Fluid Phase Equilibria 226 (2004) 333–344

Vapour–liquid equilibria in the carbon dioxide–water system,

measurement and modelling from 278.2 to 318.2 K
Alain Valtza , Antonin Chapoya , Christophe Coqueleta , Patrice Paricaudb ,
Dominique Richona,∗
a Centre d’Energétique, Ecole Nationale Supérieure des Mines de Paris CENERG/TEP, 35, rue Saint Honoré, 77305 Fontainebleau, France
b Department of Chemical Engineering, Vanderbilt University, Nashville, TN 37235-1604, USA

Received 17 September 2004; accepted 13 October 2004

Abstract

New experimental VLE data of CO2 –water binary system are reported over a wide temperature range from 278.2 to 318.2 K and pressures
up to 8 MPa. A static-analytic apparatus, taking advantage of two pneumatic capillary samplers, is used. The experimental solubility data
generated in this work are in very good agreement with previous data reported in the literature.
Three different models have been used to represent the new experimental VLE data. The first thermodynamic model is based on a
dissymmetric approach with the Peng–Robinson equation of state including classical mixing rules for the vapour phase and a Henry’s
law treatment of the aqueous phase. The second and third thermodynamic models belong to φ–φ approaches: the second model uses the
Peng–Robinson equation of state combined with the Wong–Sandler/Huron–Vidal mixing rules, and the third model the SAFT-VR equation
of state based on a variable range square-well potential.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Gas solubility; Carbon dioxide; Water; Experimental measurement; Thermodynamic model

1. Introduction Then, it appears essential to have reliable high-pressure ex-

The phase behaviour of the system carbon dioxide + water
is of great industrial interest. For example in the petroleum
industry, many natural gases contain acid gases, which have
to be removed, such as carbon dioxide and hydrogen sul-
phide. Another industrial application is the decontamination
of wastewaters containing dissolved acid gases. The capture
of carbon dioxide greenhouse gas has become a great con-
cern. Different storage techniques have been considered such
as the storage of carbon dioxide in deep saline reservoirs.
Such applications require a good knowledge of the solubil-
ity of carbon dioxide in aqueous solutions at high pressures.
∗ Corresponding author. Tel.: +33 1 64 69 49 65; fax: +33 1 64 69 49 68.
E-mail address: richon@paris.ensmp.fr (D. Richon).
perimental data and an accurate thermodynamic model over
a broad range of conditions. Three reviews [1–3] about car-
bon dioxide solubility in water have been recently published,
referring to a large number of experimental data. However,
experimental equilibrium data of the CO2 + water binary mix-
ture are scarce at high pressures.
New vapour–liquid equilibrium (VLE) data of the
CO2 + water binary mixture are reported herein in the
278.2–318.2 K temperature range up to 8 MPa. The compo-
sitions of coexisting phases have been measured by gas chro-
matography. The isotherms presented in this paper were de-
termined using an apparatus based on a static-analytic method
taking advantage of a RolsiTM capillary sampler [4]. Three
thermodynamic models have been used to represent the new
equilibrium data:

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.10.013
334 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344

• The first thermodynamic model is based on the 2. Experimental

Peng–Robinson equation of state [5] including the clas-
sical mixing rules for the vapour phase and Henry’s law
to treat the aqueous phase. The corresponding adjustable
parameters are fitted to literature data.
• The second model, the Peng–Robinson equation of
state [5] combined with the Wong–Sandler [6] mix-
ing rules + the NRTL local composition model [7] (PR-
EoS/WS-NRTL), is used to treat both phases. The binary
interaction parameters between carbon dioxide and water
are fitted to the new data.
• The third model uses the square-well version of the SAFT-
VR EoS [8,9]. Two binary interactions parameters between
water and CO2 are fitted to the new data.
The new experimental data are compared with the predic-
tions of the first model, the calculations from the two other
models and literature data. In order to evaluate the perfor-
mance of the models, the compositions of coexisting phases
have been predicted outside the temperature range of the fit-
ted data, thanks to literature data available in an extended
range.
2.1. Materials
Carbon dioxide was purchased from Air Liquide with a
certified purity greater than 99.995 vol.%. Helium (carrier
gas), from Air Liquide, is pure grade with only traces of water
(3 ppm) and of hydrocarbons (0.5 ppm). Deionised water was
used after degassing.
2.2. Apparatus and experimental procedures
The apparatus used in this work (Fig. 1) is based on a
static-analytic method with fluid phase sampling. This ap-
paratus is similar to that described originally by Laugier
and Richon [10]. The phase equilibrium is achieved in a
cylindrical cell made of sapphire, the cell volume is about
28 cm3 (internal diameter = 25 mm) and it can be operated
up to 8 MPa between 223.15 and 473.15 K. The cell is im-
mersed in a constant-temperature liquid bath (Ultra-Kryomat
from Lauda) that controls and maintains the desired temper-
ature within ±0.02 K. In order to perform accurate temper-

