Received: 28 May 2019 Revised: 7 September 2019 Accepted: 30 September 2019

DOI: 10.1002/aic.16818

EDITOR'S CHOICE: THERMODYNAMICS AND

MOLECULAR-SCALE PHENOMENA

A comprehensive thermodynamic model for high salinity

produced waters

Sheik Tanveer | Chau-Chyun Chen

Department of Chemical Engineering, Texas
Tech University, Lubbock, Texas
Correspondence
Chau-Chyun Chen, Department of Chemical
Engineering, Texas Tech University, Lubbock,
TX 79409.
Email: chauchyun.chen@ttu.edu
Funding information
J.F Maddox Foundation; Office of Energy
Efficiency and Renewable Energy, Grant/
Award Number: DE-EE0007888
Abstract
Reuse of produced waters in oil and gas production is a major concern due to high
treatment cost and regulations on disposal in the environment. To support develop-
ment of separation techniques and process innovations, we report a comprehensive
thermodynamic model for the aqueous hexary system of Na+, K+, Mg2+, Ca2+, Cl−,
and SO42−, the major ionic species present in high salinity produced waters. Based
on the electrolyte NRTL theory, the model accurately calculates thermodynamic and
phase equilibrium properties with two binary interaction parameters per water-
electrolyte pair and electrolyte-electrolyte pair sharing a common ion. This article
presents the methodology to identify the binary interaction parameters from litera-
ture data and the model results for wide varieties of thermodynamic and phase equi-
librium properties including salt solubility for selected binary, ternary, quaternary,
and quinary subsystems. The model is validated with the electrolyte concentrations
up to salt saturation and temperatures from 273 to 473 K.

KEYWORDS
aqueous electrolytes, electrolyte NRTL model, hexary oceanic salt systems, salt solubility,
thermodynamic properties

1 | I N T RO D UC T I O N revised extended UNIQUAC model.9 As summarized by Tanveer and

Hydraulic fracturing for unconventional oil and gas exploration gener-
ates enormous amount of produced water as an undesirable
byproduct. Due to the negative impact of disposing this high salinity
water in the environment as well as the high cost of desalination, the
disposition and treatment of produced waters is a major challenge in
the oil and gas industry.1 Availability of a comprehensive thermody-
namic model for produced waters is essential for the development of
novel intensified desalination technologies and treatment processes.
Also called the “hexary oceanic salt system”, the aqueous Na+-K+-
2+ 2+ − 2−
Mg -Ca -Cl -SO4 system represents the dominant electrolyte
species in high salinity produced waters.2 Numerous researchers have
made extensive efforts to develop thermodynamic models for the
hexary system. Among the most widely used thermodynamic frame-
works for modeling the system are the Pitzer activity coefficient
model,3-7 the extended UNIQUAC activity coefficient model,8 and the
Chen,10 the Pitzer models developed by Harvie and Weare,3 Harvie
et al,4 Spencer et al,5 and Marion and Farren6 have shown limited suc-
cess.2 However, these models are largely restricted to room tempera-
ture conditions and are impractical to apply in process development
studies due to the extensive parameterization requirement associated
with both the binary and ternary interaction parameters and the large
number of temperature dependence coefficients associated with the
parameters.11 Parkhurst and Appelo7 incorporated the Pitzer model in
their PHREEQC software to calculate salt solubility and species distri-
bution at “low temperatures,” that is, around 298 K. While the model
“is adequate at low ionic strength but may break down at higher ionic
strengths (in the range of seawater and above)”. Limited studies
related to the aqueous Na+-K+-Mg2+-Ca2+-Cl−-SO42− hexary system
have been reported based on the extended UNIQUAC model8 and
the revised extended UNIQUAC model.9 An extended UNIQUAC
model was reported for the aqueous Na+-M2+-Cl−-SO42− (M2+ = Ca2+,

AIChE Journal. 2020;66:e16818. wileyonlinelibrary.com/journal/aic © 2019 American Institute of Chemical Engineers 1 of 10

