bond, the only
calculated using the local compressiblity approximation. Details subscripts remaining indicate that the only association is between
of each of these terms and of the mixing rules can be found in the molecules of component 1. The corresponding Mayer
the original works.38,39 f-function is then given by F11 ) exp(HB 11 /kBT) - 1.
The chain contribution to the free energy of a mixture of The rest of the thermodynamic properties, such as the
chain model molecules formed by square-well segments can chemical potential , compressibility factor Z, and other
be written as21,39,46 thermodynamic derivatives needed in our calculations, can be
obtained easily from the Helmholtz free energy using standard
ACHAIN n

thermodynamic relations.
)- xi(mi - 1) ln ySW
ii (ii) )
NkBT i)1
III. Results
-x2(m2 - 1) ln ySW
22 (22) (4)
In this section, we present the main predictions we have
-ii/kBT. obtained using the SAFT-VR approach to describe different
where ySW
ii (ii)) gSW
ii (ii)e The contact pair radial distri-
thermodynamic properties of the water + carbon dioxide binary
bution function for a mixture of square-well molecules corre-
mixture. We aim at understanding the phase behavior, excess
sponding to the i-i interaction, gSW ii (ii), is obtained from the thermodynamic properties, and Henry constants of this mixture
high-temperature expansion.41-43 Further details can be found
as well as providing a sound approach to predict the thermo-
in refs 38 and 39.
dynamic properties of the mixture accurately.
The contribution to the free energy due to the association of
The SAFT-VR approach, as other versions of SAFT, requires
si sites on molecules of species i is obtained from the theory of
the determination of the intermolecular parameters of the model
Wertheim47-50 as
to describe the properties of real substances. In particular, each

[ ( ) ]
si Xa,i si nonassociating substance is characterized by four parameters:
AASSOC n

NkBT
)
i)1
xi
a)1
ln Xa,i -
2
+
2
(5) a parameter m associated with the molecular aspect ratio or with
the number of spherical segments forming the model chain, the
hard-core diameter of the segments, , and the depth, , and
The first sum is over species i and the second over all si sites range, , of the square well used to model the long-range
of type a on a molecule i. Because there is only one type of attractive interactions. In the case of associating compounds,
hydrogen bond (O-H) for the water molecule, the fractions, the number and type of bonding (or association) sites, the site
X, of water molecules not bound at any of the four sites are cutoff range, rc, for each site and the site-site energy, HB, are
Water + Carbon Dioxide Binary Mixture J. Phys. Chem. C, Vol. 111, No. 43, 2007 15927

TABLE 1: Optimized and Rescaled Square-Well Intermolecular Potential Parameters for Water26 and Carbon Dioxide27,28
substance m () /kB (K) HB/kB (K) KHB (3) c () c/kB (K) HB
c /kB (K) KHB 3
c ( )

H2O 1 3.033 300.4330 1.718250 1336.951 0.893687 3.469657 276.2362 1229.273 1.337913
CO2 2 2.7864 179.27 1.515727 3.136386 168.8419

further needed to characterize the molecules. Parameter values MPa) extending to higher pressures, first with a negative slope,
are obtained by comparison with experimental data, usually through a temperature minimum (540 K and 190 MPa), and
vapor pressure and saturated liquid densities. In this work, we then continuing with a positive slope to higher temperatures
use the values published previously both for carbon dioxide27,28 and pressures. At lower temperatures and pressures, a much-
and for water26 (the parameters are also given in Table 1 here shorter critical line starts at the critical point of pure carbon
for completeness). Both sets of parameters together with the dioxide (304.21 K and 7.383 MPa) and ends at slightly higher
SAFT-VR approach provide a very-good description of the pressures at an upper critical end point (UCEP), where the GL
vapor pressures and coexistence densities for a large range of region, richer in CO2, disappears into the region of LL
temperatures, with the exception of the near-critical region. This immiscibility. The three-phase line, characteristic of type-III
is an expected behavior because SAFT-VR, as any classical phase behavior, can be seen in the inset of the figure. As can
equation of state, does not consider the density fluctuations that be seen, it runs from very-low temperatures and pressures to
occur near the critical point. However, because we have an the UCEP; it corresponds to pressures and temperatures where
interest in the high-pressure phase equilibria and the critical the two immiscible liquid phases coexist with a gaseous phase.
behavior of the binary mixture, here we used here conformal As can be seen, the theory is able to provide an excellent
parameters (c and c) rescaled to the experimental critical
temperature and pressure (see the corresponding values in Table
1). Note that the change in the values of the conformal
parameters also results in different values for the nonconformal
paramters (, Kc, and HBc ) when they are reported in experi-
mental units.
The calculation of mixture properties also requires us to know
a number of cross or unlike parameters. The arithmetic mean
is used for the unlike hard-core diameter
11 + 22
12 ) (11)
2
and the unlike square-well range is given by
1111 + 2222
12 ) (12)
11 + 22

The unlike dispersive energy of the system is defined as

12 ) 12(1122)1/2 (13)

where 12 describes the departure of the system from the

geometric mean; it is usually determined by comparison with
mixture data and then used to predict properties at different
conditions. In this work, we have adjusted 12 to give the best-
possible representation of the temperature minimum of the
fluid-fluid critical line of the mixture. The value obtained (12
) 0.9742) is treated as temperature-independent and used to
study the complete pressure-temperature-composition (PTx)
phase behavior of the mixture in a wide range of conditions. In
addition, as we will show later, a number of thermodynamic
properties are also predicted using these model parameters
without the need for further adjustment.
A. High-Pressure Phase Behavior and Critical Phenom-
ena. In this section, we study the phase behavior of the mixture.
Figure 1. PT projection of the phase diagram for the water(1) + carbon
Using the molecular parameters of the pure components and dioxide(2) binary mixture. The circles correspond to the experimental
the unlike mixture parameter mentioned in the previous section, vapor pressure data of pure water,57-65 the squares correspond to the
we have obtained the PT projection of the PTx surface for the experimental vapor pressure of pure carbon dioxide,66-71 the stars72
H2O + CO2 mixture (Figure 1a). As can be seen, the phase and plusses73 correspond to the experimental gas-liquid critical line,
behavior of the system is dominated by a large region of liquid- and the triangles correspond to the three-phase line.6 The continuous
liquid (LL) immiscibility. This is a direct consequence of the curves are the SAFT-VR predictions for the vapor pressures, the dashed
curves for the critical lines, and the long-dashed curve for the LLV
self-association interaction between water molecules (hydrogen three-phase line. The inset of part a shows the region close to the critical
bonding).20 The system shows two separate gas-liquid (GL) point of pure CO2. Part b shows a larger scale on the P axis of the PT
critical lines. At high pressures and temperatures, a critical line representation, and the inset shows the Tx projection of the gas-liquid
starts from the critical point of pure water (647 K and 22.03 critical line of the mixture.
