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Bubble points of the systems isopropanol–water, isopropanol–water–sodium

acetate and isopropanol–water–sodium oleate at high pressure

Article  in  Fluid Phase Equilibria · June 2006

DOI: 10.1016/j.fluid.2006.03.021

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 Fluid Phase Equilibria 244 (2006) 78–85

Bubble points of the systems isopropanol–water, isopropanol–water–sodium

acetate and isopropanol–water–sodium oleate at high pressure
M.D. Bermejo a , A. Martı́n a , L.J. Florusse b , C.J. Peters b,∗ , M.J. Cocero a
aDepartment of Chemical Engineering and Environmental Technology, University of Valladolid, Prado de la Magdalena s/n. 47011 Valladolid, Spain
b Physical Chemistry and Molecular Thermodynamics, Department of Chemical Technology, Faculty of Applied Sciences, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands
Received 16 September 2005; received in revised form 29 March 2006; accepted 29 March 2006
Available online 6 April 2006

Abstract
Supercritical water oxidation (SCWO) is a powerful technology for destroying organic wastes with high removal efficiencies. Corrosion and salt
deposition are the main challenges for the industrial development of the SCWO process. In SCWO heteroatoms are oxidized until high oxidation
states: oxides, acids or salts. If there are enough cations, the heteroatoms precipitate as salts and eventually can be recovered. Cations can be
introduced in the system by adding organic salts to the feed. The organic part of the salt is oxidized to CO2 and water, and the cations remain free
to join the free anions and precipitate as inorganic salts. The thermodynamic study of this system it is very interesting for future modeling of the
SCWO process.
Bubble points of the systems isopropanol (IPA)–water, IPA–water–sodium acetate and IPA–water–sodium oleate were determined in the tem-
perature range (396 and 460 K), pressures higher than 0.35 MPa, with IPA concentrations lower than 5 mol% and salt concentrations of 5 and
8.2 mol% for sodium acetate, and 0.11 and 0.25 mol% for sodium oleate. Bubble points were determined using a Cailletet apparatus that operates
with the synthetic method.
As expected, the vapor pressure of the system increases as IPA concentration is increased, and in general decreases when salt concentration
increases. The measured vapor pressures of mixtures of water and IPA were consistent with literature data.
The experimental data were correlated using the Anderko–Pitzer EoS, which was specially developed for water–salt systems at high temperatures
and pressures. Densities and vapor pressures of IPA and the experimental data presented in this work were used for obtaining the parameters of the
EoS in the range of pressure and temperature of the data. In the range of temperature and concentration considered, the average deviations between
experimental and calculated vapor pressures were %
P = 1.18% for the system IPA–water, %
P = 4.03% for the system IPA–water–NaAc and
%
P = 2.77% for the system IPA–water–NaOl.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Isopropanol; Sodium acetate; Sodium oleate; LV equilibrium; Anderko–Pitzer EoS; Supercritical water oxidation

1. Introduction tion of this powerful technology to the treatment of industrial

Supercritical water oxidation is a technology for the destruc-
tion of organic wastes, which consists of the oxidation of
organic compounds using oxygen, in an aqueous medium
at a pressure and a temperature above the critical pressure
and temperature of water. With SCWO removal efficiencies
higher than 99% can be achieved. Corrosion and plugging by
salt deposition are the two main challenges in the applica-
∗ Corresponding author. Tel.: +31 15 278 26 60; fax: +31 15 278 42 89.
E-mail addresses: C.J.Peters@tudelft.nl (C.J. Peters), mjcocero@iq.uva.es
(M.J. Cocero).
wastewaters.
When heteroatoms are present in the waste, they are oxi-
dized till high oxidation states: oxides, acids or salts. If there are
enough cations present in the feed, the heteroatoms precipitate
as salts and eventually can be recovered. One way to introduce
cations in the system is adding organic salts to the feed, the
organic part of the salt is oxidized to CO2 and water, and the
cations remain free to join the free anions and precipitate as
inorganic salts.
As a first step in this study, the phase behavior of mixtures
of these salts with water and organic materials must be known.
Since isopropyl alcohol (IPA) is frequently used as fuel in SCWO
processes, the phase behavior of systems consisting of IPA, water