https://doi.org/10.1002/aic.16818

2 of 10
Sr2+, Ba2+) system at temperatures of 253–573 K with focus on salt
8 9
solubility for the subsystems. Hingerl et al later revised the solubility
model by introducing additional adjustable parameters to model the
aqueous Na+-K+-Ca2+-Mg2+-H+-Cl−-SO42− system at temperatures of
298–573 K. Recently, several equation-of-state models have been
developed for aqueous electrolyte systems, that is, e-CPA12 and e-
SAFT.13 However, these models have not been applied systematically
for the aqueous hexary system.
We adopt the symmetric eNRTL activity coefficient model11 for
the development of a comprehensive thermodynamic model for the
hexary system. With the hypotheses of local electroneutrality and
like-ion repulsion for the liquid structure, the eNRTL model has been
shown to have wide applicability, including aqueous electrolyte
systems,10,14-21 ionic liquid systems,22,23 and mixed solvent electro-
lyte systems.24,25 Furthermore, the eNRTL model parameters are
associated with the species radii, the first neighbor distance, and the
potential of mean force between the interacting species which can be
26,27
calculated from molecular dynamics simulation.
This article is structured as follows: the thermodynamic frame-
work section introduces the eNRTL model parameters that are
required to fully characterize the hexary system, the ternary sub-
system sections present the methodology to identify the model
parameters, the model prediction sections report the model results for
selected quaternary and quinary subsystems, and then the concluding
®28
remarks follow. Aspen Properties version 8.8 is used in the calcula-
tions of all thermodynamic and phase equilibrium properties.
1.1 | Thermodynamic framework
Details of the symmetric eNRTL model are readily available in litera-
11,29
ture and hence not reproduced here. In brief, the model expresses
ex
the excess Gibbs free energy of an electrolyte solution, g , as the
summation of two contributions:


ex
g =g ex,PDH
ðxÞ + g ex,lc
x, α, τij ð1Þ
here x denotes the compositions in mole fraction for the electrolyte
solution, α is the nonrandomness factor fixed to 0.2, τij denotes the
asymmetric binary interaction parameters for the interaction pair of
species i and j, that is, τij 6¼ τji, gex,PDH is the long-range ion–ion inter-
action contribution expressed by the Pitzer–Debye–Hückel (PDH)
equation and it requires no adjustable parameters, gex,lc is the short-
range interaction contribution expressed with the nonrandom two-
liquid local composition model and it requires the binary interaction
parameters τij. This work presents the binary interaction parameters
required to model the hexary and its subsystems. The binary interac-
tion parameters are associated with the water–electrolyte pairs and
the electrolyte–electrolyte pairs sharing a common ion. In other
words, the interaction species are electrolyte-specific, not ion-specific.
Note that, for simplicity, each electrolyte is expressed in terms of its
constitutive cation and anion that make up the electrolyte. For exam-
+ −
ple, electrolyte NaCl is expressed as (Na Cl ) while electrolyte
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TANVEER AND CHEN
Na2SO4 is expressed as (Na+ SO42−). Temperature dependence of the
binary interaction parameters is well represented with a Gibbs–
Helmholtz type equation with three temperature coefficients29:
 
Dij T T − T0
τij = Cij + + Eij ln − ð2Þ
T T0 T
In Equation (2), C and E are the dimensionless temperature coeffi-
cients, D is the temperature coefficient having unit in K, and T0 is the
reference temperature chosen as 298.15 K.
There are four cations and two anions for the aqueous Na+-K+-
Mg -Ca2+-Cl−-SO42− hexary system. Therefore, there are 8 water–
2+
electrolyte pairs and 16 electrolyte-electrolyte pairs sharing a com-
mon ion. Table S1 summarizes the binary interaction parameters for
the 8 water–electrolyte pairs and the 16 electrolyte-electrolyte pairs
required to fully characterize the system. Yan and Chen14 reported
the parameters for the (Na+ Cl−):H2O pair, the (Na+ SO42−):H2O pair,
and the (Na+ Cl−):(Na+ SO42−) pair. Bhattacharia and Chen15 reported
the parameters for the (K+ Cl−):H2O pair and the (Na+ Cl−):(K+ Cl−)
pair. Bhattacharia et al16 reported the parameters for the (K+ SO42−):
H2O pair, the (Na+ SO42−):(K+ SO42−) pair, and the (K+ Cl−):(K+ SO42−)
pair. Tanveer and Chen18 reported the parameters for the (Ca2+ Cl−):
H2O pair, the (Na+ Cl−):(Ca2+ Cl−) pair, and the (K+ Cl−):(Ca2+ Cl−) pair.
Tanveer et al19 reported the parameters for the (Mg2+ Cl−):H2O pair,
the (Na+ Cl−):(Mg2+ Cl−) pair, and the (K+ Cl−):(Mg2+ Cl−) pair. Though
Bhattacharia et al17 reported the parameters for the (Mg2+ SO42−):
H2O pair, the (Na+ SO42−):(Mg2+ SO42−) pair, and the (K+ SO42−):(Mg2
+
SO42−) pair, these parameters have been updated by Tanveer and
Chen10 to correct the inconsistency in treating the Mg2+ ion molar
heat capacity at the aqueous phase infinite dilution standard state. In
addition, Tanveer and Chen10 further reported the parameters for the
(Ca2+ SO42−):H2O pair, the (Na+ SO42−):(Ca2+ SO42−) pair, the (K+
SO42−):(Ca2+ SO42−) pair, and the (Mg2+ SO42−):(Ca2+ SO42−) pair. In
this work, we identify the parameters for the remaining three
electrolyte–electrolyte pairs: the (Mg2+ Cl−):(Ca2+ Cl−) pair, the (Mg2+
Cl−):(Mg2+ SO42−) pair, and the (Ca2+ Cl−):(Ca2+ SO42−) pair. In general,
the parameters are identified from and validated with data for vapor
pressure depression, osmotic coefficient, mean ionic activity coeffi-
cient, excess enthalpy or heat of solution, heat capacity, and salt solu-
bility available for the corresponding aqueous single electrolyte or
binary electrolyte systems at temperatures of 273.15–473.15 K over
the entire electrolyte concentration range from infinite dilution to salt
saturation.
In addition to the eNRTL binary interaction parameters, pure com-
ponent properties of ionic species, solvent water, and salt crystals are
needed to support thermodynamic properties and salt solubility calcu-
lations for the hexary system. Reference thermodynamic properties of
the ionic species, that is, Gibbs energy of formation, enthalpy of for-
mation, and molar heat capacity at the aqueous phase infinite dilution
standard state are retrieved from our earlier works.14-16,18,19 The
properties of pure water are retrieved from Wagman et al,30 the satu-
ration vapor pressure of water is calculated using Steam
Tables equation-of-state, and the vapor phase fugacity of water is
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TANVEER AND CHEN 3 of 10