15928 J. Phys. Chem. C, Vol. 111, No. 43, 2007 dos Ramos et al.

description of the PT projection of the PTx surface of the phase

diagram at low and high temperatures and pressures, including
the critical lines and the three-phase line of the mixture.
Particularly interesting is the prediction of the type of phase
behavior and the existence of the GG immiscibility of second
kind, a characteristic directly associated to the presence of a
temperature minimum in the gas-liquid critical line running
from the less-volatile component to high pressures and tem-
peratures. It is important to note that only one mixture parameter
is necessary in order to describe the phase behavior for the entire
fluid range. It is also important to mention that the theory is
able to predict the existence of GG immiscibility of second kind
with 12 ) 1, that is, with no correction to the geometric mean
for the unlike energy parameter of the mixture, although
agreement between theoretical predictions and experimental data
is in this case only qualitative.
The GL critical line can be seen extended to very high
pressures in Figure 1b, where a comparison of the experimental
critical compositions and those calculated can also be seen in
the inset. We have used a larger scale on the P axis of the PT
representation to have a better perspective of the GL critical
line of the mixture. Here we can clearly observe not only the
temperature minimum of the critical line (540 K) but also
how this line reaches temperatures above the critical temperature
of water at sufficiently high pressures. This is a distinct feature
of the phase behavior exhibited by the water + carbon dioxide
mixture and an example of the gas-gas immiscibility mentioned Figure 2. Px projection of the phase diagram for the water(1) + carbon
in the introduction. As can be seen in the inset of the figure, dioxide(2) binary mixture at high temperatures. Part a shows the Px
the theory is also able to provide excellent agreement with the projection in a larger scale on the P axis, and part b shows the same
experimental data term of composition as shown in the Tx results on a smaller scale. The symbols represent the experimental
projection. It is important to note that we have used two different data taken from the literature, and the curves are the predictions from
SAFT-VR at different temperatures: 523.15 K (circles72 and continuous
sets of experimental data taken from different references in the curve), 533.15 K (squares72 and dotted curve), 538.15 K (diamonds72
literature. and dashed curve), 543.15 K (triangles72 and long-dashed curves), and
Different GL and LL coexistence regions of the phase 573.23 K (crosses72 and dot-dashed curves).
diagram of the mixture become clearer in constant-temperature
Px and constant-pressure Tx slices of the PTx surface. We first move toward higher pressures and lower compositions of water
concentrate on constant-temperature Px slices at high temper- as the temperature is increased. Figure 2b shows the same
atures. Five Px slices are presented in Figure 2a. The three constant-temperature Px slice of the phase diagram in a different
lowest temperatures, 523, 533, and 538 K, correspond to scale. The theory is able to describe correctly the most important
temperatures below the temperature minimum (540 K, ap- features of the two-phase envelope as the temperature and
proximately) of the GL critical line (usually also referred to as pressure are varied. In particular, at fixed temperature the theory
fluid-fluid critical line), but still above the UCEP of the predicts quantitatively the water composition in the H2O-rich
mixture. At these temperatures, the system exhibits a continuous (liquid) phase. In contrast, only a qualitative agreement between
coexistence region, with GL character at low pressures that theory and experiments is seen in the CO2-rich (gas) phase. As
changes continuously to LL character at high pressures. The can be seen, the theory overestimates the compositions at which
corresponding Px slices are seen to exhibit the peculiar shape the gas phase is in equilibrium with the liquid phase, although
characteristic of the LL immiscibility at high pressures in is able to provide a reasonable description of the phase envelope.
mixtures exhibiting type-III phase behavior. At the two highest Agreement between theoretical predictions and experimental
temperatures, 543 and 573 K, which correspond to temperatures data can be considered remarkable if we take into account that
between the temperature minimum of the GL critical line and only one thermodynamic state, that corresponding to the
the critical point of pure water (647 K, approximately), the minimum in temperature of the GL critical line, has been used
system exhibits a GL coexistence region extending from the to fit the unlike parameter 12.
vapor pressure curve of pure water and ending at the GL critical We now turn our attention to the phase behavior at much-
point of the mixture at the corresponding temperature. It is lower temperatures, close to the UCEP of the mixture and the
interesting to note that at this range of temperatures (above the critical point of pure carbon dioxide. In Figure 3a, a constant-
temperature minimum), the Px slices have a second two-phase temperature Px slice at 298.15 K is shown. Because this
coexistence region, a fluid-fluid coexistence region at very high temperature is below the UCEP temperature of the mixture, VL
pressures. This two-phase region exists even at temperatures equilibria is observed at the lower pressures (below the pressure
above the critical temperature of pure water. This phenomenon at which the three-phase coexistence occurs), LLG coexistence
is usually referred to as gas-gas immiscibility of the second at P 6.3974MPa (the pressure corresponding to the LLG
kind. This two-phase envelope becomes wider as the pressure three-phase line at this temperature), and LL immiscibility at
is increased, and it is bound by a minimum pressure associated high pressures. Although the theory overestimates the water
to a second fluid-fluid critical point of the mixture at the molar fractions along all of the phase envelopes, agreement
corresponding temperature. The pressure minimum is seen to between experimental data and theoretical predictions is good
Water + Carbon Dioxide Binary Mixture
Figure 3. Px projection of the phase diagram for the water(1) + carbon
dioxide(2) binary mixture at temperatures close to the UCEP point.
The continuous curves and the open circles are the phase envelopes
from SAFT-VR and experimental data taken from the literature,
respectively at (a) 298.15 K,74-79 (b) 304.2 K,74,75 and (c) 308.2 K.6,74,76
The solid circles and the dashed lines in a and b represent the LLV
three-phase coexistence line. The inset in a shows the vapor-liquid
coexistence region above the three-phase pressure at the corresponding
temperature.
in terms of pressures. At a temperature of 304.2 K, which is
below the UCEP temperature of the mixture but near (and
below) the critical temperature of pure CO2 (304 K ap-
proximately), the mixture exhibits similar behavior (Figure 3b.)