0378-3812/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.03.021
 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85
and an organic salt has been studied. Two organic salts have been
analyzed: sodium acetate and sodium oleate. These salts can be
suitable for the SCWO process because of their high solubility
in water.
Information in literature about systems alcohol–water–
organic salts is very scarce. In this paper only a few representa-
tive references are mentioned:
• For the system IPA–water, Wilson and Simons [1] carried out
an experimental study at pressures ranging from 95 to 4 mm
Hg and Barr-David and Dodge [2] published experimental
data of the system IPA–water up to conditions approaching
the critical point of water.
• Tan [3] performed an experimental study of the vapor–liquid
equilibrium of the system IPA–water saturated with inorganic
salts (potassium and calcium nitrate) at atmospheric pressure.
• Vercher et al. [4] published data of vapor–liquid equilibrium
of the system ethanol–water–potassium acetate, and potas-
sium/sodium acetate at atmospheric pressure.
In this paper, experimental bubble point data are presented
for the systems: IPA–water, IPA–water–sodium acetate and
IPA–water–sodium oleate at pressures higher than 3.5 bar and
temperatures up to 470 K, with IPA concentrations lower than
5 mol% and salt molar fractions of 5 and 8.2 mol% for sodium
acetate and 0.11 and 0.25 mol% for sodium oleate.
The Anderko and Pitzer EoS [5] has been used for the corre-
lation of the experimental data. This EoS was developed in order
to represent volumetric properties as well as vapor–liquid and
solid–liquid equilibrium of aqueous salt solutions at high pres-
sures and temperatures. The equation consists of a reference
and a perturbation contribution. The reference part represents
the properties of a mixture of hard sphere ion-pair and dipolar
solvent molecules. In the Anderko and Pitzer [5] model the EoS
parameters were fitted to an extensive amount of experimental
data of the system water–NaCl. Anderko–Pitzer also used their
EoS for fitting water–KCl data and water–NaCl–KCl data [6].
Jiang and Pitzer used the EoS for the water–CaCl2 system [7].
Later Duan et al. used the EoS for the systems H2 O–CO2 –NaCl
[8], H2 O–CH4 –NaCl and H2 O–CO2 –CH4 –NaCl [9]. In 2001,
Kosinski and Anderko extended the EOS to multicom-
ponent water–salt–non-electrolyte systems and developed a
corresponding-states methodology for systems for which very
little experimental information is available. In addition, they
re-adjusted water and salt parameters for temperatures below
573 K [10]. In a previous paper, this methodology was used to
fit the parameters of the Anderko and Pitzer EoS to experimental
vapor–liquid equilibrium data of CO2 –H2 O–Na2 SO4 [11].
2. Experimental
For all measurements a Cailletet apparatus was used. It oper-
ates according to the synthetic method, i.e., a sample of known
overall composition was used.
The Cailletet tube consists of a thick-walled Pyrex tube. One
end is closed and the other end is open. The sample can be con-
fined inside the closed end of the Cailletet tube using mercury as
79
a sealing and pressure transmitting fluid. A small steel ball inside
the top of the tube allows stirring of the sample magnetically.
A pressure balance (Budenberg) in combination with a hand
screw pump was used to measure pressures and to maintain a
constant pressure. The pressure balance has been designed for a
range of 0.35–14 MPa, with a maximum accuracy of 0.005 MPa.
The Cailletet tube is jacketed and silicon oil is employed as a
thermostatic fluid. The range of working temperatures is up to
190 ◦ C. The thermometer employed is a Pt100 with an accuracy
of 0.01 K. A more detailed description about the experimental
facility and the experimental procedures as well can be found
elsewhere [11–13].
The measurements obtained from the Cailletet facility com-
prise the determination of liquid–vapor two-phase boundary.
Therefore, first the temperature is adjusted at a fixed value and
the pressure is brought to a value where two phases, liquid and
vapor, exist. Then the pressure is gradually increased until the
vapor phase just disappears. It is essential that after each change
in pressure, equilibrium between the coexisting phases be estab-
lished. At the pressure where the vapor phase just disappears
a homogeneous liquid phase is obtained and consequently the
composition of this liquid is the same as the original overall
composition. A point on the two-phase boundary is obtained
when a small change in pressure results in formation of a vapor
phase or elimination of the existing vapor phase. As the organic
salts used in this study may be subject to thermal degradation
at elevated temperatures, the measurement of the vapor pres-
sures has been made as follows: first the vapor pressures of the
samples were measured at temperatures increasing in steps of
10 K: i.e. 410 and 420 K and so on, and when the maximum tem-
perature of 460 K was reached, the temperature of the system
was decreased to 455 K and the vapor pressure of the system
is determined at this temperature. After that, the temperature is
decreased 10 K each time and the vapor pressures determined
at each temperature: i.e. 455, 445 K, etc. In all cases both series
of measurements did result in a consistent isopleth. In this way
thermal degradation of the organic salt present in the solution
was discarded.
In preparing the sample, the top of the Cailletet tube is filled
with the aqueous solution. Then the aqueous solution is degasi-
fied: the sample is frozen, employing for freezing liquid nitrogen,
and melted and the released gases are removed several times
under high vacuum conditions. The next step is adding mercury.
Finally, the Cailletet tube is removed from the gas rack and then
mounted into the stainless steel autoclave, the autoclave is closed
and by means of a hydraulic system pressure is applied. To the
solutions of sodium oleate a specially careful degasification pro-
cedure of the sample was applied, because the surface tension of
the sample decreases in the presence of the sodium oleate. Fortu-
nately, samples improperly degasified were easily detected and
rejected as they present vapor pressures several bars higher than
the vapor pressure of pure water.
For the experiments double distilled water was used. Sodium
acetate trihidrate puriss (>99%), sodium oleate (BioChemika
>99%) and 2-propanol (puriss >99.9%) was supplied by Fluka.
All chemicals were used without further purification. In the
preservation instructions provided with the sodium oleate it was
80 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85