calculated with the Redlich–Kwong equation-of-state. Summarized in double salt CaCl22MgCl212H2O(cr). For the vapor pressure data used
Table S2, standard state thermodynamic properties of the salt crystals, in the regression, the vapor pressures are set with 5% SD and the
that is, Gibbs energy of formation, enthalpy of formation, and heat other state variables are set as error free. The model results are sum-
capacity, are identified in this work or taken from our earlier marized in Table S3. The mean relative deviations (MRDs) for the
works.10,14-19 vapor pressure data are 4.1%, the water activity data are 2.1%, the
The next three sections present thermodynamic modeling of the osmotic coefficient data are in the range of 8.5–17.0%, and the appar-
aqueous Mg2+-Ca2+-Cl− ternary, the aqueous Mg2+-Cl−-SO42− ter- ent molar heat capacity data are 0.4%. The MRD values are less than
nary, and the aqueous Ca2+-Cl−-SO42− ternary. The focus is on the 7% for the salt solubility data of MgCl26H2O(cr), CaCl26H2O(cr),
methodology to identify the missing eNRTL binary interaction param- CaCl24H2Oα(cr), CaCl22H2O(cr), and CaCl22MgCl212H2O(cr).
2+ − 2+ − 2+ − 2+
eters for the (Mg Cl ):(Ca Cl ) pair, the (Mg Cl ):(Mg SO42−) Figure 1a shows the results for osmotic coefficients of the ter-
pair, and the (Ca2+ Cl−):(Ca2+ SO42−) pair from available data for ther- nary at 298.15 K as a function of square root of total ionic strength
modynamic properties and salt solubilities of these ternary systems. (in molality) of the solution with varying ionic strength fractions of
the electrolyte (Mg2+ Cl−). Also shown are the osmotic coefficient
data reported by Guendouzi et al33 for the ternary and by Robinson
1.2 | The aqueous Mg2+-Ca2+-Cl− ternary system
and Stokes37 for the aqueous MgCl2 and CaCl2 binary systems. The
2+ 2+ −
To model the aqueous Mg -Ca -Cl ternary system with the eNRTL model results are in semiquantitative agreement with the data.
2+
model, we require the binary interaction parameters for the (Mg Figure 1b presents the salt solubility results for the ternary. The sol-
Cl−):H2O pair, the (Ca2+ Cl−):H2O pair, and the (Mg2+ Cl−):(Ca2+ Cl−) ubilities of the MgCl2 and CaCl2 salts decrease with addition of elec-
pair. As mentioned earlier, the parameters for the first two pairs have trolytes (Ca2+ Cl−) and (Mg2+ Cl−) due to the common Cl− ion effect
been reported by Tanveer et al19 and Tanveer and Chen,18 respec- in the solution. The model results are in good agreement with the
2+ − 2+ −
tively. The parameters for the (Mg Cl ):(Ca Cl ) pair are identified solubility data.
in this work by regressing thermodynamic property data and salt solu-
bility data available for the ternary at temperatures of
1.3 | The aqueous Mg2+-Cl−-SO42− ternary system
288.15–383.15 K. Depending on the system temperature and the liq-
uid composition, MgCl26H2O(cr), CaCl26H2O(cr), CaCl24H2Oα(cr), To model the aqueous Mg2+-Cl−-SO42− ternary system, we retrieve
CaCl22H2O(cr), and CaCl22MgCl212H2O(cr) may form. the binary interaction parameters for the (Mg2+ Cl−):H2O pair from
The thermodynamic property literature data available for the Tanveer et al19 and the parameters for the (Mg2+ SO42−):H2O pair
2+ 2+ − 31
aqueous Mg -Ca -Cl ternary are reported in Table S3. Sako et al from Tanveer and Chen.10 This work identifies the binary interaction
published vapor pressure data at temperatures of 322.5–398.2 K. parameters for the (Mg2+ Cl−):(Mg2+ SO42−) pair from regression of