Fig. 1. Flow diagram of the equipment [1]. C: carrier gas; d.a.s: data acquisition system; DH2 O: degassed water; EC: equilibrium cell; FV: feeding valve; GCy:
gas cylinder; LB: liquid bath; LS: liquid sampler; PP: platinum resistance thermometer probe; PT: pressure transducer; SM: sampler monitoring; ST: sapphire
tube; Th: thermocouple; TR: temperature regulator; Vi: valve i, VS: vapour sampler; VSS: variable speed stirrer; VP: vacuum pump.
 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344 335

ature measurements in the equilibrium cell and to check for
thermal gradients, temperature is measured at two locations
corresponding to the vapour and liquid phases through two
100  platinum resistance thermometer devices (Pt100) con-
nected to an HP data acquisition unit (HP34970A). These two
Pt100 thermometers are carefully and periodically calibrated
against a 25  reference platinum resistance thermometer
(TINSLEY Precision Instruments). The resulting uncertainty
is not higher than ±0.02 K. The 25  reference platinum re-
sistance thermometer was calibrated by the Laboratoire Na-
tional d’Essais (Paris) based on the 1990 International Tem-
perature Scale (ITS 90). Pressures are measured by means of
a Druck pressure transducer connected to the HP data acquisi-
tion unit (HP34970A); the pressure transducer is maintained
at constant temperature (temperature higher than the highest
temperature of the study) by means of a specially made air-
thermostat, which is controlled using a PID regulator (WEST,
model 6100). The pressure transducer is calibrated against a
dead weight pressure balance (Desgranges & Huot 5202S,
CP 0.3–40 MPa, Aubervilliers, France). Pressure measure-
ment uncertainties are estimated to be within ±1 kPa in the
0.2–7 MPa range.
The HP on-line data acquisition unit is connected to a
personal computer through a RS-232 interface. This system
allows real time readings and storage of temperatures and
pressures throughout the different isothermal runs. The an-
alytical work was carried out using a gas chromatograph
(VARIAN model CP-3800) equipped with a thermal con-
ductivity detector (TCD) connected to a data acquisition sys-
tem fitted with BORWIN software (ver. 1.5, from JMBS,
Le Fontanil, France). The analytical column is Hayesep R
100/120 Mesh column (silcosteel tube, length: 1.5 m, diam-
eter: 1/8 in.). The TCD was used to detect both compounds;
it was repeatedly calibrated by injecting known amounts of
each compound through “liquid type” syringes for water and
through “gas type” syringes for carbon dioxide. The uncer-
tainties on the calculated moles of water are estimated to be
within ±2% in the 1.6 × 10−5 to 2 × 10−4 mol range (cal-
ibration for the liquid phase) and to be within ±7% in the
2 × 10−8 to 2 × 10−7 mol range (calibration for the vapour
phase). The relative uncertainties on the carbon dioxide mole
numbers are about ±1.5% (in the whole calibration range).
2.3. Experimental procedures
within experimental uncertainty (pressure is verified to be
constant all along the sample analyses step).
For each equilibrium condition, at least 10 samples of both
liquid and vapour phases are withdrawn using the pneumatic
samplers ROLSITM [4] and analysed in order to check for
measurement repeatability. As the volume of the withdrawn
samples is very small (typically less than 1 mg) compared to
the total mass inside the equilibrium cell (more than 5 g), it
is possible to withdraw many samples without significantly
disturbing the studied phase equilibrium.
3. Thermodynamic model
3.1. Pure compound properties
The critical temperature (Tc ), critical pressure (Pc ), and
acentric factor (ω), for each pure compound are provided in
Table 1. In this paper, carbon dioxide and water are labelled
as components 1 and 2, respectively.
3.2. First model
In this approach, an activity model is used for condensed
aqueous phases and an equation of state for vapour phases. At
equilibrium, the fugacity of each component must be equal
in all phases. The Peng–Robinson equation of state (PR-
EoS) [5] combined with the van der Waals one fluid mix-
ing rules is employed to calculate fugacities in the vapour
phases. The PR-EoS is selected because of its simplicity and
its widespread use in chemical engineering. The expression
of the PR-EoS for a pure compound is
RT a(T )
P= − , (1)
v − b v(v + b) + b(v − b)
where T, P and v are temperature, pressure and molar volume
of the system, and R the ideal gas constant. The parameters
a and b are given by
RTc
b = 0.07780 , (2)
Pc
a(T ) = ac α(T ), (3)
where

The equilibrium cell and its loading lines are evacuated (RTc )2
ac = 0.45724 . (4)
down to 0.1 Pa prior to introduction of about 5 cm3 of de- Pc
gassed water. Then, carbon dioxide is introduced into the cell
In this work we have chosen the generalised alpha function,
directly from the commercial cylinder (through preliminary
α(Tr ), proposed by Coquelet et al. [12], to have very accurate
evacuated transfer lines) to pressure level corresponding to
the pressure of the first measurement. More carbon dioxide
Table 1
is introduced after each sampling and analysis steps up to the Critical properties and acentric factors [11]
highest pressure of the studied solubility curve. After each
Compound Pc (MPa) Tc (K) ω
introduction of gas into the cell, efficient stirring is started,
and pressure is stabilized within a few minutes, solubility H2 O 22.048 647.30 0.3442
CO2 7.3830 304.21 0.2236
measurements are performed only when pressure is constant
336 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344

representation of the vapour pressures of pure compounds: at T and infinite dilution and vsat
2 the molar volume of satu-

  rated pure liquid water at T. As CO2 is at infinite dilution,
T
for T < Tc , α(T ) = exp c1 1 − the asymmetric convention (γ 1 → 1 when x1 → 0) is used to
Tc
express the Henry’s law for the gas (Eq. (15)) while the sym-
   2   3 2 metric convention (γ 2 → 1 when x2 → 1) is used for water
T T
× 1 + c2 1 − + c3 1 −  , (5) (Eq. (16)). By combining Eqs. (14) and (15), we get the CO2
Tc Tc mole fraction x1L as:

