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DOI 10.1002/aic.15827
1
Corresponding Author: m_dehghani@iust.ac.ir
This article has been accepted for publication and undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as
doi: 10.1002/aic.15827
© 2017 American Institute of Chemical Engineers (AIChE)
Received: Dec 05, 2015; Revised: May 17, 2017; Accepted: May 30, 2017
Abstract
In this study, a predictive model is presented for estimation of second order thermodynamic
capability of modified electrolyte PC-SAFT up to high pressure and temperature has been
studied. In addition to the first order derivative thermodynamic properties, the Gibbs free energy,
enthalpy and heat capacity of aqueous electrolyte solutions at infinite dilution are predicted.
Using new methodology, the dielectric constant is modified to keep the pressure, temperature
and ionic strength dependency. Our results show that the Born term has a significant contribution
dependent solution dielectric constant on standard state heat capacity is studied. Finally, the
isobaric heat capacity at various salt concentrations is predicted without any adjustable
parameters. The results of this work indicate an acceptable agreement with experimental data
Keyword: heat capacity, electrolyte solution, hydration enthalpy, PC-SAFT, dielectric constant
Introduction
Electrolyte solutions have lots of application in our modern world; from human body to mineral
processing industry, we are facing electrolyte solution. From chemical engineering point of view,
prediction of thermo-physical properties is the first step in any simulation process. A robust and
efficient thermodynamic model, in addition to the phase equilibrium calculations, must be able to
estimate the thermo-physical properties of the system over a wide range of operational
conditions. Thermal properties such as enthalpy of solution and isobaric heat capacity are
essential in process simulation and energy balance. Considering mentioned facts, a physically
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based model is demanded for calculation of first and second order derivative thermodynamic
properties especially at standard state. During recent years, various models have been utilized for
description of the thermo-physical properties of electrolyte solutions. In this regard, two model
paradigms have been distinguished; activity coefficient and equation of state (EOSs) models.
The first one is in terms of the excess Gibbs free energy and the second approach is based on
residual Helmholtz free energy. The activity coefficient models are dependent on reference state
coefficient models have some deficiencies like disability in solution density calculation; an
experimental value of density is required in calculations. However, these models have been
applied extensively in chemical engineering including single and mixed electrolytes as well as
mixed-solvent systems. The Pitzer model1, electrolyte Non Random Two Liquid (NRTL) 2
and
Extended UNIQUAC 3 have been widely used in this area due to simplicity and applicability. It
must be noted that, capability of aforementioned models often depend on parameter estimation
step. In the case of second order properties estimation, there are some activity coefficient
models which correlate partial molal enthalpy and isobaric heat capacity coefficient of
Approximation-NRTL (MSA-NRTL) model to describe the apparent heat capacity and dilution
enthalpy of five 1-1 aqueous electrolyte solutions. They utilized a simple polynomial form for
correlation of infinite dilution heat capacity. Then, the apparent molal heat capacity and dilution
enthalpy were correlated using five adjustable parameters per each salt. The results showed good
agreement with experimental data. K. Thomsen 5 showed that the Extended UNIQUAC model is
able to represent the phase behavior and thermal properties of electrolyte solution up to high
temperature and salt concentration. Mentioned model is one of the well-known activity
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coefficient models that shows a good result for second order properties such as solution heat
The second approach refers to as “EOSs” have been successfully extended to electrolyte
solutions for more than two decades. Among presented EOSs in the field of electrolyte solutions,
just a few ones have focused on calculation of standard state and second order derivative
properties. In most cases, prediction of phase equilibrium conditions was the primary goal of
previous works6-13. The Statistical Associating Fluid Theory (SAFT) EOSs have been also
developed to electrolyte solutions. Galindo et al. extended the SAFT-VR (variable range) to
12
electrolyte using the restricted primitive model for long range interaction . Behzadi et al.
electrolytes) approach developed through a combination of the SAFT-VR and the non-primitive
model by Zhao eta al. 15. Recently, Das et al. applied the SAFT-VR+DE to study 19 different 1-1
16
electrolyte solutions . In the mentioned work, osmotic coefficient, water activity, solution
density, Gibbs free energy of hydration and dielectric constant of solution were studied16. Ji and
Adidharma developed the SAFT2 EOS to represent the properties of aqueous single and mixed
10
electrolyte solutions at high pressure and temperature (473.15 K and 1000 bar) . The ion-
specific parameters and ion-specific coefficients were fitted to experimental activity coefficients
and solution densities data up to 473.15 K. Among all available SAFT models, the PC-SAFT
17
EOS has been widely applied to multitude of the systems including electrolyte solutions. The
electrolyte PC-SAFT versions have been developed by the combination of PC-SAFT and Debye
18 19,20 7-9,21
Hückel (DH) or Mean Spherical Approximation (MSA) long range term . Recently,
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the electrolyte polar PC-SAFT (ePPC-SAFT) has been utilized to treat aqueous solution of single
be noted that, more work is required to evaluate the capability of mentioned electrolyte SAFT-
based EOSs.
Simultaneous prediction of phase behavior and second order derivative properties is one of the
most important criterions dealing with electrolyte EOSs. Most activity coefficient models and
EOSs are able to provide good estimates of phase equilibrium calculations while have difficulty
in predicting the second order derivative properties. Therefore, some semi-empirical models or
correlations have been utilized to estimate the second order properties of electrolyte solutions,
especially in engineering software. Helgeson, Kirkham and Flowers (HKF) is one of the well-
known correlative models 22-24 which is utilized in engineering software widely. The HKF model
was formulized based on partial molar volume at infinite dilution. This model is divided into two
specific interactions; Born equation for solvation and non-Born term for internal volume.
Aforementioned model have four adjustable parameters that are fitted to partial molar properties
experimental data. Their correlative model gives good results for partial molar volume as well
25,26
the heat capacity but is not recommended for electrolytes near the critical point of water .