Because the temperature is slightly below the temperature at
which LLG coexistence occurs, the system still exhibits VL
equilibria at low pressures and LL equilibria at high pressures.
At even higher temperatures, 308.2 K, now above the UCEP
temperature of the mixture (and also above the critical point of
pure carbon dioxide), the system exhibits fluid-fluid coexist-
ence, with VL character at low pressure that changes continu-
ously to LL character as the pressure is increased (Figure 3c).
This is the expected behavior when the temperature is increased
in systems that exhibit type-III phase behavior. It is interesting
to note how the distinctive shape of the phase envelope
associated to the CO2-rich fluid phase resembles the corre-
J. Phys. Chem. C, Vol. 111, No. 43, 2007 15929
Figure 4. Px projection of the phase diagram for the water(1) + carbon
dioxide(2) binary mixture at low temperatures. The symbols correspond
to the experimental data taken from the literature, and the curves
correspond to the predictions obtained from SAFT-VR at 278.22 K
(circles6 and continuous curves), 288.26 K (squares6 and dotted curves),
298.28 K (diamonds6 and dashed curves), 308.20 K (triangles6 and long-
dashed curves), and 318.23 K (pluses6 and dot-dashed curves).
sponding envelope shown previously in Figure 2a and b. As in
the previous figures, agreement between theory and experiment
is remarkable in all cases.
The GL phase behavior in the low-temperature 278.22-
318.23 K low-pressure (below the three-phase coexistence
pressures) region can also be examined in Figure 4. The data
and calculations correspond essentially to the solubility of carbon
dioxide in the water-rich phase (Figure 4a) and the solubility
of water in the carbon dioxide-rich phase (Figure 4b) at low
temperatures and pressures. Note that we have only represented
the phase behavior at low pressures (below 5MPa) because we
are now interested in the GL phase behavior. It is important to
remember that for the temperatures considered (below the UCEP
temperature of 305 K), the three-phase equilibrium and LL
immiscibility must emerge from the phase diagram at higher
pressures. To check the accuracy of the theory in predicting
the GL phase behavior at these conditions, we have compared
the results with experimental data taken from the literature.
Although the water content of both the water-rich and the carbon
dioxide-rich phases is overpredicted by the theory, considering
that only one unlike mixture parameter has been fitted, for a
very different set of conditions a surprisingly good agreement
with experimental data is found. In addition, the theory is able
to provide the correct trends as the temperature and pressure
are varied.
We have also studied a number of constant-pressure Tx slices
of the PTx phase diagram of the mixture. Figure 5 shows the
phase envelopes at different pressures, from 20 up to 200 MPa.
The lowest pressure, 20 MPa, lies below the critical pressure
of pure water. This results in a coexistence with VL character
at high temperatures and a region of LL character at low
temperatures. At higher pressures (50, 100, 150, and 200 MPa),
the differences between the gas and liquid phases are more
difficult to identify because the two phases in coexistence are
liquids with different densities. To assess the accuracy of the
theoretical predictions, we have compared the results from
SAFT-VR with experimental data taken from the literature. As
can be seen in the figure, the theory is seen to capture the
essential features of the phase envelopes in a wide range of
pressures. In particular, the theory is able to provide a nearly
quantitative description of the envelope in the H2O-rich liquid
phase. However, significant deviations from experimental data
are seen in the CO2-rich liquid phase, where the theoretical
predictions overestimate the coexistence molar fraction of
water.
15930 J. Phys. Chem. C, Vol. 111, No. 43, 2007
Figure 5. Tx projection of the phase diagram for the water(1) + carbon
dioxide(2) binary mixture at high pressures. The symbols correspond
to the experimental data taken from the literature, and the curves are
the predictions from SAFT-VR at 20 MPa (circles72 and continuous
curve), 50 MPa (squares72 and dotted curve), 100 MPa (diamonds72
and dashed curve), 150 MPa (up triangles72 and long-dashed curve),
and 200 MPa (right triangles72 and dot-dashed curve).
Before finishing this section dedicated to examine the phase
behavior of the water + carbon dioxide mixture, it is interesting
to study in detail the mutual solubilities of water and carbon
dioxide. The experimental data for the phase equilibria of the
mixture is usually provided as mutual solubilities of H2O in a
CO2-rich gas (or liquid) phase and CO2 in an H2O-rich liquid
phase (see the work of Spycher11 and references therein for a
detailed revision of the experimental data available in the
literature). The solubility curve associated with the H2O in the
CO2-rich phase (gas or liquid depending of the thermodynamic
conditions), as function of pressure, exhibits a number of
different shapes depending on the temperature of the system.
The key point for understanding this behavior is to recognize
the existence of a LLG three-phase line and its corresponding
UCEP at 305.5 K and 7.45 MPa. Thus, different shapes of the
solubility curves are expected and observed if the temperature
of the mixture is below or above the UCEP temperature of the
mixture. If T ) 305.5 K, then the curve associated to the
solubility of H2O in CO2-rich phases, as a function of pressure,
exhibits a sharp discontinuity at the three-phase coexistence
pressure. At low pressures, the solubility is seen to decrease as
the pressure is increased. At higher pressures, or more precisely,
at pressures above the three-phase coexistence pressure (at the
corresponding temperature), the solubility of H2O in CO2-rich
phases is seen to increase as the temperature and pressure are
increased, as expected. This scenario is exactly the behavior
obtained in the corresponding constant-temperature Px slices
shown in Figure 3a-c. The apparently anomalous discontinu-
ity of the solubility of H2O in the CO2-rich phase is essentially
due to the presence of the LLG three-phase line of the mixture.