  Pϕ1V y1
T x1L = L exp[(v∞ /RT )(P − P sat )]
(17)
for T ≥ Tc , α(T ) = exp c1 1− , (6) H1,2
Tc 1 2

where c1 , c2 and c3 are correlated to the acentric factor ω The fugacity coefficients in the vapour phase are calculated
by using the PR-EoS. In this paper, the molar volume v∞ 1 is
c1 = 1.3569ω2 + 0.9957ω + 0.4077 (7) calculated with a correlation based on the work of Lyckman
c2 = −11.2986ω + 3.5590ω − 0.1146
2
(8) et al. [13] and reported by Heidemann and Prausnitz [14] in
the following form:
c3 = 11.7802ω2 − 3.8901ω + 0.5033 (9)  
Pc,i v∞
i TPc,i
For mixtures, the van der Waals one-fluid mixing rules are = 0.095 + 2.35 (18)
RTc,i c2 Tc,i
applied with cross interaction parameters kij . The expressions
of the parameters a and b become with Pc,i and Tc,i are the critical properties of the gas i, and
 c2 the cohesive energy density of water
a= xi xj aij , (10)
i j U2 vap
c2 = with U2 = H2 − RT (19)
where vsat
2
√ vap
aij = ai aj (1 − kij ), (11) where H2 is the molar enthalpy of vaporization of pure
 water at T. For a better representation of v∞
1 at high temper-
b= xi bi . (12) atures, the following correction is used
i
 
dv2 sat
where xi , xj are the mole fractions of component i and j. At v∞
1 = [v ∞
]
1 Lyckman + (T − 298.15), (20)
thermodynamic equilibrium, the fugacities fi of each compo- dT
nent i must be equal in the vapour and liquid phases.
where [v∞ 1 ]Lyckman is the molar volume of CO2 at infinite
fiL (P, T ) = fiV (P, T ) (13) dilution obtained from Eq. (18). Henry’s constant can be ad-
justed directly from experimental results and the following
The vapour fugacity comes from:
expression is used
fiV (P, T ) = ϕiV Pyi (14)
103 × d2
where ϕiV and yi are the fugacity coefficient and mole fraction
L
log10 (H1,2 ) = d1 + − d3 log10 (T ) + d4 T, (21)
T
of component i in the vapour phase. For the aqueous phase,
a Henry’s law is used to calculate the solubility of gaseous where H1,2L is in atm. The four parameters: d , d , d , and d ,
1 2 3 4
components in water. The fugacities f1L (P, T ) and f2L (P, T ) are adjusted directly on selected experimental data [15–25]
of CO2 and water in the liquid phase, at pressure P and tem- (see Fig. 2). Their values are d1 = 69.445, d2 = −3796.5,
perature T are given by d3 = −21.6253 and d4 = −1.6 × 10−5 . The NRTL model [7]

∞  (cited in Section 3.3 Eq. (30)) is used to calculate the water
v
f1L (P, T ) = H1,2
L L
x1 exp 1 (P − P2 sat ) (15) activity coefficient γ2L appearing in Eq. (16).
RT

sat 
v2 3.3. Second model
f2 (P, T ) = γ2 ϕ2 P2 x2 exp
L L sat sat L
(P − P2 )
sat
(16)
RT
The Peng–Robinson equation of state (PR-EoS) is also
where H1,2
L is Henry’s constant of CO in the liquid aque-
2 selected here. To have accurate representation of vapour pres-
ous phase at temperature T, x1L and x2L the mole fractions of sures of each component, a generalized Mathias–Copeman
CO2 and water in the liquid aqueous phase, P2sat the vapour alpha function [26], especially developed for polar com-
pressure of water at T, ϕ2sat the vapour fugacity coefficient pounds is used. It has been previously proved that pure
of saturated pure water, γ2L the activity coefficient of water compound vapour pressure calculated using this generalized
in the aqueous phase, v∞1 the partial molar volume of CO2 alpha function and the one presented in the last paragraph
 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344 337

Fig. 2. Carbon dioxide mole fraction in water-rich phase as a function of pressure at various temperatures. Literature data: ( ) 273.15 K from Wroblewski
[15]; (
) 278.15 K from Anderson [16]; (♦) 283.15 K from Anderson [16]; () 288.15 K from Oleinik [17]; () 293.15 K from Kritschewsky et al. [18]; ()
298.15 K from Oleinik [17]; ( ) 298.15 K from Zel’vinskii [19]; (×) 304.19 K from Wiebe and Gaddy [18,19]; (䊉) 308.15 K from Wiebe and Gaddy [20,21];
() 313.15 K from Wiebe and Gaddy [20,21]; ( ) 323.15 K from Oleinik [17]; ( ) 323.15 K from Zel’vinskii [19]; ( ) 323.15 K from Bamberger et al. [22];
( ) 333.15 K from Bamberger et al. [22]; Solid lines, calculated with the PR-EoS and Henry’s law with parameters from Table 2. — - —, solubility calculated
at hydrate dissociation pressure; — — —, LLV three phase line.

(Section 3.2) are identical [26]. Table 2

  Binary interaction parameters between carbon dioxide (1) and water (2)
corresponding to the model built with the PR-EoS and the classical mixing
T
for T < Tc , α(T ) = 1 + c1 1 − rules + Henry’s law
Tc
System k12 τ 12 (J/mol) τ 21 (J/mol)
  2   3 2 CO2 –H2 O 0.2324 2869 2673
T T  ,
+ c2 1 − + c3 1 − (22)
Tc Tc
where C is a constant depending on the equation of state
  2 (C = −0.62323)
T
for T ≥ Tc , α(T ) = 1 + c1 1 − ,  a  1  ai   aj 
(23)
Tc
b− = bi − + bj − (1 − kij ).
RT ij 2 RT RT
where c1 , c2 and c3 have been correlated to the acentric (28)
factor ω [14]:
where kij is a binary interaction parameter (Table 2). The
c1 = 1.0113ω2 + 1.1538ω + 0.4021, (24)
parameter a is obtained from
c2 = −7.7867ω2 + 2.2590ω − 0.2011, (25) a   a 
b− = xi xj b − , (29)
c3 = 2.8127ω2 − 1.0040ω + 0.3964. (26) RT RT ij
i j