Recently, Djamali and Cobble developed a model for calculation of standard Gibbs free energy
27,28
of ions hydration over a wide range of pressure and temperature . This model needs two
adjustable parameters per each salt. Their model was utilized to predict standard thermodynamic
Sedlbauer et al. 25 developed an EOS model based on fluctuation solution theory to estimate the
infinite dilution heat capacity of aqueous and non-aqueous solutions. An expression for infinite
dilution molar volume has been developed in an empirical form to correlate infinite dilution heat
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25
capacity, enthalpy and Gibbs free energy . In the case of electrolyte solutions, the model
parameters were regressed to experimental data of infinite dilution partial molar volume, heat
capacity and compressibility coefficient. Their results showed that the model fails near critical
temperature, in this reason a correction term was considered to compensate this deviation25.
Consequently, they used six adjustable parameters for each ion to correlate volume, heat capacity
Up to date, a systematic study, based on EOSs, on the second order derivative properties of
electrolyte solutions has not been carried out. Most of previous works focused on the phase
behavior calculations and there is no clear route for extension to prediction of second order
derivative properties. For example, in some well-known electrolyte SAFT models such as ePC-
SAFT 9, SAFT-VRE 12 and electrolyte SAFT2 10 the effect of solvation term (Born) on derivative
properties have not been studied. While in the case of derivative properties (such as heat
capacity), it is clear that considering temperature dependent dielectric constant in Born and long
range terms is essential. In this study, the influence of Born term on prediction of second order
properties has been studied and compared with other interaction terms. In the present work, first
order thermodynamic properties such as MIAC (mean ionic activity coefficient) and solution
density or AMV (apparent molar volume) up to high pressure and temperature are investigated,
then in order to calculate the second order properties, standard state properties are studied. In this
regard, infinite dilution thermal properties of electrolyte solutions using SAFT-based model over
a wide range of pressure and temperature are predicted. In addition to the solute properties, the
water properties as a main solvent are calculated. Since solvent properties play a crucial role in
the modeling of electrolyte solutions, a robust model must be able to give satisfactory results for
both solute and solvent properties over a wide range of conditions. Therefore, second order
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derivative properties of pure water are investigated. Due to the critical role of dielectric constant
in modeling of aqueous electrolyte solutions, new method is used to describe this property
account the effect of pressure, temperature and ionic strength on dielectric constant of solution.
This work is consisted of four parts; first and second order derivative thermodynamic properties
of water as the main solvent are investigated in the first part. In the second part, the modified
form of dielectric constant is coupled with ePC-SAFT EOS to consider the effect of temperature,
pressure and ion concentration on long rang and solvation terms. In the third part, the first order
derivative properties such as MIAC, AMV and osmotic coefficient are correlated and predicted
up to high pressure and temperature. Finally, Gibbs free energy, enthalpy and heat capacity of
Theory
The PC-SAFT EOS was based on perturbation theory, where the dispersion contribution derived
for chain molecules17. In the modified PC-SAFT model for electrolyte solutions, the residual
= + + + +
(1)
where the superscripts res, hc, disp, elec, assoc and Born refers to residual, hard chain,
dispersion, electrostatic, association and Born contributions, respectively. More details about
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original electrolyte PC-SAFT are given in reference17. In this work, the free energy due to the
electrostatic interactions between ions is considered by Debye Hückel (DH) theory18. In our
previous work 21, the primitive MSA was used for long range interaction. Recent investigations
31
showed that the primitive MSA performs similarly to the DH theory . Since prediction of
derivative properties is the main purpose of this study and temperature and density derivative of
the Helmholtz free energy of each term is required, the DH theory is utilized because of its
The Born equation is used to account the solvation energy as follows 32:
1
=− 1 −
(2)
4 !
It is clear that the hydrated diameter in Born term is different from hard sphere diameter. We
utilized the following empirical relationship between the ion diameter and Born diameter that
!
= ! + 1.7 Å (3)
!&
= !& + 0.2 Å (4)
Using Born diameters instead of bare ion diameter gives a good result for prediction of hydration
Permittivity calculation
Commonly empirical models are utilized for calculation of dielectric constant as a function of
26,35,36
temperature, pressure and solution density . In this work, using recent methodology
abnormality of polar liquids29. The permittivity of a continuum depends on temperature and fluid
properties such as density, optical polarizability and electric dipole moment37. Kirkwood 37
and
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38
Onsager derived an expression for relative permittivity, later, Fröhlich39 introduced the
Kirkwood g-factor to account local structure in Onsager’s relations. The Kirkwood g-factor
estimates the orientational correlation between neighbors in the liquid. The Kirkwood theory
shows that the dielectric constant of a polar liquid is related to the dipole moment, induced in the
absence of an external field37,38. Maribo-Mogensen et al.29 modified the g-factor using the
(2 + * )( − * ) ,
= Θ 0 1,
(* + 2) 9 (5)
.
where , g and 1 are the solution permittivity, Kirkwood g-factor and dipole moment,
Θ = 1 − 34
(6)
follows40:
(* − 1) ,
= 6,
(* + 2) 3
(7)
.
