Ind. Eng. Chem. Res.

2005, 44, 3289-3297 3289

Determination of Ion-Specific NRTL Parameters for Predicting

Phase Equilibria in Aqueous Multielectrolyte Solutions
Hidetoshi Kuramochi,*,† Masahiro Osako,† Akiko Kida,† Kazuyuki Nishimura,†
Katsuya Kawamoto,† Yusuke Asakuma,‡ Keisuke Fukui,‡ and Kouji Maeda‡
Research Center for Material Cycles and Waste Management, National Institute for Environmental Studies,
16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan, and Department of Chemical Engineering, University of
Hyogo, 2167 Shosha, Himeji, Hyogo 671-2201, Japan

To develop an activity coefficient model for aqueous multielectrolyte systems, ion-specific NRTL
parameters were applied to the electrolyte-NRTL model. In total, 132 ion-specific NRTL
parameters for 21 ionic species (K+, Na+, Mg2+, H+, Ca2+, Zn2+, Al3+, NH4+, Cd2+, Co2+, Cu2+,
Pb2+, Mn2+, Ni2+, Cr3+, Cl-, SO42-, NO3-, OH-, ClO4-, CrO42-) were determined from the binary
activity coefficient data of aqueous electrolytes and used to predict the activity coefficients of
electrolytes in aqueous multieletrolyte solutions without any additional parameters. Furthermore,
solubilities of inorganic salts including heavy metals in aqueous mixed electrolyte systems and
the distribution ratio of Cu in a solvent extraction process containing HCl and CuCl2 were
predicted using the activity coefficients derived from our ion-specific electrolyte-NRTL model.
The results showed that the NRTL parameters obtained in this study accurately predict phase
equilibria of systems involving inorganic salts such that this model can be used in the design of
recovery processes such as crystallization and solvent extraction.