32
Baabor et al reported osmotic coefficients at 313.15 K, Guendouzi thermodynamic property data and salt solubility data available for the
et al33 reported water activities and osmotic coefficients at 298.15 K, ternary. The salt solubility data for the ternary is available at tempera-
and Christov34 reported osmotic coefficients at 298.15 and 323.15 K. tures of 273.15–378.15 K. The precipitating salts include
Saluja et al 35
reported apparent heat capacity at temperatures of MgCl26H2O(cr), MgSO47H2O(cr), MgSO46H2O(cr), MgSO45H2O(cr),
298.15–373.15 K. Linke and Seidell36 published salt solubility data at and MgSO44H2O(cr). No double salts are reported for the ternary.
temperatures of 288.15–383.15 K. Table S4 summarizes the data available for the ternary. Wu et al38
31
The vapor pressure data reported by Sako et al and the salt solu- reported osmotic coefficients data at 298.15 K. Linke and Seidell36
bility data reported by Linke and Seidell36 are regressed simulta- and Deng et al39 reported salt solubility data at temperatures of
2+
neously to identify the binary interaction parameters for the (Mg 273.15–373.15 K. Other salt solubility data were reported by Sil-
Cl−):(Ca2+ Cl−) pair and the standard state thermodynamic parameters cock40 at temperatures of 273.15–378.15 K, by Balarew et al41 at
essential for solubility calculations involving double salt 323.15 and 348.15 K, and by Bousmina et al42 at 288 K.
CaCl22MgCl212H2O(cr): Gibbs energy of formation, ΔfGko enthalpy of The salt solubility data reported by Linke and Seidell,36 Deng
formation, ΔfHk0, and solid heat capacity, Cp,k0. The model is then vali- et al,39 and Silcock40 are regressed to identify the binary interaction
dated against the water activity data reported by Guendouzi et al, 33
parameters for the (Mg2+ Cl−):(Mg2+ SO42−) pair. We use only those
the osmotic coefficient data reported by Baabor et al, 32
Guendouzi solubility data points where MgSO47H2O(cr), MgSO4H2O(cr), and
et al,33 and Christov,34 and the apparent heat capacity data reported MgCl26H2O(cr) are saturated. For the data points saturated with
by Saluja et al. 35
In the regression, we follow our protocol established MgSO47H2O(cr) and MgSO4H2O(cr), the SDs are set to 1,000 ppm
earlier18 and assign 5% SD for the (Mg2+ Cl−) electrolyte concentra- (in mole fractions) for the (Mg2+ SO42−) concentration, and the (Mg2+
tion data (in mole fractions) saturated with MgCl26H2O(cr) and set the Cl−) concentration are considered error free. Similarly, for the data
(Ca2+ Cl−) electrolyte concentration as error free. For the (Ca2+ Cl−) saturated with MgCl26H2O(cr), the SD is set to 1,000 ppm (in mole
concentration data (in mole fractions) saturated with the CaCl2 salts, fractions) for the (Mg2+ Cl−) concentration, while the (Mg2+ SO42−)
−
the SD is set to 5%, while the (Mg 2+
Cl ) concentration is set as error concentration is set as error free. Afterward, we identify ΔfGk0 of
− −
free. Furthermore, we set 5% SD to both the (Mg 2+
Cl ) and (Ca 2+
Cl ) MgSO45H2O(cr) from the salt solubility data with MgSO45H2O(cr) in
concentrations (in mole fractions) for the solubility data saturated with saturation. Given that the salt solubility data for MgSO45H2O(cr) are
 15475905, 2020, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/aic.16818 by University Degli Studi Di Palermo, Wiley Online Library on [27/04/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
4 of 10 TANVEER AND CHEN