4 34
cos :4 1,4
0 = 1 +
3 cos ;4 + 1 1, (8)
4
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3<= > refers to the probability of association between two sites. The fraction of molecule A or B
that is not bonded to any other component are directly calculated using SAFT association
theory41. The probability (Pij) in Eq. 8 is obtained based on the number of association sites of
cation, anion and water. zij is the coordination number of molecule j around molecule i and in
this study has been set to four based on water molecules structure. Other terms are described in
Following relations are adopted from previous works 25,27,28,42 to calculate the Gibbs free energy
J K D
∆
A̅&
∗ (,
3) = D ln G& (, 3, & → 0) + ID ln( )
10003
(11)
where the second term is the conversion from hypothetically ideal gaseous ions being hydrated to
the hypothetically ideal 1m aqueous solution27,28,41,42. The reference molality is 1 molar (J = 1
mol/kg) and the standard state pressure (ideal gas) is 1 bar (3 = 1 bar). The K (0⁄LJM ) is
denoted density of pure solvent (in this work water) and I represent the stoichiometric number of
First order derivative of Eq. 11 respect to temperature leads to partial molar entropy at infinite
Q∆
A̅&
∗
̅ ∗ (, 3) = − P
∆
O& R
Q
(12)
S
U&
∆
T ∗ (,
3) = ∆
A̅&
∗ ̅ ∗ (, 3)
(, 3) + ∆
O& (13)
Q ∆
A̅&
∗
̅∗
∆
V,& (, 3) = − P R
Q
(14)
S
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The infinite dilution partial molar heat capacity of salt is obtained as follows:
Q6
̅
V,& ̅∗
(, 3) = ∆
V,& (, 3) + IVSW () − ID X1 − 26 − P R Y
(15)
Q
where 6 is the isobaric expansivity of pure water. VS is the heat capacity coefficient of gaseous
W
ions at standard state that is set to 20.785 [. \ for ions43 excluding O]^_ which is set equal to
Z
SO3 as follows:
VS ()
W
= 8.060 + 0.001056 − 202800/
D
(16)
where R and T are universal gas constant (J/mol.K) and temperature (Kelvin) respectively.
Pure water
Water as the solvent plays a key role in thermodynamic behavior of aqueous electrolyte
solutions. A robust EOS should accurately estimate water thermodynamic properties over wide
range of pressure and temperature. Usually the EOS parameters are calculated based on vapor
pressure and saturated density experimental data then the model is applied only to the phase
equilibrium calculations. A reliable EOS must be able to calculate the second order derivative
properties while most of them fail at it. Among various EOSs, the molecular-based EOSs are a
good choice due to intrinsic nature of these EOS that retain the microscopic contributions of
particle interactions. Considering previous works PC-SAFT EOS, three sets of parameters have
Table 1.
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Two types of association scheme between water molecules have been tested; 2B and 4C schemes
based on SAFT notations. The 2B scheme parameters are adopted from Gross and Sadowski45
and the 4C scheme parameters are taken from Diamantonis & Economou44 and Lee & Kim 8
works. Diamantonis & Economou estimated the water parameters thorough fitting of the
saturated liquid density and vapor pressure data at temperatures ranging from 274 K to 647 K
(considered as 4C (1)), while Lee & Kim used aforementioned experimental data at ranging from
The obtained parameters were used in prediction of the isothermal compressibility, isobaric
expansivity, isobaric heat capacity, Joule-Thomson coefficient and speed of sound of pure water.
For aforementioned three set of parameters in Table 1, at low temperatures, the PC-SAFT
overestimates the isobaric expansivity, but its performance improves as the temperature
result shows that, pressure derivative of PC-SAFT model respect to density and temperature at
low temperatures requires improvement. The speed of sound is one of the main properties to
discern some of thermodynamic model limitations. Figure 1 shows the prediction of speed of
Figure 1.
Qualitative agreement is achieved just in the case of 4C (1) at saturated and high pressure. As a
result, a comparison among three set of parameters shows that 4C (1) scheme is the most
accurate one. Consequently, the 4C (1)44 scheme and related model parameters have been
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The contribution of each term of PC-SAFT EOS in prediction of second order derivative
properties has been studied. In this regard, the first and second order derivative of Helmholtz free
energy of various terms including hard chain, dispersion and association contribution respect to
Figure 2.
The results indicate that the association term in PC-SAFT play an important role in first and
Solvent dielectric constant plays a key role due to high effect on solution polarizability and its
application by Debye-Hückel and Born terms. Derivative properties of electrolyte solutions are
was used for this purpose. In This theory dielectric constant is related to solution density,
properties such as dipole moment, internal bonding angle (d : R-OH angle for solvent molecule
i), angle between dipole moments of two neighbor molecules (e4 : angle between dipole
molecule i and j) and hydrogen bond angle between two neighbor molecules (;4 ).
planar or tetrahedral. Maribo-Mogensen et al.29 correlated Υ4 and ;4 using water density data
obtained by Cubic Plus Association (CPA) EoS47. In this study in order to have more accurate
water dielectric constant and inspired by previous work29, the two mentioned angles have been
optimized to fit the experimental dielectric constant of pure water at 20 ℃. The dipole moment
of water set to 1.85 Debye and adjusted angles Υ4 = 60.34 and ;4 = 86.24 degree were
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obtained; it is worth mentioning that the structural angles in the case of tetrahedral network are
of orientation of neighboring dipole moments. It must be mentioned that this quantity cannot be
37
calculated with high accuracy due to requiring detail and high level accuracy of molecular
interactions. Heger et al.48 measured water dielectric constant up to high temperature and
pressure then back-calculated Kirkwood g-factor48,49. In this work the dielectric constant was
predicted using described method and obtained density by PC-SAFT then was compared with
estimated experimental data; In Figure 3 predicted dielectric constant of water at high pressure
and temperature is presented. It can be seen that using Wertheim’s association theory and
modification on probability function quantity in Kirkwood model, satisfactory results over wide
Figure 3.
dielectric constant derivative respect to temperature has been compared with experimental data.
Figure 4.