And also related with the same phenomenology, if the temper-
ature of the system is above the UCEP temperature of the
mixture, then the solubility curve does not exhibit a discontinuity
but shows a minimum at low pressures, which smoothly
diminishes as the temperature is increased. The particular
pressure value at which the minimum occurs is seen to increase
as the temperature is raised. The presence of this minimum in
the solubility curve of H2O in the CO2-rich phase is a direct
consequence of the type of phase behavior exhibited by the
mixture. The solubility of CO2 in the H2O-rich liquid phase
also exhibits an interesting behavior because it decreases with
rising temperature, but increases sharply with increasing pressure
up to the pressure corresponding to the three-phase coexistence,
and at a lesser rate thereafter. A discontinuity in the slope exists
for the CO2 solubility because of the presence of two different
dos Ramos et al.
curves, one corresponding to the solubility of CO2 in the H2O-
rich phase (in coexistence with a CO2-rich vapor phase) and
another corresponding to the solubility of CO2 in the H2O-rich
phase (in coexistence with a CO2-rich liquid). Above the UCEP
temperature, the CO2 solubility is given by one curve (CO2 in
the H2O-rich liquid phase), with a curvature that smoothly
diminishes as the temperature is increased.
To recap, if we follow the phase envelopes corresponding to
the H2O-rich (liquid) phase and the CO2-rich (gas and liquid)
phase, then we find that the peculiar mutual solubility behavior
associated to CO2 and H2O is essentially the scenario observed
in the vicinity of the vapor-pressure curve of the more-volatile
component (in this case CO2) and the UCEP of a mixture that
exhibits type-III phase behavior according to the classification
of Scott and Konynenburg. In fact, the discontinuities observed
in the solubility of H2O in the CO2-rich phase and in the slope
of the solubility of CO2 in the H2O-rich phase is a consequence
of crossing the three-phase coexistence line as the pressure is
varied. In addition, the existence of a minimum in the solubility
of H2O in the CO2-rich phase below the UCEP temperature is
a reminiscence of the disappearance of the small GL coexistence
region located in the CO2-rich zone of the phase diagram, which
is still present at temperatures as high as 538 K, as shown
previously in Figure 2a and b.
B. Excess Thermodynamic Properties of the Mixture. In
this section, we examine two of the most-important excess
thermodynamic functions, namely, the excess volume and the
excess enthalpy, for the water + carbon dioxide binary mixture.
We apply the SAFT-VR approach with the same molecular
parameters and the same unlike parameter, 12, to predict these
two important excess properties without further adjustment. The
investigation of excess thermodynamic properties of the mixture,
such as excess volume and enthalpy, is useful to assess the
validity of our model because it is a very-stringent test of any
theory and molecular model.
We first consider the excess thermodynamic volume of the
mixture at different conditions. The excess volume is one of
the most-important functions. It gives, by definition, an idea of
the difference between the real molar volume of the mixture
and the ideal volume of the mixture, and it is therefore one
indicator of the degree of nonideality in the mixing of dissimilar
species. Positive values suggest net repulsive interactions
between components, and negative values suggest net attractive
interactions. The excess molar volume of the mixture is
calculated from the theoretically determined molar volumes of
the pure fluids (Vi ) and the molar volume of the mixture (Vm)
using the standard thermodynamic relationship
n
VE ) V m -
i)1
xiVi (14)
where the index i runs for all of the n components of the mixture.
Note that the ideal volume of mixing is zero so that this excess
property is also equal to the mixing volume.
We study first the excess volume of the mixture at fixed T
) 573.15 K and several pressures ranging from 29.94 up to
99.93 MPa. It is useful to note that the temperature selected is
below the critical temperature of pure water (647 K ap-
proximately). The two lowest pressures considered, 29.94 and
39.93 MPa, correspond to states below the high temperature
gas-liquid critical line, and therefore the system exhibits fluid-
fluid phase separation at these thermodynamic conditions. The
theoretical predictions and experimental data taken from the
literature are shown in Figure 6a. As can be seen, at 573.15 K
Water + Carbon Dioxide Binary Mixture
Figure 6. Excess molar volume for the water(1) + carbon dioxide(2)
binary mixture at different pressures. The symbols correspond to the
experimental data taken from the literature, and the curves are the
predictions from SAFT-VR at: (a) 573.15 K and 29.94 MPa (triangles80
and continuous curve), 39.94.4 MPa (squares81 and dotted curve), 49.93
MPa (diamonds81 and dashed curve), 69.93 MPa (circles81 and thin
continuous curve), and 99.93 MPa (crosses81 and dotted curve); (b)
673.15 K and 29.94.4 MPa (circles9 and continuous curve), 34.94 MPa
(pluses9 and dash-dash-dotted curve), 39.94 MPa (squares9 and dotted
curve), 49.93 MPa (diamonds9 and dashed curve), 59.93 MPa (right
triangles9 and dot-dashed curve), 79.93 MPa (left triangles9 and dot-
dot-dashed curve), and 99.93 MPa (down triangles9 and dot-dashed
curve). At T ) 673.15 K and P ) 29.94 MPa, the molar volumes of
pure H2O and CO2 are 56.07 and 191.09 cm3/mol, respectively. The
theoretical predictions at the same conditions are 74.15 and 223.10
cm3/mol, respectively. The thinner lines in a correspond to the
theoretical predictions at the two-phase fluid-fluid phase region.
the excess volume curves exhibit sigmoidal behavior, with V E
< 0 for mixtures rich in water and V E > 0 for those rich in
carbon dioxide. V E is positive in a wide range of compositions,
an expected result because the water + carbon dioxide mixture
is highly nonideal due to the specific interactions (extensive
hydrogen bonding) between water molecules. This behavior is
in agreement with the trends observed by the isobaric density
data obtained by Seitz and Blencoe (see Figure 3 of ref 8). At
each pressure, the composition range for which positive values
of V E are observed is characterized by the existence of a
maximum, which is seen to displace toward lower water
compositions as the pressure is increased. It is also important
to note that the curves at the two-lowest pressures (29.94 and
39.94 K) exhibit discontinuities in the slope of the excess
volume. In particular, these discontinuities are located at molar
compositions of water x1 0.65 (at 29.94 MPa) and x1 0.70
(at 39.94 MPa), which correspond to the compositions at which
the homogeneous liquid phase disappears. As can be seen in
Figure 6a, this means that the system exhibits vapor-liquid (or
fluid-fluid) phase separation in the range x1 0.65 - 0.94 (at
29.94 MPa) and x1 0.70 - 0.97 (at 39.94 MPa). An inspection
of the constant-pressure Tx slices of the phase diagram presented
in Figure 5 corroborates the behavior observed in the excess
J. Phys. Chem. C, Vol. 111, No. 43, 2007 15931
thermodynamic property (note that these particular pressures
are not shown in Figure 5, but one can clearly see that the
corresponding phase envelopes should lie between those shown
in the figure).