Table 1
Bubble points of the systems IPA–water
xIPA = 0.005969 xIPA = 0.01691 xIPA =0.02391 xIPA = 0.05447

P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)

0.404 410.65 0.420 405.76 0.431 405.82 0.426 400.97

0.459 415.51 0.465 410.70 0.486 410.78 0.496 405.76
0.519 420.38 0.535 416.10 0.551 415.62 0.561 410.65
0.584 425.29 0.600 420.41 0.626 420.57 0.631 415.51
0.659 430.14 0.675 425.29 0.706 425.42 0.716 420.41
0.739 434.98 0.755 430.17 0.796 430.28 0.806 425.31
0.829 439.91 0.845 435.04 0.891 435.17 0.906 430.14
0.924 444.79 0.945 439.91 0.996 440.07 1.011 435.04
1.039 449.65 1.050 444.79 1.111 444.95 1.131 439.88
1.154 454.52 1.170 449.65 1.236 449.87 1.261 444.79
1.279 459.40 1.295 454.52 1.371 454.63 1.396 449.68
1.435 459.40 1.516 459.59 1.546 454.58
1.711 459.43

indicated to keep the material at a temperature lower than −19◦
centigrade. Additional recommendations assured that for short
preservation periods, it was acceptable that the reagent is stored
in a conventional fridge. The sodium oleate was used within a
month after its reception. It was packed in 1 g bottles, and every
time a bottle was used, a solution was prepared with its whole
content, eliminating in this way the degradation problem.
3. Experimental results
3.1. System IPA–water
For the system IPA–water, samples with less than 5 mol% in
IPA were studied because higher concentrations of IPA are never
used in the SCWO process. Experimental data are presented in
Table 1.
Fig. 1 shows the measured isopleths and also some literature
data [2]. The new experimental data is consistent with the litera-
ture data. As expected the vapor pressure of the system increases
as the IPA concentration is increased.
3.2. System IPA–water–sodium acetate
The isopleths of the system IPA–water–sodium acetate have
been measured for two molar fractions of sodium acetate
(NaAc): 5 and 8.2%, and several concentrations of IPA. For
high NaAc concentrations low concentrations of IPA are used,
because IPA is an antisolvent of the NaAc. The experimental
data are presented in Tables 2 and 3.
The isopleths for a 5% of NaAc are represented in Fig. 4(a)
and those for an 8.2% of NaAc are represented in Fig. 4(b). As
expected, the vapor pressures of the salt–sodium acetate solution
are lower than those of pure water, and they decrease for higher
salt concentrations. When IPA concentration increases the vapor
pressure grows too.
3.3. System IPA–water–sodium oleate
The isopleths of the system IPA–water–sodium oleate have
been measured for two molar fractions of sodium oleate (NaOl):
0.25 and 0.11%, and several concentrations of IPA. The experi-
mental data are shown in Tables 4 and 5.
The influence of the salt concentration on the vapor pressure
depends on the concentration of the salt. In binary mixtures of
water and sodium oleate, at low salt concentrations, the vapor
pressure increases with the concentration of salt, but with higher
concentrations, then vapor pressure declines, being still higher
than that of pure water. This behavior is shown in Fig. 2 for a
temperature of 430 K. This behavior may be an indication of
azeotropic behavior. No literature data about the LV behavior of
aqueous oleate solutions to confirm or contradict this behavior
has been found.