Here, we use the Wong–Sandler (WS) mixing rules [6] that

allow matching up the excess molar Helmholtz energy of The excess Gibbs energy GE (T, xi ) of the NRTL [7] model
the mixture AE (T, P = ∞, xi ) given by PR-EoS at infinite is given by
pressure to the excess molar Gibbs free energy of the mixture
GE (T, xi )   xj exp(−αji (τji /RT ))
GE (T, xi ) given by the NRTL local composition model [7]. = xi  τji , (30)
The parameter b of the PR-EoS is given by: RT k xk exp(−αki (τki /RT ))
i j

i j xi xj (b − (a/RT ))ij with τ ii = 0 and αii = 0; αji , τ ji and τ ij are adjustable parame-
b=   ,
1− i xi (ai /bi )/RT + (A (T, P = ∞, xi )/CRT )
E
ters. It is recommended [7] to use αji = 0.3 for polar–non-polar
(27) systems. τ ji and τ ij are adjusted directly to VLE data (Table 3).
338 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344

Table 3
NRTL and Wong–Sandler parameters
T (K) τ 12 (J/mol) τ 21 (J/mol) k12
278.22 4051 227 1.092
288.26 6486 2579 0.559
298.28 8392 4185 0.224
308.20 6861 4050 0.394
318.23 9458 5288 0.179

3.4. Third model

The third thermodynamic model is the square-well ver-

sion of the SAFT-VR theory [8,9], used for both vapour and
liquid phases (φ–φ approach). The SAFT-VR theory, derived
from statistical mechanics, is based on a representation of
the interactions at the molecular level with a well-defined
intermolecular potential. Hence, the parameters of the ther-
modynamic model have physical meanings, and the equation
of state can be compared with molecular simulations using
the same intermolecular potential [8,9]. In the SAFT-VR the-
ory, molecule i is modelled as a flexible object of mi tangent
spherical segments of diameter σ ii , and the dispersive inter-
actions between segments of type i and j are modelled with a
square-well potential uji of depth εij and range λij defined as
 
 +∞, r < σij ,
 
 where N is the number of molecules in the system, and k the
uij (r) = −εij , σij ≤ r < σij λij . (31)

 

0, r ≥ σij λij
Although the square-well potential is a crude approxima-
tion of the real intermolecular potential, it enables to have
simple analytical expressions, while keeping the essential
of the physics of the system. Moreover, the range variable,
λij , is a particularly useful to describe polar and quadrupolar
molecules such as water and carbon dioxide. Water is repre-
sented as a hard sphere (m1 = 1) with four association sites, as
suggested by Nezbeda et al. [27]. Water–water interactions
are splitted into dispersive interaction and hydrogen bonding
represented by square-well potentials and site–site associa-
tions. By studying the phase behaviour of binary mixtures of
CO2 and n-alkanes, Galindo and Blas [28] have shown that
CO2 molecule is better represented by a square-well dimer
(m2 = 2) in the SAFT-VR model. Water–CO2 interactions are
modelled with a square-well potential between segments. The
Fig. 3. Molecular models for carbon dioxide and water used in the SAFT-
VR model. (a) The carbon dioxide molecule is represented by two tangent
segments of diameter σ 11 . (b) The water molecule is represented as a hard
sphere of diameter σ 22 . Dispersion interactions are described with square-
well potentials. Hydrogen bonding between water molecules is modelled
by site associations: sites E and H are represented by spherical square-well
potentials such that the bonding energy is equal to εEH when two square-well
sites E and H overlap. KEH denotes the overlap (or bonding) volume.
expressed in terms of Helmholtz free energy is a sum of four
different contributions:
A AIDEAL AMONO ACHAIN AASSOC
= + + + , (32)
NkT NkT NkT NkT NkT
Bolztmann constant. The term AIDEAL is the free energy of
the chain molecule system considered as an ideal gas mix-
ture. The first residual term AMONO takes into account the
interactions between square-well segments, and is obtained
from the Barker–Henderson high temperature perturbation
theory [32]
A1 A2
AMONO = AHS + + , (33)
kT (kT )2
where AHS is the residual Helmholtz free energy of a mixture
of hard spheres, derived independently by Boublı́k [33] and
Mansoori et al. [34]. The attractive terms A1 and A2 are ob-
tained from Barker and Henderson’s perturbation theory by
using the van der Waals one-fluid mixing rule called MX1b in
refs. [9,30]. The general expression of the chain contribution
ACHAIN , derived from Wertheim’s theory [35–40] is
SAFT molecular representations of water and carbon diox-
ide are shown in Fig. 3. Since we are interested in regions of
the phase diagram closed to the critical point of CO2 , we use
here the SAFT-VR parameters for CO2 from ref. [28], which
are rescaled to the critical point of CO2 , and the SAFT-VR
parameters of water from refs. [29,30], which are fitted to
vapour pressures and saturated liquid densities of pure wa-
ter. Note that it would be more appropriate to use the recent
crossover version of SAFT-VR [31] to have predictions that
are more accurate over the entire range of conditions. We plan
to use it in future studies. The reader can find a full descrip-
tion of the theory in refs. [8,9,30]. The SAFT-VR equation
ACHAIN 
=− xi (mi − 1) ln yiiSW (σii ), (34)
NkT
i
where xi is the mole fraction of molecule i, and yiiSW (σii ) the
contact value of the cavity function between two square-well
spheres of diameter σ ii in a mixture of square-well spheres.
One can replace the cavity function yiiSW (σii ) by the radial
distribution function giiSW (σii ) at contact in Eq. (34), without
affecting phase equilibrium calculations. The expression of
giiSW (σii ) can be found in refs. [8,9]. In this work, the chain
contribution ACHAIN is only due to the formation of square-
well dimers representing CO2 molecules, then Eq. (34) re-
 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344 339