We now consider the excess volume of the mixture at higher
temperatures. In particular, we study the V E at fixed T ) 673.15
K and several pressures in the same range of pressures
previously considered (P ) 29.94 - 99.93 MPa). The selected
temperature now lies above the critical temperature of pure
water, and the mixture exhibits a homogeneous fluid phase in
the whole range of compositions at all of the pressures
considered. Figure 6b shows the theoretical predictions and
experimental data taken from the literature for the excess
volume, as a function of water molar compositions. V E is seen
to exhibit positive values at all pressures considered, with a
pseudo-quadratic shape. As mentioned previously, positive
values are expected because they are identified with an
expansion in the system due to weak interactions between the
components of the mixture, which is the particular case of the
water + carbon dioxide binary mixture. The V E curves show
relatively large maximum values at different pressures, with a
sharp decrease of V E as the pressure is increased. In terms of
shape, the curves are very asymmetric at lower pressures, and
become more symmetric as the pressure is increased, with the
maximum displaced toward mixture compositions rich in carbon
dioxide. In a preliminary study of the thermodynamic properties
of the water + carbon dioxide mixture,54 we have predicted
the opposite behavior for V E at the same temperature but at
lower range of pressures (9.94 - 29.94 MPa). This phenomenon
is related to the fact that the highest degree of asymmetry occurs
where the maximum values are achieved, at 29.94 MPa, which
is very close to the PT condition of the critical isochore for
pure water (29.2 MPa at 673.15 K). From an experimental
point of view, the existence of a maximum in the V E versus
pressure curve (at constant composition) has been accurately
determined and characterized in the works of Seitz and Blencoe8
and Blencoe and Seitz.9
It is remarkable that the SAFT-VR approach is able to provide
an excellent description of a property so sensitive to molecular
details as V E. In particular, the theory accounts for the behavior
of the excess volume at two different temperatures (in a range
of 100 K) and in a wide range of pressures (from relatively
low pressures up to high pressures). We should emphasize again
that no single additional binary mixture parameter has been
adjusted, and although a truly quantitative agreement is not seen,
the SAFT-VR equation of state provides an excellent picture
of the most-relevant physical features exhibited by the excess
volume of the water + carbon dioxide binary mixture.
We have also studied the excess enthalpy of the water +
carbon dioxide binary mixture at different temperatures and
pressures. This excess function is defined in the same way as
V E (see eq 14). We first consider the behavior of the excess
enthalpy as a function of pressure. In Figure 7a, the excess
enthalpy is seen to exhibit a peculiar shape, which is due to the
existence of large regions of LL immiscibility in the phase
diagram. As can be seen, the excess function is positive in the
entire composition range and increases in magnitude as the
pressure is decreased. Because all of the curves at different
pressures exhibit the same qualitative behavior, we analyze in
detail the behavior observed for one of the pressures studied.
For the intermediate pressure, P ) 12.4 MPa, the experimental
excess enthalpy shows three different regions along the entire
range of compositions. In a first region, which goes from x1 )
0.0 to x1 0.416 water compositions, the system exhibits one
15932 J. Phys. Chem. C, Vol. 111, No. 43, 2007
Figure 7. Excess molar enthalpies for the water(1) + carbon dioxide-
(2) binary mixture. The symbols correspond to the experimental data
taken from the literature, and the curves are the predictions from
SAFT-VR at (a) 523.15 K and 10.4 MPa (circles82 and dotted curve),
12.4 MPa (squares82 and long-dashed curve), and 15.0 MPa (diamonds82
and continuous curve); (b) 12.4 MPa and 498.15 K (circles82 and
continuous curve), 523.15 K (squares82 and dotted curve), 548.15 K
(diamonds82 and dashed curve), and 573.15 K (diamonds82 and dot-
dashed curve). The thinner lines and the open symbols correspond to
the theoretical predictions and experimental data at the two-phase fluid-
fluid phase region, respectively.
homogeneous (liquid) phase. Note that the theory overestimates
the size in compositions of this region (the theoretical prediction
estimates the end of the liquid region at x1 0.53). Although
the shape of the H E curve appears to be a straight line, the
function exhibits a slightly convex shape, ending at the
composition corresponding to a two-phase boundary. A second
region exists, from x1 0.416 to x1 0.987, at which the system
exhibits two-phase fluid-fluid phase separation. Note that the
theoretical predictions underestimate the size of the immiscibility
region, as stated in the comment mentioned above. In this case,
both the experimental data and the theoretical predictions
describe a straight line that connects the values of the excess
enthalpy at the coexistence compositions of the two-phase
region. Finally, from x1 0.987 to x1 ) 1.0, the system again
exhibits one homogeneous phase, although in this case cor-
respond to a gas phase. See the inset of the figure, which shows
in detail the region close to x1 ) 1.0. In this context, the sharp
turning point at molar compositions of water x1 0.416 and
the change in the slope of the excess enthalpy at molar fractions
close to 1, represent the points, in terms of compositions, at
which the homogeneous liquid-phase disappears and the gas
homogeneous phase appears again as the water composition is
increased. This means that for water molar fractions between
approximately 0.416 and 0.987, the system is in the VL two-
phase region. Theoretical predictions are able to provide an
excellent description of the excess enthalpy at the three pressures
dos Ramos et al.
considered, including the trend observed when the pressure is
varied. The theory is seen to underestimate the values of the
excess enthalpy at all compositions and to overestimate the range
of compositions at which the water + carbon dioxide mixture
exhibits a homogeneous liquid phase. This is due to the
overestimation of the coexistence molar fraction of water in
the CO2-rich liquid phase.
It is also interesting to mention that the excess enthalpy (and
also the excess volume) of a mixture that exhibits two-phase
coexistence can be measured directly from experiments. This
is done by measuring the enthalpy exchanged in the measure-
ment cell from the moment at which the second component is
added to the first one until the system stabilized (including the
stabilization of the two phases and the interface). The data
presented correspond to the experimental data taken from the
literature with the exact measurement of the enthalpy of the
system in this setup. In the case of the theory we have just
calculated, the excess enthalpy in the two regions in which the
system exhibits one homogeneous phase, and the straight line
joins the boundary points of these regions.
We have also studied the excess enthalpy of the mixture at
different temperatures. As can be seen in Figure 7b, the
SAFT-VR approach is able to provide an excellent description
of this property in a wide range of temperatures, from ap-
proximately 498 to 573 K. Agreement between experimental
data and theoretical predictions is excellent at all compositions.