Fig. 1. Bubble points of the system IPA–H2 O compared to literature data (lit.)
from [2]. Fig. 2. Vapor pressure of the system water–NaOl for a temperature of 430 K.
 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85 81

Table 2
Bubble points of the system IPA–H2 O–NaAc, with about 5 mol% NaAc
xNaAc = 0.04991; xNaAc = 0.04971; xNaAc = 0.04911; xNaAc = 0.0501; xNaAc = 0.04741;
xIPA = 0.000 xIPA = 0.004071 xIPA = 0.01607 xIPA = 0.02237 xIPA = 0.0500
P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)

0.437 420.49 0.430 415.54 0.433 405.74 0.461 405.82 0.408 396.31
0.492 425.34 0.480 420.41 0.488 410.65 0.516 410.65 0.463 400.99
0.552 430.17 0.545 425.26 0.548 415.51 0.581 415.56 0.528 405.87
0.617 435.01 0.610 430.14 0.623 420.41 0.656 420.49 0.603 410.75
0.687 439.94 0.680 435.04 0.693 425.31 0.741 425.34 0.683 415.59
0.772 444.85 0.770 439.94 0.777 430.20 0.831 430.22 0.768 420.46
0.862 449.79 0.860 444.82 0.867 435.09 0.931 435.12 0.868 425.34
0.957 454.66 0.955 449.71 0.967 439.99 1.036 440.02 0.973 430.25
1.067 459.51 1.065 454.63 1.082 444.85 1.146 444.76 1.093 435.12
1.180 459.51 1.187 449.68 1.281 449.71 1.213 439.96
1.322 454.52 1.416 454.60 1.348 444.82
1.462 459.40 1.561 459.53 1.498 449.71
1.653 454.60
1.828 459.48

Table 3
Bubble points of the system IPA–H2 O–NaAc, with about 8.2 mol% NaAc
xNaAc = 0.08153; xIPA = 0.000 xNaAc = 0.08075; xIPA = 0.004221 xNaAc = 0.08068; xIPA = 0.01046 xNaAc = 0.08150; xIPA = 0.01611

P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)

0.434 425.37 0.438 415.56 0.407 405.76 0.418 405.82

0.489 430.22 0.483 420.41 0.447 410.65 0.473 410.75
0.549 435.09 0.553 425.31 0.512 415.54 0.533 415.56
0.624 439.94 0.613 430.17 0.562 420.41 0.608 420.41
0.699 444.87 0.678 435.01 0.627 425.29 0.683 425.23
0.779 449.71 0.758 439.88 0.707 430.14 0.763 430.17
0.874 454.58 0.838 444.82 0.782 434.98 0.858 435.01
0.974 459.43 0.933 449.68 0.872 439.91 0.958 439.83
1.037 454.52 0.962 444.74 1.063 444.74
1.137 459.43 1.072 449.57 1.178 449.65
1.182 454.47 1.308 454.58
1.307 459.51 1.443 459.45

Table 4
Bubble points of the system IPA–H2 O–NaOl, with about 0.11 mol% NaOl
xNaOl = 0.001134; xIPA = 0.0000 xNaOl = 0.001106; xIPA = 0.024102 xNaOl = 0.001095; xIPA = 0.03403 xNaOl = 0.001077; xIPA = 0.05035

P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)

0.4206 415.48 0.4263 405.66 0.4532 405.68 0.4129 400.76

0.4706 420.41 0.4863 410.65 0.5183 410.62 0.4779 405.63
0.5306 425.26 0.5513 415.51 0.5833 415.51 0.5429 410.54
0.5956 430.17 0.6213 420.38 0.6633 420.38 0.6179 415.43
0.6756 435.04 0.7013 425.29 0.7433 425.26 0.6979 420.30
0.7556 439.91 0.7863 430.17 0.8383 430.12 0.7879 425.18
0.8456 444.79 0.8813 435.01 0.9383 435.04 0.8829 430.09
0.9506 449.65 0.9863 439.91 1.0483 439.88 0.9929 435.01
1.0606 454.55 1.0964 444.79 1.1683 444.79 1.1079 439.86
1.1806 459.43 1.2214 449.65 1.2933 449.68 1.2329 444.74
1.3514 454.55 1.4383 454.55 1.3679 449.60
1.4963 459.40 1.5883 459.43 1.5179 454.47
1.6779 459.32
82 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85