duces to
ACHAIN
= −x1 ln g11
SW
(σ11 ). (35)
NkT
The association term AASSOC derived from Wertheim’s theory
[35–40] is given by
s   
AASSOC   i
Xa,i si
= xi ln Xa,i − + , (36)
NkT 2 2
i a=1

where Xa,i is the fraction of molecule i non-bonded at site

a. The first sum is over all associating molecules i. The sec-
ond sum is over the si sites a of molecule i. Here, water is
the only associating molecule, with two equivalent E sites
representing the electronic pair of the oxygen atom, and two
H sites representing the hydrogen atoms. As the fractions of
non-bonded water molecules at the sites E and non-bonded
at H are all equal, the association contribution AASSOC can
then be written as [29,30]:
AASSOC
= x2 [4 ln X2 − 2X2 + 2], (37)
NkT
where X2 is the fraction of non-bonded water molecules at a
given site (E or H). X2 is the solution of the quadratic equation
1 tion F:
X2 = , (38)
1 + 2x2 ρX2 ∆22
Fig. 4. Pressure–temperature, PT, diagram of the binary mixture carbon
dioxide + water, determined with the SAFT-VR equation of state. The con-
tinuous lines represent the vapour pressures (VP) of the pure compounds.
The dashed lines represent the vapour–liquid (VL) and fluid–fluid (FF) crit-
ical lines. The dashed–dotted line represents the three-phase line (VLL) that
ends at the upper critical end point (UCEP, grey triangle). The circles repre-
sent the critical points of the pure compounds.
For the three models, binary parameters are adjusted with
a Simplex algorithm [41] using the following objective func-
  L 2 
Nexp  2 N
100   ycal − yexp  xcal − xexp
exp L
F= + ,
where ∆22 = K22 EH (exp(εEH /kT ) − 1)gSW (σ ), and εEH and
22 22 22 22 Nexp yexp xexp
L
1 1
K22 are the energy and bonding volume of the EH site–site
EH

association. The values of the parameters εEH (40)

22 and K22 are
EH

given in Table 4. The Lorentz–Berthelot mixing rules for ε12 L , xL ) and (y ,

and σ 12 , and a simple mixing rule for the square-well range
λ12 are applied with two binary parameters k12 ε and k λ
12
σ11 + σ22 √ ε
σ12 = , ε12 = ε11 ε22 (1 − k12 ),
2
σ11 λ11 + σ22 λ22 λ
λ12 = (1 − k12 ),
σ11 + σ22
where σ 12 , ε12 and λ12 are the hard sphere diameter, depth
and width of the square-well potential between water and
CO2 segments. Note that we do not use any binary parameter
for σ 12 , otherwise the fundamentals of the SAFT-VR theory
based on the hard sphere mixture would be lost. Moreover,
we use the same values for k12ε and k λ over the entire range
12
of temperatures, as an intermolecular potential should not
depend on temperature. The phase equilibrium is obtained
when the pressure and the chemical potentials (or fugacities)
of each component are equal in all coexisting phases.
where Nexp is the number of data points (xexp exp
cal
ycal ) the measured and calculated compositions of the coex-
isting liquid and vapour phases at fixed T and P.
4. Results and discussions
(39)
The system CO2 –H2 O is a type III binary mixture ac-
cording to Scott and van Konynenburg’s classification [42].
The pressure–temperature PT diagram displayed on Fig. 4 for
the CO2 –H2 O mixture has been determined with the SAFT-
VR EoS and the parameters given in Tables 4 and 5. Two
critical lines appear on this theoretical pressure–temperature
PT diagram: a small vapour–liquid critical line starting at
the critical point of carbon dioxide and ending at an up-
per critical end point (UCEP), and a second fluid–fluid
critical line extending at high pressures from the critical
point of water. As shown in the zoomed part of Fig. 4, the

Table 4
SAFT-VR pure component parameters: number of segments (m), square-well potential (εii , σ ii , λii ) and site association (εEH
ii , Kii ) parameters from refs.
EH

[29,30]
Component mi εii /k (K) σ ii (Å) λii Sites εEH
ii /k (K) KiiEH (Å3 )
CO2 2 168.89 3.1364 1.5157 No site – –
H2 O 1 253.30 3.0360 1.8000 2 E, 2 H 1365.923 1.0202
340 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344

Table 5 vapour–liquid–liquid (VLL) three-phase line is very close

Parameters of the square-well potential (ε12 , σ 12 , λ12 ) between water and to the vapour pressure of carbon dioxide. Note that hydrate
CO2 segments in the SAFT-VR model, and corresponding binary interaction phases are not mentioned on this PT diagram. According
ε λ )
parameters (k12 , k12
to Chapoy et al. [1], the pressure of the hydrate dissoci-
ε λ
System ε12 /k (K) σ 12 (Å) λ12 k12 k12 ation is around 1.3 MPa at 273.15 K and around 4.5 MPa
CO2 –H2 O 364.31 3.0862 1.3785 −0.76138 0.16732
at 283.15 K. In this paper, we study the region of the PT