The theory not only gives the correct shape of the excess
enthalpy but also predicts the expected behavior when the
temperature is varied, keeping the rest of thermodynamic
variables constant. Unfortunately, the theory is unable to predict
quantitatively the molar fraction range at which the mixture is
homogeneous.
C. Henrys Law Constants. We now consider the infinite-
dilution mixture property of the Henrys law constant of a solute
in a solvent. An accurate prediction of this kind of property is
difficult to obtain because it is very sensitive to small molecular
detail. McCabe et al.55 have shown that the SAFT approach
can be used in a predictive way to study this property in aqueous
mixtures. This is of special interest because Henrys law constant
can also be straightforwardly related to the free energies of
hydration of the solute in the solvent of interest.
Here, we use the theory, with the same intermolecular model
parameters, including the same binary interaction parameter
values, to predict Henrys constant of carbon dioxide in water
under saturated vapor pressure. We compare our theoretical
predictions with experimental data taken from the literature as
well as with predictions obtained by Lsal et al.56 using
molecular simulation of different molecular models of water
and/or carbon dioxide. These authors use two models for
CO2, the Harris and Yung model (EPM2) and the Errington
and Panagiotopoulos model (EP-CO2), and five models for
water, SPC, SPC/E, the Errington and Panagiotopoulos model
(EP-H2O), TIP4P, and TIP5P. As can be seen in Figure 8a, this
property exhibits an interesting behavior as a function of
temperature: it is an increasing function at low temperatures,
and a decreasing function at high temperatures, exhibiting a
temperature maximum at approximately 450 K. The equivalent
ln H2,1 versus T representation has also been included in Figure
8b. As can be seen from the figures, the simulation data are in
qualitative agreement with the experimental values; they predict
the correct temperature dependence of the Henrys constant.
With the exception of the EP-H2O + EP-CO2 molecular model
used by Lisal et al.56 (see the down triangles in Figure 8a and
b), all simulation molecular models predict the maximum of
Water + Carbon Dioxide Binary Mixture
Figure 8. (a) Henrys coefficients and (b) ln H2,1 vs T representation
for the water(1) + carbon dioxide(2) binary mixture under saturation
vapor pressure. The continuous (12 ) 1.0) and dotted (12 ) 0.9742)
curves are the predictions from SAFT-VR, and the solid circles are
the experimental data taken from the literature.83-85 The rest of symbols
correspond to the simulation data results obtained by Lsal et al.56 using
different models for both substances: open circles (EPM2 and SPC
models), up triangles (EPM2 and SPC/E models), diamonds (EPM2
anc MSPC/E models), down triangles (EP-CO2 and EP-H2O models),
squares (EPM2 and TIP4P models), and asterisks (EPM2 and TIP5P
models). See the work of Lsal et al. and the text for the nomenclature
used to denote the different models.
the Henrys constant at temperatures lower (400 K) than the
one observed experimentally. We have used two different unlike
parameter 12 values: 12 ) 1, which corresponds to the usual
geometric mean, and 12 ) 0.9742, which is the value obtained
previously by fitting the theoretical results to the temperature
minimum of the gas-liquid critical line of the mixture. As can
be seen, both values overestimate Henrys constant at low
temperatures and underestimate it at high temperatures. Both
values result in the prediction of the same value of the
temperature maximum, which is also below the experimental
value. Although the predictions from the SAFT-VR are only
qualitative, it is encouraging to see that a simple approach,
without a further adjustment, is able to predict the main features
of this property. It is also noticeable that, in the comparison
with the experimental data, the error of the SAFT-VR predic-
tions is of the same order of magnitude as that of the simulation
data.
IV. Conclusions
We have studied the thermodynamic properties of the water
+ carbon dioxide binary mixture using the SAFT-VR equation
of state. We use the simple united-atom approach to model the
carbon dioxide molecule, which is represented as a chain formed
by attractive spherical segments tangentially bonded together
interacting via square-well potentials. The water molecule is
modeled as spherical with four off-center association sites (two
sites are of type H and two of type O). Because in this work
J. Phys. Chem. C, Vol. 111, No. 43, 2007 15933
we are interested studying the phase behvior for a wide range
of pressures and temperatures, including the near critical, critical,
and supercritical regions, we have used intermolecular param-
eters rescaled to the experimental critical points of the pure
components. Standard geometric and arithmetic combining rules
are used to obtain unlike mixture parameters, and in addition
an unlike energy parameter is adjusted according to the modified
geometric mean rule to give the best representation of the
minimum temperature of the gas-liquid critical line. This
parameter is then used in a transferable manner to study other
thermodynamic properties at different conditions.
In the first part of this work, we have studied the high-pressure
phase behavior of the mixture. The theoretical results correspond
to type-III phase behavior according to the classification of Scott
and Konynenburg,13 in agreement with experimental data. In
particular, the theory accounts for the gas-gas immiscibility
of second kind and the temperature minimum of the gas-liquid
critical line of the mixture. We have also studied the phase
equilibria at high and low pressures and temperatures. All of
the calculations show good qualitative agreement with experi-
mental data. We have provided an analysis of the mutual
solubilities of H2O and CO2 and find that the theory is able to
reproduce the peculiar behavior of these properties. In particular,
it predicts the discontinuity at low temperatures and the
minimum at higher temperatures observed in the solubility curve
of H2O in the CO2-rich phase, as well as the change of the slope
of the CO2 solibility in the H2O-rich liquid phase. All of these
features are a consequence of the presence of a three-phase
boundary chracteristic of mixtures that exhibit type-III phase
behavior.
In the second part, we examine two of the most-important
excess thermodynamic functions, namely, the excess volume
and the excess enthalpy. We use the same molecular parameters
and unlike interaction parameter (12) to predict the key features
of these properties. Agreement between experimental data and
theoretical predictions for both magnitudes, in a wide range of
temperatures and pressures, is nearly quantitative. This result
is remarkable because excess properties are characterized by
very-small values and are very sensitive to the molecular details
of the theory used.
Finally, we have analyzed the behavior of Henrys law
constant of carbon dioxide in water as a function of temperature.
The SAFT-VR theory is able to predict in good qualitative
agreement with experimental data, and with some molecular
simulation data, the most important features of this property.