In addition to accurate prediction of dielectric constant, the results show that the temperature
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The presented methodology in the previous section indicates an excellent description of the static
permittivity of water up to high pressure and temperature. The dielectric constant in electrolyte
solutions depends on salt concentration; therefore, the proposed model should be extended to
handle charged particles. Dielectric constant of electrolyte solution reduces by increasing ions
concentration due to direct effect on electrical field. When cation and anion ions dissociate in a
solvent, an electric field between counter ions generates and polarized water molecules get
oriented as a result of electric field. Therefore, the acceptor sites on lone pairs of oxygen atoms
directed to cation and the donor sites on hydrogen atom directed anions. So, a hydration shell by
water molecules shield charge particles, consequently external field and dielectric constant
decreases. Considering this fact the presence of charged particles cannot be neglected in
utilized for prediction of electrolyte solution dielectric constant. As described earlier, dielectric
probability function, the association contribution was considered between cation-anion, water-
Parameter estimation
The model parameters are segment number (m), segment diameter (!), segment energy ( ⁄ ),
association energy ( < ⁄ ) and association volume (h < ) of ions. The segment number for ions
set to one and the association volume of cation and anion set to 0.03 based on previous works
6,21
. The binary interaction parameters (BIP) between all particles are set to zero (kij=0.0).
Finally, three parameters contained segment diameter (!), segment energy ( ⁄ ) and
association energy ( < ⁄ ) have been adjusted for each ion; see Table 2.
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The MIAC and AMV of twelve aqueous electrolyte solutions at 298.15 K and 1 bar have been
simultaneously utilized for parameters optimization. The obtained parameters at 298.15 K and 1
bar were utilized for prediction of first and second order derivative properties up to high
temperatures. For the sake of parameter optimization accuracy, a robust and efficient
optimization algorithm namely, the Shuffled Complex Evolution (SCE)51 was utilized. Following
where i and j are counter over salts and data points, respectively. The w is weight parameter.
Table 2.
The number of association sites for mono valence cations and anions set to 6 and 5, respectively
as previous works 30. For divalent ions such as Ca2+ eight association sites have been considered.
As mentioned earlier, the association volume set to 0.03 and one association parameter ( < ) is
needed to take into account ions association. As shown in Table 2, the association energy of ions
are salt-independent and transferable to different salts containing the same ion.
The AMV shows the difference between solution and solvent density and is considered as one of
the most important properties in electrolyte solutions. A small deviation between experimental
and model value results a high deviation for AMV. Inclusion of AMV in objective function
complicates the model optimization procedure however improves the accuracy of physical
parameters. On the other hand, regression of the MIAC is more effective than the application of
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osmotic coefficient data for parameter estimation. Therefore, in Eq. 17 two effective properties
The reported errors in Table 2 show a good agreement between the model and experimental
values. The average deviation of MIAC and AMV are about 3.8% and 4.5%, respectively. It can
be seen that K2SO4 has the highest AMV deviation (Table 2); the largest deviation occurs at
concentration lower than 0.1 molal. It must be noted that, in this work weighted objective
function has been used for parameter optimization. The weight parameters could be incorporated
into objective function based on experiment to improve the correlation results. It was found that
the MIAC and AMV impose different weights during optimization procedure. Due to large error
value of AMV compared to MIAC, small weight parameter for AMV has been utilized to
balance the objective function. Finally, weight parameters for MIAC and AMV have been set to
form industrial point of view. In this study, we aimed at modeling of thermo-physical properties
of electrolyte solutions over wide ranges of pressure, temperature and salt concentration. In
improve the fitting over a wide temperature range while in this work, temperature-independent
ion parameters are utilized to reduce the model parameters; at least two extra parameters should
be considered for each parameter when the temperature-dependent approach is utilized. Using
ion-specific temperature-independent parameters, the MIAC and AMV up to 573.15 K and 1000
bar have been predicted without loss of accuracy. Consequently, the model predictions for
mentioned salts at high pressure and temperature gave satisfactory results compared to the
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experimental data. Figure 5 depicts MIAC of CaCl2 and Na2SO4 aqueous solution at different
Figure 5.
It can be seen that this model is able to predict the MIAC and solution density up to extreme
temperature and pressure using the ion-specific parameters that obtained at ambient condition. It
is found that, present model is useful for describing of thermodynamic properties of 1-1, 1-2 and
2-1 electrolyte solutions over a wide range of temperature, pressure and salt concentration.
Considering dielectric constant as function of ionic strength directly affects Born and
electrostatic terms of solvent and solvent activity; if one uses the concentration-independent
dielectric constant, the Born and electrostatic contribution of the chemical potential of solvent is
vanished. The results can be evaluated using osmotic coefficient or water activity calculation.
After parameter estimation, dielectric constant of the electrolyte solutions has been predicted and
compared to the experimental data to determine its reasonability. For example, in Figure 6 the
dielectric constant of aqueous NaCl solution at 298.15 K and 1 bar is presented. As can be seen,
Figure 6.
11
Myers et al. emphasized that the Born term depend on the dielectric constant of the solution.
To analyze how this new model affects the Born and electrostatic terms, the derivative of
mentioned terms respect to volume up to high NaCl molality has been studied. Figure 7 shows
that Born term has a significant effect on compressibility factor, while considering a
concentration-independent function cancel out the Born contribution. On the other hand the sum
of compressibility factor of electrostatic and Born terms give a negative value; while it became a
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positive value when concentration-independent dielectric constant is utilized. This result has a
Figure 7.
As shown in figure 7, due to temperature, pressure and ionic concentration dependency of static
permittivity, derivative properties are affected. In the following section, the temperature
derivative of Helmholtz free energy and chemical potential has been analyzed to study the
It must be noted that, an accurate prediction of second order derivative properties such as heat
capacity and enthalpy directly relates to the accuracy of temperature derivative of Helmholtz free
energy. In this regard, the contribution of temperature derivatives of various terms is investigated
here (Figures 8 and 9). Figures 8 and 9 show that the solvation and association terms have a
Figure 8.
Figure 9.