Table 6
Experimental and calculated mole fractions of carbon dioxide in the aqueous phase, in the system carbon dioxide (1) + water (2)
T (K) Pexp (MPa) x1L × 102 (exp) x1L × 102 (cal)
Model 1 AD % Model 2 AD % Model 3 AD %
318.23 0.465 0.182 0.179 1.4 0.161 11.4 0.183 0.5
318.23 1.045 0.394 0.394 0.1 0.361 8.3 0.402 2.1
318.23 1.863 0.68 0.673 1.1 0.632 7.1 0.687 1.0
318.23 1.984 0.73 0.712 2.5 0.671 8.1 0.726 0.5
318.23 2.97 1.036 1.007 2.8 0.975 5.9 1.029 0.7
318.23 3.001 1.018 1.015 0.3 0.984 3.3 1.038 2.0
318.23 3.969 1.293 1.267 2.0 1.259 2.6 1.298 0.4
318.23 3.977 1.259 1.269 0.8 1.262 0.2 1.300 3.3
318.23 4.952 1.508 1.489 1.3 1.513 0.3 1.529 1.4
318.23 4.982 1.532 1.495 2.4 1.52 0.8 1.535 0.2
318.23 5.978 1.72 1.684 2.1 1.748 1.6 1.735 0.9
318.23 5.992 1.726 1.687 2.3 1.751 1.5 1.737 0.7
318.23 6.923 1.895 1.834 3.2 1.935 2.1 1.895 0.0
318.23 6.984 1.905 1.842 3.3 1.946 2.2 1.904 0.0
318.23 7.933 2.031 1.962 3.4 2.101 3.5 2.042 0.5
308.20 0.579 0.276 0.273 1.0 0.249 9.7 0.282 2.1
308.20 1.889 0.856 0.826 3.4 0.786 8.2 0.850 0.7
308.20 2.95 1.212 1.205 0.6 1.187 2.1 1.239 2.2
308.20 3.029 1.259 1.231 2.2 1.212 3.8 1.266 0.5
308.20 4.005 1.563 1.525 2.4 1.541 1.4 1.569 0.4
308.20 4.985 1.837 1.774 3.4 1.837 0 1.828 0.5
308.20 5.949 2.033 1.975 2.9 2.089 2.7 2.039 0.3
308.20 6.077 2.066 1.998 3.3 2.119 2.6 2.064 0.1
308.20 6.972 2.229 2.14 4.0 2.307 3.5 2.217 0.5
308.20 6.986 2.152 2.142 0.5 2.31 7.3 2.219 3.1
308.20 7.029 2.221 2.148 3.3 2.318 4.4 2.225 0.2
308.20 7.963 2.304 2.247 2.5 2.456 6.6 2.335 1.3
298.28 0.504 0.314 0.303 3.6 0.287 8.5 0.312 0.7
298.28 1.007 0.614 0.586 4.5 0.568 7.5 0.602 2.0
298.28 1.496 0.887 0.842 5.0 0.833 6.1 0.862 2.8
298.28 2.483 1.356 1.304 3.8 1.341 1.1 1.330 1.9
298.28 3.491 1.772 1.703 3.9 1.815 2.4 1.734 2.2
298.28 4.492 2.089 2.03 2.8 2.234 6.9 2.066 1.1
298.28 5.524 2.323 2.296 1.2 2.598 11.8 2.338 0.7
288.26 0.496 0.401 0.394 1.6 0.362 9.7 0.399 0.5
288.26 1.103 0.867 0.839 3.3 0.79 8.9 0.843 2.8
288.26 1.941 1.434 1.384 3.5 1.347 6.1 1.378 3.9
288.26 2.777 1.882 1.852 1.6 1.859 1.2 1.834 2.5
288.26 3.719 2.343 2.292 2.2 2.376 1.4 2.262 3.5
288.26 4.601 2.673 2.622 1.9 2.792 4.4 2.583 3.4
288.26 5.059 2.797 2.761 1.3 2.976 6.4 2.720 2.8
278.22 0.501 0.585 0.551 5.7 0.559 4.5 0.538 8.0
278.22 0.755 0.852 0.813 4.6 0.83 2.6 0.789 7.4
278.22 1.016 1.111 1.071 3.6 1.101 0.9 1.033 7.0
278.22 1.322 1.403 1.358 3.2 1.408 0.4 1.302 7.2
278.22 1.674 1.747 1.669 4.5 1.747 0 1.590 9.0
278.22 2.031 2.015 1.963 2.6 2.074 2.9 1.860 7.7
AAD % 2.6 4.4 2.2

With AAD: average absolute deviation, AAD = (1/Nexp ) Nexp |(xexp − xcal )/xexp | and AD: absolute deviation, AD = |(xexp − xcal )/xexp |.
 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344 341

Table 7
Experimental and calculated mole fractions of water in the CO2 -rich vapour phase, in the system carbon dioxide (1) + water (2)
T (K) Pexp (MPa) y2 × 102 (exp) y2 × 102 (cal)
Model 1 AD % Model 2 AD % Model 3 AD %
318.22 0.464 2.5 2.09 16.3 2.15 13.9 2.14 14.6
318.22 1.044 1.25 0.97 22.3 1.02 18.6 1.00 19.8
318.22 1.863 0.65 0.58 10.7 0.62 4.2 0.60 8.0
318.22 3.001 0.44 0.4 9.9 0.44 0.5 0.41 7.5
318.22 3.98 0.38 0.33 14.1 0.38 0.8 0.33 12.1
318.22 4.956 0.35 0.29 17.7 0.35 1.1 0.29 16.0
318.22 5.992 0.33 0.27 19.4 0.34 1.8 0.27 18.0
318.22 6.93 0.29 0.26 11.0 0.34 18.6 0.26 9.8
308.21 0.582 0.96 0.99 3.5 1.00 3.9 1.03 6.8
308.21 0.819 0.79 0.72 8.9 0.72 8.7 0.74 6.0
308.21 1.889 0.34 0.34 0.5 0.34 0.3 0.35 3.4
308.21 2.97 0.23 0.24 4.3 0.24 2.6 0.25 7.0
308.21 3.029 0.23 0.24 2.9 0.23 1.3 0.24 5.4
308.21 4.005 0.20 0.2 1.3 0.19 3.5 0.20 0.8
308.21 4.985 0.17 0.18 4.1 0.17 1.8 0.18 5.9
308.21 5.949 0.16 0.17 4.9 0.17 3.1 0.17 6.3
308.21 7.056 0.17 0.17 0.0 0.17 0.6 0.17 0.7
308.21 7.93 0.23 0.2 12.0 0.23 0.4 0.21 9.3
308.21 7.963 0.25 0.21 17.4 0.24 3.6 0.21 14.3
298.28 0.504 0.65 0.65 0.1 0.66 1.2 0.67 3.2
298.28 1.007 0.38 0.34 10.6 0.35 8.2 0.35 7.8
298.28 1.496 0.28 0.24 14.5 0.25 11.1 0.25 12.0
298.28 2.483 0.14 0.16 13.4 0.17 21.4 0.16 16.3
298.28 3.491 0.13 0.13 3.3 0.14 6.9 0.13 1.2
288.26 0.496 0.31 0.36 15.5 0.35 11.6 0.37 19.3
288.26 1.103 0.14 0.17 21.9 0.16 14.3 0.18 25.6
288.26 1.941 0.09 0.11 17.5 0.1 5.6 0.11 20.6
278.22 0.501 0.15 0.18 22.2 0.16 8.7 0.19 26.1
278.22 0.755 0.11 0.12 13.5 0.11 3.6 0.13 17.0
278.22 1.016 0.07 0.1 36.2 0.08 10 0.10 40.3
AAD % 11.7 6.4 12.0