from the solubility data points associated with the salt. In identifying
the salt solubility parameters of MgSO45H2O(cr) and MgSO44H2O(cr)
from the regression, we assign the SD to 1,000 ppm for the (Mg2+

F I G U R E 1 (a) Osmotic coefficients versus total ionic strength at

different ionic strength fractions, y, of (Mg2+ Cl−) for aqueous Mg2
+
-Ca2+-Cl− ternary system with experimental data in symbols and
model results in lines at 298.15 K: ( )37 and ( ) for y = 0, ( )33
33
and ( ) for y = 0.33, ( ) and ( ) for y = 0.50, ( )33 and ( )
for y = 0.80, ( )33 and ( ) for y = 1. (b) solubility of aqueous Mg2
+ −
F I G U R E 2 (a) Osmotic coefficients versus total ionic strength at
-Ca -Cl ternary system with experimental data36 in symbols and
2+
different ionic strength fractions, y, of (Mg2+ Cl−) for aqueous Mg2+-Cl−-
model results in lines at 298.15 K: ( ) and ( ) for CaCl26H2O(cr),
SO42− ternary system with experimental data in symbols and model
( ) and ( ) for CaCl22MgCl212H2O(cr), ( ) and ( ) for
results in lines at 298.15 K: ( ),38 ( ),37 and ( ) for y = 0, ( )38 and
MgCl26H2O(cr); at 348.15 K: ( ) and ( ) for CaCl22H2O(cr), ( )
( ) for y = 0.25, ( )38 and ( ) for y = 0.49, ( )38 and ( ) for y = 0.75,
and ( ) for CaCl22MgCl212H2O(cr), ( ) and ( ) for
( ),38 ( ),37 and ( ) for y = 1. (b) solubility of aqueous Mg2+-Cl−-SO42−
MgCl26H2O(cr) [Color figure can be viewed at wileyonlinelibrary.com]
ternary system with experimental data in symbols and model results in
lines at 298.15 K: ( ),39 ( ),40 and ( ) for MgSO47H2O(cr), ( )39
and ( ) for MgSO46H2O(cr), ( ), ( ), and (
40 39 40
) for
available only at 298.15 K, only ΔfGk0 of MgSO45H2O(cr) can be iden-
MgSO45H2O(cr), ( ),39 ( ),40 and ( ) for MgSO44H2O(cr), ( ),39
tified. For MgSO44H2O(cr), we estimate 0
Cp,k of the salt
( ),40 and ( ) for MgCl26H2O(cr); at 348.15 K: ( ),39 ( ),40 and ( )
MgSO44H2O(cr) from the corresponding values of MgSO46H2O(cr) for MgSO4H2O(cr); ( ),39 ( ),40 and ( ) for MgCl26H2O(cr) [Color
and H2O(cr).30 We then identify ΔfGk0 and ΔfHk0 of MgSO44H2O(cr) figure can be viewed at wileyonlinelibrary.com]
 15475905, 2020, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/aic.16818 by University Degli Studi Di Palermo, Wiley Online Library on [27/04/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANVEER AND CHEN 5 of 10

SO42−) concentration and set the (Mg2+ Cl−) concentration as
error free.
2+ −
The model results for the aqueous Mg -Cl -SO42− ternary are
given in Table S4. The MRD for the osmotic coefficient data from Wu
et al38 is 8.6%. Figure 2a shows the osmotic coefficient results versus
square root of the total ionic strength for the ternary at 298.15 K with
varying ionic strength fractions of (Mg2+ Cl−). Also shown are the data
from Wu et al38 and from Robinson and Stokes.37 It is evident that
the model results are in satisfactory match with the data. Figure 2b
presents the model results and solubility data for the ternary at tem-
peratures of 298.15 and 348.15 K. The results suggest the data satu-
rated with MgSO46H2O(cr) as reported by Deng et al39 and by
40
Silcock are metastable. The MRDs for the data points saturated with
MgSO47H2O(cr) and MgCl26H2O(cr) are less than 17%, while the
MRDs for the data saturated with MgSO4H2O(cr) show a much wider
range of deviation (7–77%) due to the relatively low salt solubility.
The data points with the metastable salt MgSO46H2O(cr) show the
MRDs in the range of 36–89%.
1.4 | The aqueous Ca2+-Cl−-SO42− ternary system
The aqueous Ca2+-Cl−-SO42− system is modeled by using the binary
interaction parameters for the (Ca2+ Cl−):H2O pair reported by Tanveer
et al,18 the parameters for the (Ca2+ SO42−):H2O pair reported by
Tanveer and Chen,10 and the parameters for the (Ca2+ Cl−):(Ca2+ SO42
− solubility of the CaSO4 salts, the model results are expressed in
) pair as identified in this work. For the ternary system, salt solubility
data are available at temperatures of 293.15–383.15 K with
CaSO42H2O(cr) and CaSO4(cr) as precipitating salts.
Table S5 summarizes the data available for the aqueous Ca2+-Cl−-
SO42− ternary. Linke and Seidell36 compiled salt solubility data at tem-
peratures of 298.15 and 328.15 K, and Silcock40 compiled salt solubil-
ity data in the temperature range of 293.15–383.15 K. The data
reported by Linke and Seidell36 and by Silcock40 are identical at
328.15 K. The data reported by Silcock are regressed to identify the
binary interaction parameters for the (Ca2+ SO42−):(Ca2+ Cl−) pair.
Only those data points where CaSO42H2O(cr) and CaSO4(cr) precipi-
tate as stable salts are used in the regression. Both CaSO42H2O(cr)
and CaSO4(cr) salts show trace solubility in the ternary. In the regres-
sion, we set the SD to 50 ppm (in mole fractions) for the (Ca2+ SO42−)
saturation concentration and error free for the (Ca2+ Cl−)
concentration.
Figure 3 presents the salt solubility model results for the ternary
at 298.15, 328.15, and 383.15 K. The system exhibits exceedingly
low saturation concentrations for electrolyte (Ca2+ SO42−). With
addition of electrolyte (Ca2+ Cl−), the solubility of the CaSO4 salts
decreases sharply due to the common Ca2+ ion effect, and then
increases with the increase in total ionic strength of the solution due
to the dominating contribution of the Debye–Hückel limiting law to
the ionic activity coefficients at such low ionic strengths. Further
addition of electrolyte (Ca2+ Cl−) results in decrease in the CaSO4
solubility due to the common Ca2+ ion effect. The model results are
in qualitative agreement with the data. Due to the exceedingly low
terms of mean absolute deviations (MADs) as shown in Table S5.
The MADs for data points saturated with the CaSO4 salts are less
than 57 ppm.