We conclude that the Born term plays the main role at infinite dilution. At infinite dilution, the
Born equation is a function of dielectric constant and ionic radius, consequently the heat capacity
will be a function of (Qv⁄Q) and (Q v⁄Q ) . This results show that solvation term (Born)
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Gibbs free energy and enthalpy of hydration: Gibbs free energy of hydration is defined as the
amount of energy required to overcome the attractive forces between solute molecules when
The Gibbs free energy of hydration is used in solvation thermodynamics such as dissociation and
of Gibbs free energy of hydration, estimation and prediction of its value is highly of interest
however most of thermodynamic models are inaccurate or fail. A capable electrolyte EOS must
be able to predict hydration energy especially at standard condition. In Table 3, the results of
simple and primitive version of electrostatic interaction has been utilized and comparison
between primitive and Non-primitive models is not a fair judgment 16 while the results show that
our model gives the best performance compared to other models. This result can be referred to
application of a suitable model for dielectric constant and secondly because of considering the
Table 3.
In order to check the capability of model at higher temperatures, Gibbs free energy of hydration
of NaCl aqueous solution at higher temperatures were estimated and compared with molecular
simulation results by Liu et al. 58 . The results have been presented in Table 4, it can be seen that
Table 4.
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As seen, the result of Djmali and Cobble is better than our new model. But it is worth mentioning
Table 5 gives a comparison between predicted enthalpy of hydration and experimental data.
Table 5.
As it was explained in the introduction part, several works have estimated electrolyte solutions
standard properties with a good accuracy through correlation but not prediction while all
Heat capacity. The standard state heat capacity of pure crystalline salts is constant between 0 to
100 °C 5. In the case of ions as temperature increases, infinite dilution heat capacity increases
then decreases. At low temperature, the infinite dilution heat capacity is affected by solvent
structure. The concave down increasing trend of infinite dilution heat capacity cannot be
captured accurately by a predictive model such as EOSs. There are several models for estimation
of the standard state properties of electrolyte solutions. Helgeson et al. model (HKF) is the most
famous one that was built on correlation of measured apparent heat capacity. The main
disadvantage of this model is that this approach requires a large number of parameters and high-
quality data. The activity coefficient-based models such as the Extended UNIQUAC5 utilized a
26
three parameters correlation based on Helgeson et al. work to correlate ions infinite dilution
heat capacity. When an EOS is used to calculate the heat capacity of electrolyte solution, the
differences between the ideal gas standard state and the aqueous electrolyte standard state must
be described by EOS terms. This is the big challenge in electrolyte EOSs that has been neglected
in previous works. In this work, the modified ePC-SAFT model was used to predict standard
state heat capacity up to high pressure and temperature without any fitting parameters or
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additional correlative term. The results was satisfactory, as an example in figure 10, error of
Figure 10.
As seen, the new model gives more accurate results, especially at low temperatures. Figure 11
shows a comparison between model prediction and three correlative or semi-empirical models
27,60,61 27
including unified theory proposed by Djamali and Cobble (a) and Pitzer based models
(b and c). The results show that, modified PC-SAFT gives an acceptable prediction compared to
other correlations.
Figure 11.
In Figures 12, predicted infinite dilution heat capacity of three electrolyte solutions at various
temperatures were compared with experimental values. The results show that as temperature
increases the accuracy of the model increases. It must be noted that for T <373 K the pressure is
1 bar while for T≥ 373 y pressure corresponds to vapor pressure of water at same temperature.
Figure 12.
The model capability has been studied in supercritical region as well. The results show that the
model can predict infinite heat capacity trend at supercritical region with an acceptable accuracy.
Mentioned results show that, the standard state heat capacity of salt can be predicted using ion-
specific parameters obtained by first order derivative properties (MIAC and AMV) at 298.15 K
and 1 bar. Deviation from experimental data at low temperature is relatively high, especially at
ambient condition while it decreases as temperature increases. The experimental infinite dilution
heat capacity of aqueous NaCl solution at ambient condition is about -85 j/mol.K 26 while it was
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64
predicted about -340 j/mol.K by M-Mogensen et al. using electrolyte Cubic Plus Association
(CPA) EOS 47. In this work it was predicted -10 j/mol.K, however this result is not surprising but
reveals that present work gives acceptable results. In their work, only infinite dilution heat
Our literature survey shows that heat capacity of electrolyte solutions at infinite dilution has not
been studied by predictive models, on the other hand, comparison between a predictive model
(this work) and correlative one (such as Pitzer model that has been shown in Figure 11) could not
give reasonable justification. As we noted earlier, it is difficult to predict the concave downward
trend of infinite dilution heat capacity of some electrolyte while the HKF or Pitzer model
correlated this region accurately. However Figure 11 shows that the overall results of new model
In the case of Gibbs free energy of hydration and heat capacity, we showed that the Born term
must be incorporated into electrolyte model to reach acceptable results. To check the capability
of new model, the results of original version of ePC-SAFT have been compared with new model.
It is clear that the original ePC-SAFT without Born term is not applicable here. In this regard, the
Born term was added to the original version of ePC-SAFT model without readjusting the model
The Gibbs free energy of hydration was predicted using the original version of ePC-SAFT+Born
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Table 6.
These results reveal that in the case of thermal properties such as heat capacity and enthalpy, the
solvation term must be accurately incorporated into electrolyte EOS to improve the model
estimation.
The impact of temperature-dependent static permittivity on standard state heat capacity was also
tested. The infinite dilution heat capacity of NaCl was predicted using different approaches in the
Figure 13.
The variation of standard state heat capacity with temperature is quite reasonable for new model.