In particular, the theory predicts the existence of the maximum
shown by this function at intermediate temperatures.
It is interesting as a final comment to emphasize how a simple
molecular approach, such as SAFT-VR, is able to predict a
number of different thermodynamic properties of the water +
carbon dioxide binary mixture, including the phase behavior,
excess functions, and Henrys law constants, relying on very-
limited experimental mixture information (in this case a single
point in the high-temperature GL critical line) and a unique
adjustable mixture parameter. The components of the mixture
studied in this work, water and carbon dioxide, are not
particularly easy to model. In particular, water has a strong
electric dipole moment and carbon dioxide has a permanent
electrical quadrupole moment. As we have mentioned, it is
possible to introduce additional contributions to the free energy
to treat these interactions explicitly; we have, however, taken
the view that the orientationally averaged interactions can be
treated in an effective way via square-well potentials of variable
range and hence implemented the SAFT-VR approach in its
15934 J. Phys. Chem. C, Vol. 111, No. 43, 2007
original form. The excellent overall agreement we observe in
the comparison with experimental data suggests that the
approach used in this work contains the essential ingredients to
predict the most-important features of the properties studied.
Acknowledgment. M.C.dR. acknowledges the Programme
Alan from European Union Programme of High Level
Scholarships for Latin America (identification no. E03D21773VE)
for a Fellowship. We also acknowledge financial support from
project no. FIS2004-06627-C02-01 of the Spanish Direccion
General de Investigacion. Additional support from Universidad
de Huelva and Junta de Andaluca is also acknowledged. We
also thank Eduardo J. M. Filipe and Manuel M. Pineiro for
useful discussions concerning to the excess enthalpy experi-
mental results.
References and Notes
(1) Kenan Center Web Page. http//www2.ncsu.edu/champagne, 2006.
(2) DeSimone, J. M. Science 2002, 297, 799-803.
(3) IPCC Special Report Carbon Dioxide Capture and Storage http://
www.ipcc.ch/index.html, 2005.
(4) CO2 sequestration http://www.princeton.edu/chm333/2002/fall/
co_two/intro/, 2002.
(5) The U.S. Department of Energy. Fossyl Energy http://www.
fossil.energy.gov/sequestration/, 2006.
(6) Valtz, A.; Chapoy, A.; Coquelet, C.; Paricaud, P.; Richon, D. Fluid
Phase Equilib. 2004, 226, 333.
(7) Ji, X.; Tan, S. P.; Adidharma, H.; and Radosz, M. Ind. Eng. Chem.
Res. 2005, 44, 7584.
(8) Seitz and, J. C.; Blencoe, J. G. Geochim. Cosmochim. Acta 1999,
63, 1559.
(9) Blencoe, J. G.; Seitz, J. C.; and Anovitz, L. M. Geochim.
Cosmochim. Acta 1999, 63, 2393.
(10) Diamond, L. W.; Akinfiev, N. N. Fluid Phase Equilib. 2003, 208,
265.
(11) Spycher, N.; Pruess, K.; Ennis-King, J. Geochim. Cosmochim. Acta
2003, 67, 3015.
(12) Chapoy, A.; Mohammadi, A. H.; Chareton, A.; Tohidi, B.; Richon,
D. Ind. Eng. Chem. Res. 2004, 43, 1794.
(13) Scott, R. L.; van Konynenburg, P. H. Discuss. Faraday Soc. 1970,
49, 87.
(14) van Konynenburg, P. H.; Scott, R. L. Philos. Trans. 1980, A298,
495.
(15) Rowlinson, J. S.; Swinton, F. L. Liquids and Liquid Mixtures, 3d
ed.; Butterworth Scientific: London, 1982.
(16) Sun, L.; Zhao, H.; Kiselev, S. B.; McCabe, C. J. Phys. Chem. B
2005, 109, 9047.
(17) Kiselev, S. B.; Ely, J. F.; Tan, S. P.; Adidharman, H.; Radosz, M.
Ind. Eng. Chem. Res. 2006, 45, 3981.
(18) Bol, W. Mol. Phys. 1982, 45, 605.
(19) Nezbeda, I.; Kolafa, J.; Kalyuzhnyi, Y. V. Mol. Phys. 1989, 68,
143.
(20) Galindo, A.; Whitehead, P. J.; Jackson, G.; Burgess, A. N. J. Phys.
Chem. 1996, 100, 6781.
(21) Galindo, A.; Whithead, P. J.; Jackson, G.; Burgess, A. N. J. Phys.
Chem. B 1997, 101, 2082.
(22) Garca-Lisbona, M. N.; Galindo, A.; Jackson, G.; Burges, A. N.
Mol. Phys. 1998, 93, 57.
(23) Garca-Lisbona, M. N.; Galindo, A.; Jackson, G.; Burgess, A. N.
J. Am. Chem. Soc. 1998, 120, 4191.
(24) Patel, B. H.; Paricaud, P.; Galindo, A.; Maitland, G. C. Ind. Eng.
Chem. Res. 2003, 42, 3809.
(25) Ji, X.; Tan, S. P.; Adidharma, H.; Radosz, M. Ind. Eng. Chem.
Res. 2005, 44, 8419.
(26) Clark, G. N. I.; Haslam, A. J.; Galindo, A.; Jackson, G. Mol. Phys.
2006, 104, 3561.
(27) Blas, F. J.; Galindo, A. Fluid Phase Equilib. 2002, 194-197, 501.
(28) Galindo, A.; Blas, F. J. J. Phys. Chem. B 2002, 106, 4503.
(29) Walsh, J. M.; Guedes, J. R.; Gubbins, K. E. J. Phys. Chem. 1992,
96, 10995.
(30) Kraska, T.; Gubbins, K. E. Ind. Eng. Chem. Res. 1996, 35, 4727.
(31) Kraska, T.; Gubbins, K. E. Ind. Eng. Chem. Res. 1996, 35, 4738.
(32) Tang, Y.; Wang, Z.; Lu, B. C.-Y. Mol. Phys. 2001, 99, 65.
(33) Dominic, A.; Chapman, W. G.; Kleiner, M.; Sadowski, G. Ind. Eng.
Chem. Res. 2005, 44, 6928.
(34) Eirini, Karakatsani K.; Theodora, Spyriouni.; Economou, G. E.
AIChE J. 2005, 51, 2328.