2 | M O D E L P R E D I C T I O N S F O R TH E
AQUEOUS QUATERNARY AND QUINARY
SUBS YS TEMS

Having fully identified the binary interaction parameters for the

8 water–electrolyte pairs and 16 electrolyte–electrolyte pairs as
reported in Table S1 and the standard state thermodynamic proper-
ties of the salt crystals as reported in Table S2, the model can be

T A B L E 1 Salt solubility predictions using eNRTL model for

aqueous quaternary systems

Subsystems Sources
Na+-K+-Cl−-SO42− Bhattacharia et al16
Na+-K+-Ca2+-Cl− Tanveer and Chen18
+ + 2+ −
Na -K -Mg -Cl Tanveer et al19
Na+-K+-Mg2+-SO42− Tanveer and Chen10
+ 2+ − 2−
Na -Ca -Cl -SO4 This work
F I G U R E 3 Solubility of aqueous Ca2+-Cl−-SO42− ternary system
+ 2+ 2+ −
with experimental data in symbols and model results in lines at Na -Mg -Ca -Cl This work
298.15 K: ( ),36 ( ),40 and ( ) for CaSO42H2O(cr); at 328.15 K: K+-Mg2+-Ca2+-Cl− This work
( )40 for CaSO42H2O(cr), ( ) for CaSO4(cr); at 383.15 K: ( )40 and +
Na -Mg -Cl2+ −
-SO42− This work
( ) for CaSO4(cr) [Color figure can be viewed at
K+-Mg2+-Cl−-SO42− This work
wileyonlinelibrary.com]
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6 of 10 TANVEER AND CHEN

utilized to calculate and predict thermodynamic properties and salt
solubilities of the hexary and its subsystems.
There are 14 quaternary subsystems with the hexary system.
Table 1 shows the salt solubility predictions have been reported by
Bhattacharia et al16 for the aqueous Na+-K+-Cl−-SO42− quaternary
−
18 + + 2+
system, by Tanveer and Chen for the aqueous Na -K -Ca -Cl
quaternary, by Tanveer et al19 for the aqueous Na+-K+-Mg2+-Cl−
quaternary, and by Tanveer and Chen10 for the aqueous Na+-K+-Mg2
+
- SO42− quaternary. The presence of electrolyte (Ca2+ SO42−) results
in trace solubility of the CaSO4 salts in the systems. In this study, we
choose not to present the salt solubility predictions for the six quater-
nary systems involving electrolyte (Ca2+ SO42−) with one exception: the
aqueous Na+-Ca2+-Cl−-SO42− quaternary. The aqueous Na+-Ca2+-Cl−-
SO42− quaternary is presented as a model system to illustrate the effect

F I G U R E 4 Solubility of aqueous Na+-Ca2+-Cl−-SO42− system with

F I G U R E 6 Jänecke phase diagram of aqueous K+-Mg2+-Ca2+-Cl−
experimental data in symbols and model results in lines at 298.15 K:
quaternary system with experimental data36 in symbols ([ ] for stable
( ),43 ( ),44 and ( ) for CaSO42H2O(cr), ( )43 and ( ) for
salts and [ ] for metastable salts) and model results in solid lines
CaSO4(cr); at 323.15 K: ( )43 and ( ) for CaSO42H2O(cr), ( )43 and
( ) at 348.15 K
( ) for CaSO4(cr); model results ( ) for natural logarithm of
mole fraction scale mean ionic activity coefficient of (Ca2+ SO42−) at
infinite dilution at 298.15 K [Color figure can be viewed at
wileyonlinelibrary.com]