phase diagram close to the critical point of carbon diox-
ide.
The experimental and calculated compositions of the
vapour and liquid phases are reported in Tables 6 and 7, and
plotted in Figs. 2 and 5. Our new data are in very good agree-
ment with previous experimental studies [15,25]. In the first
model (PR-Eos + Henry’s law), the binary parameters haven
been fitted to literature data [15,25] and are given in Table 2.
As shown in Fig. 5a, the CO2 solubility data are well
represented with the first model (Henry’s law), and the av-
erage absolute deviation, AAD, from the new data is 2.6%
(Table 6). The AAD for the water content predicted by the
first model is 11.7% (Table 7). In the second model (PR-
Eos + WS + NRTL), temperature dependant binary interac-
tion parameters have been adjusted to the new CO2 solubility
data and are given in Table 3. The average deviation is 4.6%
(Table 6). The representation of the gas phase composition
with the second model is more accurate than those obtained
with the first and third models, especially at low tempera-
tures. In his case, the AAD is only of 6.4% (Table 7). For
the last model, the overall accuracy is comparable to those
of the other models, and the predictions of CO2 solubility
is slightly better (AAD = 2.2%). However, the AAD for the
water content predicted by this model is 12% (Table 7).
As shown in Fig. 5, the representation of the new
data with the second model is good but not as accu-
rate as with the first model. Deviations are bigger at high
pressures for the second model. This mixture is highly
asymmetric, as the pure compounds have very different
vapour–pressure curves, which could explain the devia-
tion at high pressures. In the Peng–Robinson EoS, the ra-
tio b1 /b2 = (Tc1 Pc2 )/(Tc2 Pc1 ) = 1.4 is large between the two
molar covolumes b1 and b2 , showing that the mixture
is very asymmetric. Coutsikos et al. [43] argue that the
Wong–Sandler mixing rules are less suitable to model such
asymmetric systems at high pressures, as the matching be-
tween GE and AE is less accurate at high pressures. Note that
Coutsikos et al. [43] use a different excess enthalpy models
from ours. Different mixing rules for such systems have been
developed like the non-density dependent mixing rules [44]
where no excess enthalpy models are used.
With SAFT-VR only two binary parameters are used for
the whole range of temperatures. The obtained values for
the binary parameters are large (Table 5), showing that the
342 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344

Table 8
Temperature, pressure and compositions along the three-phase line
Texp = Tcal Pexp Pcal AD % Calculated compositions
(K) (MPa) (MPa)
y2 × 102 x1L2 × 102 x2L1 × 102
283.12 4.484 4.568 1.9 0.048 2.879 0.145
285.17 4.716 4.796 1.7 0.053 2.825 0.153
288.67 5.13 5.206 1.5 0.064 2.737 0.166
288.69 5.132 5.208 1.5 0.064 2.736 0.166
293.08 5.693 5.760 1.2 0.082 2.633 0.182
298.16 6.405 6.448 0.7 0.11 2.524 0.198
298.19 6.408 6.451 0.7 0.11 2.523 0.198
304.58 7.403 7.402 0.0 0.179 2.399 0.192
304.62 7.409 7.409 0.0 0.181 2.398 0.191
304.63 7.411 7.410 0.0 0.182 2.398 0.190
The mole fractions of water in the vapour phase (y2 ), of CO2 in the liquid
aqueous phase (x1L2 ), and of water in the CO2 -rich liquid phase (x2L1 ) are
calculated with the SAFT-VR EoS. Experimental data are from ref. [45].