Figure 13 shows that using temperature–dependent dielectric constant leads to good agreement at
lower temperatures (T < 100 ◦C) while using constant static permittivity (D=78.4), unusual
infinite dilution heat capacity is obtained. In the case of new model, the deviation at higher
temperature is still reasonable. In previous works, constant static permittivity at 298.15K was
used to calculate first order derivative properties such as MIAC or density, however accurate
phase equilibrium calculation can be obtained using constant static permittivity, the model faild
Utilizing residual Helmholtz free energy, its derivatives and standard state heat capacity of salts
and water the isobaric heat capacity of aqueous electrolyte can be predicted. Using new model,
the isobaric heat capacity of several salts up to 3 molal was predicted. In Figure 14, the model
capability in prediction of specific heat capacity of 1-1 electrolyte solutions have been depicted.
Figure 14.
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In Figure 15 the specific heat capacity of 2-1 electrolyte solutions is compared with experimental
data.
Figure 15.
These figures show that the model is able to predict the variation of specific heat capacity of
Solid-Liquid equilibrium
The capability of the model in prediction of solid-liquid phase equilibrium (SLE) of mixed
electrolyte solution was studied. The calculation of phase diagrams starts with locating all curve
intersections5. Next, two salt saturation points (limits of solubility) are located. The solubility
limits has been calculated using solubility product (Ksp) of the salt and the activity coefficients of
ions. Similar approach as mentioned in Thomsen thesis5 was utilized for calculation of phase
equilibrium. In this work, the experimental values of Ksp have been estimated using formation
Gibbs free energy (∆A | ) of species. The solubility product is defined as follows:
where :k is the activity coefficient of water, : and : are activity coefficient of cation A and
anion B, respectively. The a and b are the stoichiometric coefficient of ion A and B. Using the
experimental solubility products, the equilibrium concentration of salt can be calculated using
Eq. 19.
The solubility limits at 298.15 K and 1.01 bar for a number of aqueous electrolyte solutions were
predicted, the results were presented in Table 7. Our predicted values are in good agreement with
experimental data. It is worth to mentioning that, in SLE predictions, several salts have a
solubility limit beyond the salt concentration for which the model was tuned, however good
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predictions were obtained. Performance of our model in prediction of salt solubility in two-salt
solutions has also been studied (SLE calculations). In this regard, the multi-component systems
consisting of water, , y , V , V _ , _ and O]^_ have been chosen as the test samples.
Table 7.
Among all electrolyte EOSs, the electrolyte CPA (eCPA) 68, SAFT-RPM69 and SAFT270 are the
most famous ones that widely focused on SLE calculations in mixed electrolyte solutions. The
SLE results of eCPA show that in addition to ion-specific model parameters, binary interaction
coefficient (kij) between particles needs to be considered to improve the model calculations. In
the case of electrolyte SAFT-RPM69 and SAFT270 EOSs, same as eCPA model, binary
interaction coefficients between particles were used in mixed electrolyte systems. While In this
study, SLE of systems containing NaCl-NaBr and NaCl-CaCl2 were predicted without any
further parameter. In the case of NaCl-KCl, NaBr-KBr and NaCl-Na2SO4, except for −
y , y − _ , − O]^ _ and O]^ _ -O]^ _ , all others ion-ion or ion-solvent binary interaction
coefficients were set to zero. In this regard, the MIAC, AMV and SI (saturation index= activity
product of the salt divided by its solubility product68) of three mentioned systems were
<
simultaneously fitted using obtained fixed values of ion-specific parameters (!, , < , h and
parameters during optimization process. The binary interaction parameters for − y , y −
_ , − O]^ _ and O]^ _ -O]^ _ , were obtained -0.871, -0.482, -0.120 and 1.0, respectively.
As it is apparent, the sulfate ion was modeled without accounting for dispersion interactions. The
best results were obtained using zero dispersion interaction between sulfate ions (kij=1.0).
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In Figure 16, the SLE phase diagram of NaCl-NaBr and NaCl-CaCl2 as the ternary systems have
been depicted.
Figure 16.
As it is shown, the predicted results are in good agreement with experimental data. In the case of
In Figure 17 the SLE phase diagram of NaCl-Na2SO4 system has been depicted.
Figure 17.
Our results show that this model can be utilized for SLE calculation with minimum adjustable
parameters efficiently. We are doing more calculation to optimize phase equilibrium especially
SLE which are the most complicated ones. More detailed study on SLE and solubility of multi-
Conclusion
During last decade numerous studies focused on extension of electrolyte SAFT-based model to
correlate the first order derivative properties and its application in phase equilibrium
calculations; while their capability in estimation of second derivative properties such as heat
capacity were neglected. In this work, the predictive capability of electrolyte SAFT-based EOS
in estimation of standard state and residual heat capacity of aqueous electrolyte solutions up to
high pressure and temperature was studied. In this regard, the electrolyte PC-SAFT model has
been modified and utilized to estimate first and second order derivative properties of electrolyte
solution up to high pressure and temperature. The Onsager, Kirkwood, and Fröhlich framework
coupled with Wertheim’s association theory have been used to represent an appropriate
definition for dielectric constant. This theory has been utilized to account the effect of
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temperature and pressure derivation on dielectric constant. Our results show that at infinite
dilution the solvent properties and solvation contribution play an important role, in this reason
second order derivative properties of pure water has been studied in detail. At infinite dilution
the Debye-Hückel term approaches to zero while the Born term play an important role compared
to the other contributions. It is shown that, the present model is able to predict infinite dilution
heat capacity of electrolyte solution up to high pressure and temperature. In addition, the model
capability in prediction of MIAC and AMV at high pressure and temperature was satisfactory.
Then the isobaric heat capacity of aqueous electrolyte solutions up to 3 molal have been
predicted with reasonable deviation compare to experimental data. Finally, the model was
extended to multiple-salt solutions and the equilibrium concentrations of salts have been
calculated accurately. The results show that the new model can be utilized for SLE calculations
of ternary electrolyte systems containing 1-1, 1-2 and 2-1 type salts. We are working on robust
dispersion term to represent the charge-dipole short-range interaction to improve the capability
of model in prediction of first and second order derivative properties of electrolyte solutions. A
detailed study on solvation and dispersion terms will be the subject of our future work.