Introduction ficients in that as the concentration increases, the

The industrial production and treatment processes
dealing with inorganic compounds usually involve elec-
trolyte solutions. Mineral drinks, foods, seawater, and
wastewater all involve electrolyte solution chemistry.
The recovery or removal of inorganic salts including
heavy metals from wastewater and wastes is an emerg-
ing problem for the construction of sustainable societies
in terms of environmental protection and resource
recovery. These recovery and removal processes include
crystallization or precipitation, solvent extraction, sorp-
tion, and ion-exchange. These processes are currently
the topics of many studies.1-8 Generally speaking, these
separation processes are predicated on the phase equi-
librium between an aqueous phase and one other
additional phase. For example, solvent extraction is
based on the dissociation equilibrium of each salt in a
homogeneous phase and the distribution equilibrium of
individual ions between an aqueous phase and an
organic phase. Crystallization is based on solid-liquid
equilibrium, or the solubility product defined by the
activity coefficient and molality of aqueous ions. A
review of the various thermodynamic models of elec-
trolyte solutions from an engineering approach was
reported by Loehe and Donohue.9
The activity coefficient represents the phase equilib-
rium properties of the aqueous phase. However, the
activity coefficient data of binary aqueous electrolyte
solutions are not sufficient in calculating the phase
equilibrium in an aqueous multielectrolyte solution, as
the addition of other electrolytes affects the phase
equilibrium of the electrolyte of interest. There is also
a concentration dependence regarding activity coef-
* To whom correspondence should be addressed. Tel.:
+81-(0)29-850-2841. Fax: +81-(0)29-850-2091. E-mail:
kuramochi.hidetoshi@nies.go.jp.
†
National Institute for Environmental Studies.
‡
University of Hyogo.
10.1021/ie049377u CCC: $30.25 © 2005 American Chemical Society
Published on Web 03/12/2005
greater the effect on the phase equilibrium. In the case
of crystallization, highly concentrated electrolyte solu-
tions are necessary. In addition, for solvent extraction
and ion exchange, highly concentrated solutions of other
electrolytes must be used even if the concentration of
the electrolyte of interest is low or dilute.4-6 From this
point of view, the desired activity coefficient model
would be capable of representing the activity coefficient
behavior of a given ion in not only a wide concentration
range but also in multielectrolyte solutions.
Conventionally, in organic chemical and petroleum
industries, local composition models that express the
excess Gibbs free energy due to short-range inter-
molecular interactions such as the Wilson, NRTL, and
UNIQUAC models10 have been used as activity coef-
ficient models and contributed to the design process
regarding distillation, extraction, and absorption. More-
over, activity coefficient prediction models such as
UNIFAC11 have been proposed by combining the group
contribution concept with the local composition model.
In terms of inorganic chemical industries, activity
coefficient models are still being developed for waste-
water treatment, hydrometallurgy, desalination, and
crystallization processes, as well as for the understand-
ing of electrolyte solutions. Generally, activity coef-
ficients in a dilute electrolyte solution can be expressed
by the Debye-Hückel equation,12 which describes the
excess Gibbs energy due to long-range (electrostatic)
interaction. In early studies on concentrated solutions,
some equations were proposed and these are briefly
described below. In the 1970s, Pitzer13-16 suggested the
Debye-Hückel equation be followed by a virial expan-
sion of terms. In 1978, Cruz and Renon17 first considered
that the NRTL model18 was combined with the Debye-
Hückel model. The former and latter models represent
short-range and long-range interactions, respectively.
In the 1980s, Chen et al.19,20 developed an electrolyte-
NRTL model similar to the above model that resulted
3290 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005
Figure 1. Behavior of mean ionic activity coefficients (γ(,i
parentheses refers to the distribution in all the electrolytes used in this study.
in a good correlation of the activity coefficient between
measured and calculated values over a wide concentra-
tion range of salt in aqueous solution. Recently, Jaretun
and Aly21,22 applied additional empirical parameters to
the electrolyte-NRTL model for better representation of
aqueous activity coefficient of electrolytes. In particular,
the local composition model plays an important role in
representing activity coefficients of electrolytes over
wide concentration ranges. Similarly, using the UNI-
QUAC model23 as the local composition term, Lu and
Maurer,24 and Thomsen’s group25,26 developed the elec-
trolyte-UNIQUAC model and the extended UNIQUAC
model, respectively. Among these models including the
local composition model, Chen’s electrolyte-NRTL model
is the simplest and requires fewer parameters in the
calculation. Unfortunately, the model’s extension to
multielectrolyte solutions requires some additional pa-
rameters besides binary NRTL parameters between an
electrolyte and water. However, this disadvantage can
be solved by replacing the electrolyte-specific NRTL
binary interaction parameters used in the model with
ion-specific parameters.
The objective of this study is to determine ion-specific
NRTL parameters via correlating the activity coefficient
data of inorganic compounds containing heavy metals
with the electrolyte-NRTL model having these param-
eters. These results will then be used to predict the
activity coefficients and solubilities of inorganic salts
in mixed electrolyte solutions, and also to predict the
distribution ratio of Cu between xylene and an aqueous
HCl solution.
Activity Coefficients of Inorganic Salts in Water
In this study, we assumed that an aqueous electrolyte
solution consists of water, anions, and cations. This
complete dissociation assumption was extended to aque-
ous multielectrolyte systems. Since the activity coef-
ficient of an individual ion i (γ/i ) cannot be measured,
the activity coefficients of aqueous ions are usually
expressed as the mean ionic activity coefficient of
neutral electrolytes a-c. The mean activity coefficient
/
(γ(,ac ) is given by
/
νa ln γ/a + νc ln γ/c
ln γ(,ac )
νac
where νa is the stoichiometric coefficient of the anion,
or the number of moles of the anion produced by the
dissociation of one mole of a-c; νc denotes that of the
cation, and νac is
νac ) νa + νc
The activity coefficient of an electrolyte or ion is based
/
) of aqueous electrolytes as a function of molality (m). The percentage in
on unsymmetric convention, while that of organic
compounds is symmetric.
Activity coefficients of inorganic compounds show a
negative or positive deviation from one with an increase
in salt molality. These behaviors are categorized into
three different patterns, as shown in Figure 1. The
activity coefficient of Type I significantly decreases with
an increase in molality. In the case of Type II, the
activity coefficient approaches a constant value much
lower than one at moderate to high molalities. Contrary
to Type I and II, Type III significantly increases above
moderate molalities. The distribution of the electrolytes
in this study among the three types was 17%, 27%, and
56% for Types I, II, and III, respectively.
Activity Coefficient Models for Aqueous
Electrolytes
In a dilute solution (less than 0.1 mol kg-1), it is well-
known that the activity coefficient of an electrolyte can
be expressed by the Debye-Hückel equation:12
A|zi ‚zi|xI
ln γ/i ) (3)
1 + BrxI
where z and r denote the ion charge and distance of the
closest approach, respectively. A and B are the Debye-
Hückel constants calculated from the dielectric constant
of the solvent and temperature. The ionic strength is
defined by
N
1
I) ∑
2 i
z2mi (4)
Up to an ionic strength of a few tenths molal, the Davies
equation27 is considered to be accurate. In the Davies
equation, an additional term is introduced into the
Debye-Hückel equation as follows:
A|zi ‚zi|xI
ln γ/i ) + 0.1|zi ‚zi|I (5)
1 + BrxI
Neither equation is able to express the decreasing and
increasing behavior of an activity coefficient over a
(1) moderate concentration range like those seen in the
activity coefficient profiles of Types I and III. In addi-
tion, eqs 3 and 5 give similar values using the same
concentration and electric charge when only ionic
strength is taken into account. This indicates that these
equations cannot distinguish the significant differences
in the behavior of activity coefficients among ionic
species.
(2) To describe all types of activity coefficients, local
composition models such as the NRTL, Wilson, and
UNIQUAC models are added as a correction term to the