(35) Spyriouni, T.; Economou, I. E. AIChE J. 2005, 51, 2328.
dos Ramos et al.
(36) Zhao, H. G.; Morgado, P.; Gil-Villegas, A.; McCabe, C. J. Phys.
Chem. B 2006, 110, 24083.
(37) Israelachvili, J. Intermolecular and Surface Forces, 2nd ed.;
Academic Press: London, 1991.
(38) Gil-Villegas, A.; Galindo, A.; Whitehead, P. J.; Mills, S. J.; Jackson,
G.; Burgess, A. N. J. Chem. Phys. 1997, 106, 4168.
(39) Galindo, A.; Davies, L. A.; Gil-Villegas, A.; Jackson, G. Mol. Phys.
1998, 93, 241.
(40) Hansen, J. P.; McDonald, I. R. Theory of Simple Liquids, 2nd ed.;
Academic Press: London, 1990.
(41) Barker, J. A.; Henderson, D. J. J. Chem. Phys. 1967, 47, 2856.
(42) Barker, J. A.; Henderson, D. J. J. Chem. Phys. 1967, 47, 4714.
(43) Barker, J. A.; Henderson, D. J. ReV. Mod. Phys. 1976, 48, 587.
(44) Mansoori, G. A.; Carnahan, N. F.; Starling, K. E.; Leland, T. W.
J. Chem. Phys. 1971, 54, 1523.
(45) Boublk, T. J. Chem. Phys. 1970, 53, 471.
(46) Chapman, W. G. J. Chem. Phys. 1990, 93, 4299.
(47) Wertheim, M. S. J. Stat. Phys. 1984, 35, 19.
(48) Wertheim, M. S. J. Stat. Phys. 1984, 35, 35.
(49) Wertheim, M. S. J. Stat. Phys. 1986, 42, 459.
(50) Wertheim, M. S. J. Stat. Phys. 1986, 42, 477.
(51) Jackson, G.; Chapman, W. G.; Gubbins, K. E. Mol. Phys. 1988,
65, 1.
(52) Chapman, W. G.; Gubbins, K. E.; Jackson, G.; Radosz, M. Ind.
Eng. Chem. Res. 1990, 29, 1709.
(53) Chapman, W. G.; Jackson, G.; Gubbins, K. E. Mol. Phys. 1988,
65, 1057.
(54) dos Ramos, M. C.; Blas, F. J.; Galindo, A. Fluid Phase Equilib.,
2007, doi: 10.1016/j.fluid.2007.07.012.
(55) McCabe, C.; Galindo, A.; Cummings, P. T. J. Phys. Chem. B 2003,
107, 12307.
(56) Lsal, M.; Smith, W. R.; Aim, K. Fluid Phase Equilib. 2005, 228-
229, 345.
(57) Apelblat, A. J. J. Chem. Thermodyn. 1999, 31, 869.
(58) Keyes, F. J. Mech. Eng. Sci. 1931, 53, 132.
(59) Abdulagatov, I. M. J. Chem. Thermodyn. 1997, 29, 1387.
(60) Abdulagatov, I. M. J. Chem. Eng. Data 1998, 43, 830.
(61) Gildseth, W. J. J. Chem. Eng. Data 1972, 17, 402.
(62) Osborne, N. S. J. Res. Natl. Bur. Stand. 1933, 10, 155.
(63) Douslin, D. R. J. Sci. Instrum. 1965, 42, 369.
(64) Egerton, A. Philos. Trans. R. Soc. London, Ser. A 1932, 231, 147.
(65) Besley, L. J. Chem. Thermodyn. 1973, 5, 397.
(66) Jenkin, C. F.; Pye, D. R. Philos. Trans. R. Soc. London, Ser. A
1914, 213, 67.
(67) Sengers, J. M.; Levelt, H.; Chen, W. T. J. Chem. Phys. 1972, 56,
595.
(68) Meyers, C. H.; van Dusen, M. S. J. Res. Natl. Bur. Stand. 1933,
10, 281.
(69) Webster, L. A.; Kidnay, A. J. J. Chem. Eng. Data 2001, 46, 759.
(70) Harris, J. G.; Yung, K. H. J. Phys. Chem. 1995, 99, 12021.
(71) Nowak, P.; Tielkes, T.; Kleinrahm, R.; Wagner, W. J. Chem.
Thermodyn. 1997, 29, 885.
(72) Toedheide, K.; Franck, E. U. Z. Phys. Chem. NF. 1963, 37, 387.
(73) Takenouchi, S.; Kennedy, G. C. Am. J. Sci. 1964, 262, 1055.
(74) Wiebe, R. W.; Gaddy, V. L. J. Am. Chem. Soc. 1940, 62, 815.
(75) Wiebe, R. W.; Gaddy, V. L. J. Am. Chem. Soc. 1941, 63, 475.
(76) King, M. B.; Mubarak, A.; Kim, J. D.; Bott, T. R. J. Supercrit.
Fluids 1992, 5, 296.
(77) Coan, C. R.; King, J. A. D. J. Am. Chem. Soc. 1971, 93, 1857.
(78) Guillepsie, P. C.; Wilson, G. M. Vapor-liquid and liquid-liquid
equilibria: Water-methane, water-carbon dioxide, water-hydrogen sul-
fide, water-n-pentane, water-methane-n-pentane. Research Report
RR-48, Gas processors association, Tulsa, OK, 1982.
(79) Song, K. Y.; Kobayashi, R. SPE Form. EVal. 1987, pp 500-508.
(80) Singh, S. Phys. Rep. 2000, 324, 107.
(81) Singh, J.; Blencoe, J. G.; Anovitz, L. M. In steam, water, and
hydrothermal systems, Proceedings of the 13th International Conference
on the Properties of Water and Steam; Tremaine, P. R., Irish D. E.,.
Balakrishnan, P. V., Eds.; 2000.
(82) Chen, X.; Gillespie, S. E.; Oscarson, J. L.; Izatt, R. M. J. Sol. Chem.
1992, 21, 825.
(83) Matous, J.; Sobr, J.; Novak, J. P.; Pick, J. Collect. Czech. Chem.
Commun. 1969, 34, 3982.
(84) Schulze, G.; Prausnitz, J. M. Ind. Eng. Chem. Fund. 1981, 20, 175.
(85) Crovetto, R.; Wood, R. H. Fluid Phase Equilib. 1992, 74, 271.