Table 5
Bubble points of the system IPA-H2 O-NaOl, with about 0.25 mol%Nao1
xNaOl = 0.002695; xIPA = 0.0000 xNaOl = 0.002409; xIPA = 0.017094 xNaOl = 0.002390; xIPA = 0.024997 xNaOl = 0.002326; xIPA = 0.050948
P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)

0.4466 420.35 0.4580 410.67 0.4352 405.79 0.4142 400.76

0.5116 425.26 0.5180 415.51 0.4952 410.65 0.4692 405.66
0.5766 430.12 0.5880 420.43 0.5602 415.54 0.5341 410.54
0.6516 435.01 0.6630 425.29 0.6352 420.41 0.6091 415.46
0.7416 439.88 0.7430 430.17 0.7151 425.31 0.6891 420.38
0.8316 444.71 0.8330 435.04 0.8051 430.20 0.7791 425.26
0.9316 449.57 0.9280 439.94 0.9001 435.06 0.8691 430.14
1.0416 454.50 1.0380 444.79 1.0051 439.86 0.9841 435.01
1.1616 459.43 1.1530 449.68 1.1201 444.76 1.0991 439.88
1.2829 454.55 1.2401 449.65 1.2241 444.79
1.4179 459.45 1.3751 454.55 1.3591 449.65
1.5201 459.43 1.5090 454.50
1.6690 459.40

In mixtures of IPA–water–sodium oleate, for 2.5% IPA the fitted using experimental volumetric and equilibrium data. The
influence of the salt in vapor pressure is negligible, but for 5% expression developed for mixtures by Anderko and Pitzer [5] is
IPA the vapor pressure decreases with higher salt concentrations presented in Eq. (5):


aper 1 a acb adb2 aeb3
4. Modeling =− + 2 + + . (5)
RT RT v 4v 16v3 64v4
4.1. The Anderko–Pitzer EoS In the mixing rules binary, ternary etc. interaction parameters
((, γ, δ and ε) are used. These parameters are estimated by fit-
The Anderko–Pitzer EoS for aqueous salt solutions [5,10] ting experimental data of the binary or ternary systems. Further
has been used to correlate the experimental data presented in this information about the calculations with this EoS is available in
work. This EoS consists of a reference part and a perturbation Ref. [5].
contribution, which can be expressed in terms of the Helmholtz
free energy as presented in Eq. (1): 5. Parameters
ares = aref + aper . (1)
5.1. Pure component parameters
The reference part represents the properties of a mixture of
hard sphere ion pairs and dipolar solvent molecules, as illustrated 5.1.1. Water parameters
in Eq. (2): The parameters a, b, c, d, and e of pure water were fitted by
Kosinski and Anderko [10] to data generated from the compre-
aref (T, v, x) = aionpair–ionpair + aionpair–solvent + asolvent–solvent . hensive EoS of Hill. PVT data from 373 to 1200 K and pressures
(2) up to 550 MPa were used for this purpose. With these parame-
ters, the EoS reproduces vapour pressures and densities of pure
The ion pairs can be treated as a strong dipole, and the solvent water from 373 to 1200 K.
molecules can be approximated by dipoles of smaller magnitude.
Therefore, Eq. (2) can be written as shown in Eq. (3): 5.1.2. Isopropanol parameters
Pure IPA parameters were fitted using density and vapour
aref (T, v, x) = arep (v, x) + adip (T, v, x). (3) pressure data from [14,15]. The dipole moment of IPA was taken
The perturbation contribution takes into account effects that µ = 0. The resulting parameters are shown in Eqs. (6) and (7).
are not represented by the reference terms and comprises a The symbol p in Eq. (7) represents the coefficients a, c, d and
virial-type expansion truncated after the fifth virial coefficient, e. The values of the coefficients pi (=ai , ci , di , ei ) of Eq. (7) are
as shown in Eq. (4): presented in Table 6:

aper 4a bIPA (cm3 mol−1 ) = 112, (6)