Notation
List of Symbol
̅
V,& infinite dilution heat capacity of salt (j/mol.K)
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VS
W ideal gas heat capacity (j/mol.K)
DH Debye-Hückle
g Kirkwood g-factor
T temperature (K)
P pressure (bar)
x molar fraction
Z compressibility factor
zi ionic charge
Greek letters
:4 angle between dipole moment of central molecule i and surrounding molecule j
∆
V̅ ∗ heat capacity change of hydration
∆
A̅&
∗ Gibbs free energy of hydration
U&
∆
T ∗ enthalpy of hydration
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̅∗
∆
O& entropy of hydration
ε segment energy
η packing fraction
<
h association volume between sites A and B
ρ molar density
Superscripts
assoc association
calc calculated
disp dispersion
exp experimental
hc hard chain
res residual
∞ infinitely diluted
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Page 31 of 76 AIChE Journal
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62. Gates AJ. Thermodynamic of aqueous electrolyte solutions at high temperature and
63. Smith-Magowan D, Wood RH. Heat capacity of aqueous sodium chloride from 320 to
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65. Tan SP, Adidharma H, Radosz M. Statistical Associating Fluid Theory Coupled with
66. Rossini FD. Apparent and partial molal haet capacity in aqueous solutions of 19 uni-
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Figure captions
Figure 1. Speed of sound for water at (a) saturated and (b) 500 bar 46.
Figure 2. (a) First and (b) second derivative of Helmholtz free energy respect to temperature for
38
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Figure 4. Temperature dependency of water dielectric constant (symbols are experimental data
50
)
Figure 5. Model calculated (lines) and experimental data (points) MIAC for CaCl2 (right) at 400
bar and Na2SO4 (left) at 200 bar. (○) 298.15, (□) 323.15, (∆) 373.15, (◊) 423.15 and (*) 473.15 K
54,55
.
temperatures at infinite dilution (Right figure is a magnification of left figure between -0.02 and
infinite dilution (Right figure presents a magnification of the left figure between -0.02 and 0.02).
Figure 10. Absolute deviation between models predictions and experimental data for aqueous
solution of NaCl.
Figure 11. Standard partial molal heat capacity of NaCl aqueous solutions at infinite dilution up
Figure 12. Standard partial molal heat capacity of aqueous electrolyte solutions at infinite
dilution at high pressure; NaCl (179 bar), KCl (179 bar) and NaBr (175 bar). Experimental data
from 62,63.
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Figure 13. Infinite dilution heat capacity of NaCl solution at 179 bar. The solid line is new
model, dotted and dashed lines are ePC-SAFT+Born using D=Constant and D=f(T),
respectively.
Figure 14. Predicted heat capacity of aqueous electrolyte solutions at 1 bar and 298.15 K 66.
Figure 15. Predicted heat capacity of aqueous 2-1 electrolyte solutions at 1 bar and 298.15 K 67.
Figure 16. Phase diagram for the ternary aqueous system; a) NaCl-NaBr and b) NaCl-CaCl2.
Figure 17. Phase diagram for the ternary aqueous system NaCl and Na2SO4 at 298.15 K and 1
Table 1. PC-SAFT Parameters for Pure Water: Parameters were obtained using Vapor Pressure
Table 2. Adjusted Ion Parameters and Average Deviation at 25 ○C and 1 bar: Experimental Data
1 2.6780 75.03787 1283.497 0.03 6
1 2.8500 642.1423 647.3689 0.03 6
y 1 2.9629 110.0381 130.3039 0.03 6
Ca2+ 1 3.7314 1411.569 3197.902 0.03 8
V _ 1 2.4576 49.4767 281.4294 0.03 5
_ 1 2.9502 122.7321 234.2157 0.03 5
_ 1 3.5538 172.5888 352.6175 0.03 5
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Table 3. Prediction of Gibbs Free Energy of Hydration (KJ/mol) at 1 bar and 298.15 K
¡¢ _£¤¥£
Err (%) =
Experiment This SAFT- npmsa + ¡¢
Salt 52
work VR+DE 16 PC-SAFT 57 npmsa + PC-
This work SAFT-VR+DE SAFT
LiCl -831.78 -767.59 -693.08 -741.3 7.71 16.67 10.87
LiBr -805.83 -736.05 -652.21 -715.8 8.65 19.06 11.17
NaCl -727.6 -755.53 -653.77 -667.9 3.83 10.14 8.20
KCl -659.81 -710.51 -630.55 -604.1 7.68 4.43 8.44
NaBr -701.65 -729.99 -616.92 -647.6 4.03 12.07 7.70
KBr -633.87 -678.97 -593.77 -578.9 7.11 6.32 8.67
NaI -668.18 -694.58 -568.23 -617.6 3.95 14.95 7.56
KI -600.40 -649.56 -548.81 -562.6 8.18 8.59 6.29
Average Error 6.39 11.53 8.61
Table 4. Prediction of Gibbs Free Energy of Hydration (KJ/mol) of Sodium Chloride at High
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T = 573 K
-657 -728.9 -658
ρ = 0.725 g/cm3
¡¢ _£¤¥£
Salt Experiment59 Model Prediction Err (%) =
¡¢
LiCl -878.22 -858.24 2.27
LiBr -847.67 -826.68 2.47
NaCl -766.92 -847.41 10.49
KCl -688.26 -790.01 14.78
NaBr -736.38 -821.85 11.60
KBr -657.72 -758.44 15.31
NaI -697.47 -786.81 12.80
KI -617.55 -729.41 18.11
Table 6. Prediction of Gibbs Free Energy of Hydration (KJ/mol) at 1bar and 298.15 K from
different Approaches
¡¢ _£¤¥£
Err (%) =
ePC- ¡¢
Salt Experiment 52 This work ePC-
SAFT+Born
This work SAFT+Born
LiCl -831.78 -767.59 -1191.12 7.71 43.20
LiBr -805.83 -736.05 -1375.23 8.65 70.66
NaCl -727.6 -755.53 -980.33 3.83 34.73
KCl -659.81 -710.51 -806.30 7.68 22.20
NaBr -701.65 -729.99 -926.75 4.03 32.08
KBr -633.87 -678.97 -806.79 7.11 27.28
NaI -668.18 -694.58 -877.51 3.95 31.32
KI -600.40 -649.56 -757.45 8.18 26.15
Average Error 6.39 35.9
Table 7. The Solubility Limit msat for Aqueous Solutions of Salts at 298.15 K and 1 bar: the
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Figure 1.