[28] were rescaled to the critical temperature and pressure of

Fig. 5. Compositions of the coexisting liquid and vapour phases for the car-
bon dioxide + water binary mixture, as a function of pressure. (a) CO2 mole
fraction in aqueous liquid phase; (b) water mole fraction in the CO2 -rich
vapour phase. New solubility data: () 318.2 K; () 308.2 K; (
) 298.2 K;
(䊉) 288.2 K; () 278.2 K. (a) Literature solubility data: (×) 308.15 K from
Wiebe and Gaddy [20,21]; (
) 298.15 K from Zel’vinskii [19]; (♦) 288.15 K tal UCEP has been found at T = 304.63 K and P = 7.411 MPa
CO2 , resulting in a less accurate representation of CO2 -rich
phases at low temperatures. The representation of water at
these temperatures is accurate as the parameters of water were
fitted to saturated liquid densities and vapour pressures [29].
However, the model overestimates the critical temperature
and pressure of water, as shown in the PT diagram of Fig. 4.
It would be useful to use the crossover version of SAFT-VR
[31] to have very accurate predictions over the entire range
of temperatures. We leave that issue for future studies. We
have predicted the three-phase line with SAFT-VR and ob-
tained very good agreement with experimental pressure data
(see Table 8). The predicted upper critical end point (UCEP)
is at T = 304.68 K and P = 7.418 MPa, while the experimen-
from Anderson [16]; () 278.15 K from Anderson [16]; (b) Literature water [45]. To test the extrapolation capabilities of the SAFT-VR
content data: (+) 323.15 K from [24]; ( ) 323.15 K from [24]; ( ) 323.15 K
EoS, we have predicted the compositions of the CO2 -rich
from [43]; ( ) 323.15 K from [44]; ( ) 348.15 K from [24]; ( ) 348.15 K
from [24]; () 348.15 K from [25]. Models: dashed lines: PR-EoS + Henry’s
law (model 1); thick dotted line, limit of appearance of CO2 hydrate, calcu-
lated with model 1; grey solid lines, PR-EoS/WS-NRTL model (model 2);
black solid lines, SAFT-VR EoS (model 3); dashed and dotted line, VLL
three phase line calculated with SAFT-VR EoS (model 3), delimiting the
vapour–liquid and liquid–liquid coexistence regions; ( ) upper critical end
point (UCEP) calculated with SAFT-VR EoS (model 3).
mixture is particularly non-ideal. Note that range λ12 of the
square-well potential between water and CO2 is small, and the
depth ε12 large (see Table 5), suggesting that association may
occur between both molecules. We have tried to use associa-
tion sites between water and CO2 and fitted the corresponding
energy and bonding volumes to the new data. However, the
obtained bonding energy was close to zero and we decided
not to use any association between water and CO2 . As shown
in Tables 6 and 7 and in Fig. 5, the SAFT-VR represents con-
veniently the new experimental data in both phases. However,
as seen in Fig. 5b, water content predictions at high pressures
and temperatures deviate from literature data and the devia-
tions are larger at low temperatures in the CO2 -rich vapour
phase. This result can be explained by the choice of the pa-
rameters for carbon dioxide. In fact, these parameters for CO2
phase at high temperatures outside the range the new data,
with the same binary parameters. The representation of the
data is accurate and the deviations are slightly larger that
those of the first model (see Fig. 5b). The liquid–liquid coex-
istence curve at high pressures has also been predicted with
SAFT-VR and is shown in Fig. 5b.
With SAFT EoS, the only fitted property is the dispersive
part of the potential between water and CO2 . In SAFT EoS,
the kij are used indirectly on the energetic terms through the
molecular parameters characterizing the intermolecular po-
tential between water and CO2 . These kij have to be indepen-
dent of temperature to keep a consistent theory and avoid a
too empirical approach, as intermolecular potential parame-
ters should not depend on temperature. Then, the energy dis-
persive terms corresponding to this intermolecular potential
has the natural temperature dependence coming from the the-
ory. This is why we only used two parameters for the binary
mixture, which do not depend on temperature, as a test of the
theory. Oppositely, in PR type model, the binary parameters,
kij, are used directly on the energy dispersive terms of equa-
tion of state. This is may be why it is sometimes necessary
to use kij temperature dependant binary parameters.
 A. Valtz et al. / Fluid Phase Equilibria 226 (2004) 333–344 343

5. Conclusion Subscripts
a site a
New experimental data on the solubility of carbon diox- c critical property
ide in water were generated over a wide temperature range cal calculated property
(from 278.2 to 318.2 K). The new data have been represented exp experimental property
by three different models. All three approaches are in very i, j component i, j
good agreement with the new data and the solubility of CO2
in water is particularly well represented. The first model, Superscripts
whose parameters were adjusted from literature data, allows ASSOC association contribution in SAFT-VR
us to validate these new generated data. The second model CHAIN chain contribution in SAFT-VR
gives the most accurate predictions of the composition of the E excess property
vapour phase for all temperatures; however, the deviations EH association between site E and H
on the CO2 solubility are more important at high pressures. IDEAL ideal term in SAFT-VR
The third model (SAFT-VR) gives accuracy similar to the L liquid phase
first model in predicting the CO2 solubility. The UCEP was MONO monomer contribution in SAFT-VR
extrapolated by the SAFT-VR model. However, these results SW square-well term
could be improved by using the SAFT-VR theory combined V vapour phase
with a crossover approach.

List of symbols
a attractive term in PR-EoS (Pa m6 /mol2 )
A Helmholtz free energy (J)
b co-volume in PR-EoS (m3 /mol)
c1 , c2 , c3 constants used in the alpha function (PR-EoS)
C constant used in Wong–Sandler mixing rules
d1 , d2 , d3 , d4 constants used in Eq. (21)
gSW radial distribution function of the square-well fluid
G Gibbs free energy (J)
k Boltzmann constant (J/K)
kij binary parameter used in PR-EoS and SAFT-VR
K bonding volume in SAFT-VR (m3 )
m number of segments of a chain in SAFT-VR
N number of molecules
Nexp number of experimental points
P pressure (MPa)
R ideal gas constant (J/(mol K))
si number of associating sites on molecule i
T temperature (K)
u square-well potential (J/mol)
v molar volume (m3 /mol)
x composition (mole fraction)
X fraction of non-bonded molecules
ySW cavity function of the square-well fluid
Y composition in vapour phase (mole fraction)
Greek letters
α alpha function in PR-EoS
αii binary parameter in NRTL
ε depth of a square-well potential in SAFT-VR (J)
σ segment diameter in SAFT-VR (m)
γ activity coefficient in the aqueous phase
λ range of a square-well potential in SAFT-VR
ρ number density in SAFT-VR
τ ij binary parameter in NRTL (J/mol)
ω acentric factor
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