F I G U R E 5 Jänecke phase diagram of aqueous Na+-Mg2+-Ca2 F I G U R E 7 Jänecke phase diagram of aqueous Na+-Mg2+-Cl−-
+
-Cl− quaternary system with experimental data36 in symbols ( ) and SO42− quaternary system with experimental data39 in symbols ( ) and
model results in solid lines ( ) at 298.15 K model results in solid lines ( ) at 348.15 K
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TANVEER AND CHEN 7 of 10

of electrolyte (Na+ Cl−) on CaSO4 salt solubility. The next sections pre-
sent the model predictions for five aqueous quaternary systems: Na+-
Ca2+-Cl−-SO42−, Na+-Mg2+-Ca2+-Cl−, K+-Mg2+-Ca2+-Cl−, Na+-Mg2+-Cl−-
SO42−, and K+-Mg2+-Cl−-SO42−, and two aqueous quinary systems: Na+-
K+-Mg2+-Ca2+-Cl− and Na+-K+-Mg2+-Cl−-SO42−.

2.1 | The aqueous Na+-Ca2+ -Cl−-SO42− quaternary

system
In the quaternary, the electrolyte (Ca2+ SO42−) concentration is in
trace amount when compared to the (Na+ Cl−) concentration in the
liquid phase. We examine the solubility of CaSO4 salts with increase
of the electrolyte (Na+ Cl−) concentration in the system.
Table S6 presents the salt solubility data and the model predictions
at temperatures of 298.15–473.15 K. Within these temperatures,
CaSO42H2O(cr), CaSO4(cr), Na2SO410H2O(cr), and NaCl(cr) may satu-
rate. Bock43 reported the salt solubility data at temperatures of
298.15–323.15 K. Madgin and Swales44 reported the data at 298.15
and 308.15 K. Marshall et al45 published the data at temperatures of
−
F I G U R E 8 Jänecke phase diagram of aqueous K -Mg -Cl -SO4
+ 2+ 2
313.15–473.15 K. Blount and Dickson46 also reported the data at high
−
quaternary system with experimental data39 in symbols ( ) and
temperatures of 373.15–723.15 K and pressures from 1 to 1,000 bars.
model results in solid lines ( ) at 328.15 K
Focusing on CaSO4 salts, Figure 4 presents the salt solubility

F I G U R E 9 Jänecke phase diagram of aqueous Na+-K+-Mg2+-Ca2+-Cl− quinary system with experimental data36 in symbols ( ) and model
results in solid lines ( ) at ~300 K

8 of 10
predictions at 298.15 and 323.15 K. Also shown are the natural loga-
rithm of mole fraction scale mean ionic activity coefficients of electro-
lyte (Ca2+ SO42−) at infinite dilution at 298.15 K. Addition of electrolyte
(Na+ Cl−) increases the total ionic strength of the solution for which the
activity coefficient of electrolyte (Ca2+ SO42−) decreases per Debye–
Hückel limiting law and the solubility of the CaSO4 salts increases. Tak-
ing into consideration the trace solubility of the CaSO4 salts, the model
predictions reasonably capture the solubility data trend. As shown in
Table S6, the MRDs are found within 60% for the CaSO4 salts.
2.2 | The aqueous Na+-Mg2+-Ca2+-Cl− quaternary
system
Linke and Seidell36 reported a few solubility data points for the quater-
nary at 298.15 K. Figure 5 presents the Jänecke phase diagram for the
quaternary along with the data at 298.15 K. It shows the model clearly
captures the solubility data including the invariant points.
F I G U R E 1 0 Jänecke phase diagram of aqueous Na+-K+-Mg2+-Cl−-SO42− quinary system with experimental data36,39 in symbols ( ) and
model results in solid lines ( ) at 298.15 K
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TANVEER AND CHEN
2.3 | The aqueous K+-Mg2+ -Ca2+-Cl− quaternary system
Linke and Seidell36 reported the salt solubility data for the quaternary at
temperatures 298.15, 308.15, 328.15, and 348.15 K. Figure 6 shows the
Jänecke phase diagram for the model predictions at 348.15 K. It is evi-
dent that the model captures well the solubility data along with the invari-
ant points except the CaCl2 hydrate salt regions, consistent with the salt
solubility results for the aqueous K+-Ca2+-Cl− ternary reported by
Tanveer and Chen.18 Figure 6 also presents the literature data points with
the metastable double salt 2KClCaCl22H2O(cr). The natural logarithm of
solubility product constant for the double salt is −8.258 at 348.15 K.
2.4 | The aqueous Na+-Mg2+-Cl−-SO42− quaternary
system
The salt solubility data for the quaternary has been reported by Deng
et al39 at temperatures of 263.15–373.15 K and by Linke and