a) 3000
Exp. data
4C (1)
2500 2B
4C (2)
2000
U(m/s)
1500
1000
500
0
250 300 350 400 450 500 550 600 650
T(K)
b) 2500
2000
1500
U (m/s)
1000
500
0
300 400 500 600 700 800 900 1000
T(K)
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Figure 2.
0.05
a) HC
0.04 Disp
Assoc
Res
0.03
(dA/dT)
0.02
0.01
-0.01
300 350 400 450 500 550 600
T(K)
-4
x 10
0.5
b)
0
-0.5
-1
d2 A/dT2
-1.5
-2
-2.5
HC
-3 Disp
Assoc
-3.5 Res
-4
300 350 400 450 500 550 600
T (K )
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Figure 3.
25
20
Dielectric constant
15
10
0
0 0.2 0.4 0.6 0.8 1
Density (g/cm3)
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Figure 4.
-0.2
-0.22
-0.24
-0.26
(dD/dT)p , (1/K)
-0.28
-0.3
-0.32
-0.34
-0.36
-0.38
300 320 340 360 380 400 420
T(K)
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Figure 5.
0.7 1.1
1
0.6
0.9
0.5 0.8
0.7
0.4
M IA C
M IA C
0.6
0.3 0.5
0.4
0.2
0.3
0.1 0.2
0.1
0 0 0.5 1 1.5 2
0 0.5 1 1.5 2 mol/kg solvent
mol/kg solvent
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Figure 6.
90
80
Dielectric constatnt
70
60
50
40
30
0 1 2 3 4 5
Molality (mol/kg solvent)
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Figure 7.
0.4
0.2
-0.2
Z
-0.4
-0.6
Z DH
Z Born
-0.8 Z DH+Z Born
Z Born (D=Constant value)
-1
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Molality (mol/kg solvent)
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Figure 8.
0.05 0.05
Hard Chain
0
0.04 Dispersion
-0.05 Association
0.03
-0.1
-0.15 0.02
dA/dT
-0.2 0.01
-0.25
Hard Chain 0
-0.3 Dispersion
Association -0.01
-0.35
Born
-0.4 -0.02
300 400 500 600 300 400 500 600
T(K) T(K)
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Figure 9.
0.6 0.02
HC+Disp HC+Disp
Assoc 0.015 Assoc
0.5
Born
0.01
0.4
0.005
0.3
(dµ/dT)
0
0.2
-0.005
0.1
-0.01
0
-0.015
-0.1 -0.02
300 400 500 300 350 400 450 500 550
T(K) T(K)
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Figure 10.
400
200
(Cp Model - Cp Experiment) (j/mol.K)
-200
-400
-600
-800
-1000
This Work
-1200
Sedlbauer et al.
-1400
300 320 340 360 380 400 420 440 460 480
T(K)
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Figure 11.
500
-500
-1000
Cp (j/mol. K)
-1500
-2000
This work
-2500
a
b
-3000
c
-3500
300 350 400 450 500 550 600
T(K)
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Figure 12.
0 0
Cp (J/mol. K)
-1000 -1000
-2000 -2000
-3000 -3000
NaCl NaBr
-4000 -4000
300 400 500 600 300 400 500 600
T(K) T(K)
0 0
Cp (J/mol. K)
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Figure 13.
0.5
-0.5
Cp (kj/mol.K)
-1
-1.5
-2
-2.5
-3
-3.5
300 350 400 450 500 550 600
T(K)
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Figure 14.
4.3
4.2 NaCl
4.2 NABr
4.1
4
4
Cp (J/g.K)
Cp (J/g.K)
3.9 3.8
3.8
3.6
3.7
3.6 3.4
3.5
0 0.5 1 1.5 2 2.5 3.2
mol/kg solvent 0 0.5 1 1.5 2 2.5 3
mol/kg solvent
C p (J/g.K)
3.6 3.8
3.4 3.6
3.2
3.4
3
0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3
mol/ kg solvent mol/kg solvent
56
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Figure 15.
4 4
3.9
C p (J/g.K )
3.9
Cp (J/g.K)
3.8
3.8
3.7
3.7
3.6
3.6
3.5
3.5 3.4
3.4 3.3
3.3 3.2
0 0.5 1 1.5 2 0 0.5 1 1.5 2
mol/ kg solvent mol/kg solvent
57
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AIChE Journal Page 58 of 76
Figure 16.
7
a)
6
4
NaCl
0
0 2 4 6 8 10
NaBr
10
b) 9
6
CaCl2
0
0 1 2 3 4 5 6 7 8
NaCl
58
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Page 59 of 76 AIChE Journal
Figure 17.
2.5
Na2SO4.10H2O
2
1.5
Na2SO4
Na2SO4
NaCl
0.5
0
0 1 2 3 4 5 6 7
NaCl
59
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