=− η(1 + cη + dη2 + eη3 ).
RT RTb
The first term of this equation is equivalent to the Van der
Waals attractive term. The coefficients c, d and e are necessary
to represent the properties of pure water accurately enough for
the application of the equation to mixtures. The coefficients a,
c, d and e are different for each pure component, and may be
(4)
p = p2 /T 2 + p1 /T + p0 . (7)
5.1.3. Sodium acetate and sodium oleate parameters
The parameters a, b, c, d and e for the NaAc and NaOl were
calculated with the corresponding states principle proposed by
Kosinski and Anderko [10] for systems where the experimental
 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85 83

Table 6
Coefficients for calculating pure IPA parameters

i/p a × 106 (bar cm6 mol−1 ) c d × 10−3 e

0 18.7595 3.2298 1.3075 −8.9882

1 −2.1081 × 10−2 1.4802 × 10−4 −2.4857 × 10−3 −1.2078 × 10−2
2 −8.9572 × 10−7 4.7372 × 10−6

data are scarce. As shown in Eqs. (8)–(10), with this method the
parameters of the salt are calculated as a function of the NaCl
parameters fitted by Kosinski and Anderko:
aNaAc = kNaAc–NaCl aNaCl ,
bNaAc = lNaAc–NaCl bNaCl ,
µNaAc = mNaAc–NaCl µNaCl .
In these equations, k, l, m are temperature-independent pro-
portionality constants that must be fitted for each salt, a and
b are the first parameters of the pure salt and µ is the dipole
moment of NaCl (µNaCl = 6.4 D). For the other parameters those
adjusted for NaCl can be taken in the same temperature range. In
the case of this work, k l and m parameters have been adjusted
with the equilibrium data of the binary systems water–NaAc
and water–NaOl, respectively. The value of these parameters is
shown in Table 7.
5.2. Binary systems parameters
sented by Kosinski and Anderko [10] for the system H2 O–NaCl
were used.
5.2.3. IPA–NaAc and IPA–NaOl
(8) The binary parameters of the systems IPA–NaAc and
(9) IPA–NaOl were considered 1 as presented in Eq. (15):
αij = γijk = δijkl = εijklm = 1, (15)
(10)
where i, j, k, l, m = IPA and NaAc or NaOl depending on the case.
This approximation is justified by the small concentrations of
IPA and the salts in the mixtures considered in this work, which
makes negligible the influence of the interactions between these
substances.
5.3. Parameters of the ternary systems
The ternary parameters were fitted using the equilibrium data
of the ternary systems. For the system IPA–H2 O–NaAc, the
ternary interaction parameters are presented in Eqs. (16) and
(17):

5.2.1. IPA–water γijk = −0.1047T + 55.2571, (16)

The binary interaction parameters of the systems IPA–H2 O
δijkl = εijklm = 1. (17)
were obtained from the correlation of the measured equilibrium
data of the system IPA–water. These parameters are only valid in For the system IPA–H2 O–NaOl, the parameters are shown in
the temperature interval from 400 to 460 K, which is the temper- Eqs. (18) and (19):
ature interval of the experimental data. Parameters are displayed
γijk = 0.1745T − 73.8094, (18)
in Eqs. (11)–(14):
δijkl = εijklm = 1, (19)
αij = −0.1038T + 50.7535, (11)
where i, j, k, l, m = IPA, H2 O, NaOl.
γijk = 0.004126T − 3.7312, (12) Note that γ 112 = γ 121 = γ 122 = γ 211 = γ 221 = γ 212 , γ 113 =
δijkl = 0.1620T − 65.4844, (13) γ 131 = γ 133 = γ 311 = γ 331 = γ 313 , γ 223 = γ 232 = γ 233 = γ 322 =
γ 332 = γ 323 and γ 123 = γ 231 = γ 213 = γ 312 = γ 321 = γ 132 . So for a
εijklm = 1, (14) ternary system only four γ are used.
where i, j, k, l, m = IPA and water. Note that γ 112 = γ 121 =
γ 122 = γ 211 = γ 221 . So for a binary system only one γ is used.