TANVEER AND CHEN
Seidell36 at temperatures of 273.15, 298.15, and 328.15 K. Figure 7
shows the Jänecke phase diagram to illustrate the salt solubility pre-
dictions at 348.15 K. The model results are in semiquantitative agree-
ment with the solubility data including the invariant points.
2.5 | The aqueous K+-Mg2+-Cl−-SO42− quaternary
system
Deng et al39 reported the salt solubility data for the quaternary at temper-
atures of 273.15–328.15 K. In their report, saturation data is found
with double salt KClMgSO43H2O(cr) within temperatures of
298.15–328.15 K. We identify the salt solubility parameters, that is, ΔfGk0
and ΔfHk0, of the double salt by regressing the 21 data points reported
0
for the double salt. The corresponding Cp,k of the salt is estimated from
the corresponding values for the salts KCl(cr), MgSO46H2O(cr), and
H2O(cr).30 We set the SD to 5% (in mole fractions) of the data for the (K+
Cl−), (Mg2+ Cl−), and (Mg2+ SO42−) concentrations. The identified salt solu-
bility parameters for the KClMgSO43H2O(cr) are reported in Table S2.
Figure 8 presents the Jänecke phase diagram illustrating the salt solu-
bility predictions for the quaternary at 328.15 K. The model predictions
are in semi-quantitative agreement with the solubility data including
invariant points except for the MgSO4 hydrate salt regions. These dis-
crepancies are consistent with the salt solubility model results reported in
Figure 2b for the aqueous Mg2+-Cl−-SO42− ternary system.
2.6 | The aqueous Na+-K+-Mg2+-Ca2+-Cl− quinary
system
The Jänecke phase diagram for the quinary system has the shape of a tri-
angular pyramid. Figure 9 shows the four sides of the pyramid for the
quinary at ~300 K by combining the Jänecke phase diagrams for the
aqueous Na+-K+-Ca2+-Cl− quaternary at 291.15 K, the aqueous Na+-K+-
2+ − + 2+ 2+ − overview on exploration and environmental impact of unconventional
Mg -Cl quaternary at 298.15 K, the aqueous Na -Mg -Ca -Cl qua-
ternary at 298.15 K, and the K+-Mg2+-Ca2+-Cl− quaternary at 308.15 K.
2.7 | The aqueous Na+-K+-Mg2+ -Cl−-SO42− quinary
system
The Jänecke phase diagram for the quinary system is a triangular
prism. Figure 10 presents the five sides of the prism by combining the
Jänecke phase diagrams for the aqueous Na+-K+-Cl−-SO42−, Na+-K+-
Mg2+-Cl−, Na+-K+-Mg2+-SO42−, Na+-Mg2+-Cl−-SO42−, and K+-Mg2
+
-Cl−-SO42− quaternary systems at 298.15 K.
3 | CO NC LUSIO N
A comprehensive molecular thermodynamic model has been developed
for the aqueous Na+-K+-Mg2+-Ca2+-Cl−-SO42− hexary system. The
model builds on our prior series of thermodynamic modeling work for
the various binary, ternary, quaternary, and quinary subsystems of the
hexary. This work reports the eNRTL binary interaction parameters,
including their temperature coefficients, for the following three
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9 of 10
electrolyte–electrolyte pairs with common ion: (Mg2+ Cl−):(Ca2+ Cl−)
pair, (Mg2+ Cl−):(Mg2+ SO42−) pair, and (Ca2+ Cl−):(Ca2+ SO42−) pair.
Identification of these binary interaction parameters along with integra-
tion of the binary interaction parameters from literature and the pure
component thermodynamic parameters for salts allow for complete
characterization of thermodynamic properties including calorimetric
properties, phase equilibria, and salt solubility for the hexary and its
subsystems at temperatures of 273.15–473.15 K and electrolyte con-
centrations up to saturation. The model reproduces the essential fea-
tures of the hexary system although the model results do not
necessarily agree with experimental data to within realistic experimen-
tal uncertainties. The model does not address volumetric and transport
properties. The simplicity of the model, the rigor of the thermodynamic
foundation, and the reliable model predictions should make the model
highly valuable in the development of novel and intensified process
technologies for desalination and brine treatment processes. The model
is currently being extended to include HCO3− ion.
ACKNOWLEDG MENTS
Funding support is provided by the U.S. Department of Energy under
the grant DE-EE0007888. The authors gratefully acknowledge the finan-
cial support of the Jack Maddox Distinguished Engineering Chair Profes-
sorship in Sustainable Energy sponsored by the J.F Maddox Foundation.
OR CID
Chau-Chyun Chen https://orcid.org/0000-0003-0026-9176
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SUPPORTING INF ORMATION
Additional supporting information may be found online in the
Supporting Information section at the end of this article.
How to cite this article: Tanveer S, Chen C-C. A
comprehensive thermodynamic model for high salinity
produced waters. AIChE J. 2020;66:e16818. https://doi.org/
10.1002/aic.16818