5.2.2. Water–NaAc and water–NaOl

Following the corresponding-states methodology proposed
by Kosinski and Anderko, for the binary interaction parameters
of the systems H2 O–NaAc and H2 O–NaOl, the parameters pre-

Table 7
Corresponding states parameters for NaAc and NaOl
k l m

NaAc 0.0153 0.8308 −0.7010

NaOl 0.5473 0.3938 0.0114 Fig. 3. Bubble points of the system IPA–water. Comparison of the experimental
data with the model calculations.
84 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85
Fig. 4. Bubble points of the system IPA–water–NaAc. Comparison to the calculated results. (a) 5% NaAc in mol in aqueous solution; (b) 8.2% NaAc in mol in
aqueous solution.
Fig. 5. Bubble points of the system IPA–water–NaOl. Comparison to the calculated results. (a) 0.11% NaOl in mol in aqueous solution; (b) 0.24% NaOl in mol in
aqueous solution.
6. Results
6.1. System IPA–water
Fig. 3 shows the comparison between the experimental data of
bubble points of the system IPA–water and the data calculated
with the Anderko–Pitzer EoS. In general, the calculated data
agree well with the experimental data, being the relative average
deviation in total pressure of %
P = 1.2%.
6.2. System IPA–water–sodium acetate
Fig. 4 illustrates the comparison of the experimental bubble
points of the system IPA–water–sodium Acetate with the bub-
ble points calculated by the Anderko and Pitzer EoS. Fig. 4(a)
shows the bubble points for the system with a 5 mol% NaAc
in water. Fig. 4(b) shows data for the system with a 8.2 mol%
NaAc in water. The predicted data do agree well with the
experimental data. The relative average deviation in totalpres-
sure results %
P = 4%, being the maximum average devia-
tion of %
P = 18.4% for a T = 405.8 K, xNaAc = 0.0807 and
xIPA = 0.0105.
6.3. System IPA–water–sodium oleate
Fig. 5 shows the comparison of the experimental vapor pres-
sures of the system IPA–water–sodium Oleate with those pre-
dicted by the Anderko and Pitzer EoS. Bubble points of the
system with 0.25% and 0.11 mol%, NaOl in water are shown
in Fig. 5(a) and (b) respectively. In general, the calculations
of the model agree with experimental measurements, being the
relative average deviation in total pressure of %
P = 2.8%. In
general, the agreement of the model and experimental data
is better in this system that in the system IPA–water–NaAc,
because in this case lower salt concentrations have been
used.
7. Conclusions
The bubble points of the system IPA–water, IPA–water–
sodium acetate and IPA–water sodium oleate were determined
in the temperature range between 396 and 460 K, and at pres-
sures higher than 0.35 MPa. IPA concentrations up to 5 mol% in
water were studied because this is the range of IPA concentra-
tions used in the SCWO process. In the system IPA–water–NaAc
concentrations of 5 and 8.2 mol% NaAc in water were used.
In the system IPA–water–NaOl, mixtures with 0.25% and
0.11 mol%NaOl were studied.
The measured data of the system IPA–water is consistent
with literature data. No literature data were available for the
other systems.
The systems were modeled using the Anderko–Pitzer EoS.
Experimental data were used for obtaining parameters in the
range of pressure and temperature of the data. In this range,
model calculations differ from the experimental results with
average deviations in total pressure of %
P = 1.2% for the
 M.D. Bermejo et al. / Fluid Phase Equilibria 244 (2006) 78–85
system IPA–water, %
P = 4% for the system IPA–water–NaAc
and %
P = 2.8% for the system IPA–water–NaOl.
List of symbols
a pure substance parameter of Anderko–Pitzer EOS
(bar cm6 mol−1 )
b pure substance parameter of Anderko–Pitzer EOS
(cm3 mol−1 )
c pure substance parameter of Anderko–Pitzer EOS (−)
d pure substance parameter of Anderko–Pitzer EOS (−)
e pure substance parameter of Anderko–Pitzer EOS (−)
P pressure (MPa)
R ideal gases constant (J mol−1 K−1 )
T temperature (K)
v molar volume (cm3 mol−1 )
x molar fraction in the liquid (−)
Greek letters
α interaction parameter of Anderko–Pitzer EOS (−)
δ interaction parameter of Anderko–Pitzer EOS (−)
ε interaction parameter of Anderko–Pitzer EOS (−)
γ interaction parameter of Anderko–Pitzer EOS (−)
η reduced density (−)
µ dipole moment (D)
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