/ ∆gij or τij denotes the NRTL binary interaction param-
Debye-Hückel term (ln γi,D-H ) as follows:
/ /
ln γ*i ) ln γi,D-H + ln γi,local•composition
These models can predict the increase or decrease in
the values of activity coefficients, depending on the
values of the binary interaction parameters between
water and ion or ion and ion. The variance in this
increase or decrease is proportional to electrolyte mo-
lality. Among these models, the NRTL model is consid-
ered to be the simplest and most convenient from a
calculation perspective because only the interaction
parameters are required for the activity coefficient
calculation. In the other models, such as the UNIQAUC
model, size parameters of ionic or molecular species
except for the interaction parameters are required. In
this study, therefore, the electrolyte-NRTL model pro-
posed by Chen et al.19 was used for predicting the
activity coefficients of electrolytes in single and mixed
salt aqueous systems.
Correlation Method
Chen’s Electrolyte-NRTL Model. In the electrolyte-
NRTL model proposed by Chen et al.,19 the activity
coefficient of an aqueous ion i is represented by the
combination of the Pitzer-Debye-Hückel equation and
NRTL equation as follows:
ln γ/i ) ln γi,pdh
/ /
+ ln γi,NRTL
The Pitzer-Debye-Hückel equation is a function of
ionic strength only, and is given by
/ between an electrolyte ac and another electrolyte a′c′
ln γi,pdh )
Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005 3291
eter of the i-j combination for any species, respectively.
(6) ∆gij is defined as the difference in the interaction energy
between the i-j and j-j combinations. The NRTL-
derived activity coefficient (γi, NRTL) is based on sym-
metric convention. This convention is different from that
of the activity coefficient of aqueous salts. Therefore,
the activity coefficient must be transformed to
/
the unsymmetric activity coefficient (γi,NRTL ) using the
NRTL-derived infinite dilution activity coefficient
∞
(γi,NRTL ) as follows:
∞
ln γi,/ NRTL ) ln γi,NRTL - ln γi,NRTL (11)
According to the original NRTL equation,18 the following
six NRTL parameters (∆gij) are required for the water-
single electrolyte system: ∆gwa for water-anion, ∆gaw
for anion-water, ∆gwc for water-cation, ∆gcw for cation-
water, ∆gac for anion-cation, and ∆gca for cation-anion.
In all the electrolyte-NRTL-type models, the use of the
local electric neutralization concept led to the reduction
of the six parameters to the following two parameters:
∆gacw or τacw for electrolyte (ac)-water and ∆gwac or τwac
for water-electrolyte (ac). These NRTL parameters are
referred to as the electrolyte-specific NRTL parameters,
and make the NRTL term much simpler. Unfortunately,
these parameters, which are determined from activity
(7) coefficient data of binary aqueous systems, are some-
times difficult to predict activity coefficients in aqueous
multielectolyte solutions because the electrolyte-NRTL
model is a correlative model for aqueous multielectrolyte
solutions and thus two additional NRTL parameters

( ) {( ( )}
∆gaca′c′ and ∆ga′c′ac are required for a ternary solution of

) zi2Iz1/2 - 2Iz3/2
1/2
2zi2 multielectrolytes.
1000
- Aφ ln (1 + FIz1/2) + Modifications of Chen’s Electrolyte-NRTL Model.
Ms F 1 + FIz1/2 The disadvantage of Chen’s model is the electrolyte-
(8) specific parameters, which require some additional
parameters and mixing rules to predict phase equilib-
where Ms, Aφ, and F refer to the molecular weight of rium in water-multielectrolyte systems such as waste-
the solvent, the Pitzer-Debye-Hückel parameter, and water and wet wastes. The parameters and rules cannot
the closest approach parameter () 14.9), respectively. be determined from only binary activity coefficient data.
Aφ is calculated according to Chen’s paper.19 Ix is the The ion-specific parameter proposed by Liu et al.28 is
ionic strength based on the mole fraction x defined by considered to be a convenient and adaptable modifica-
tion for overcoming this disadvantage. The difference
1 N between electrolyte-specific and ion-specific parameters
Ix )
2
∑i z2xi (9) can be briefly explained as follows. For a water-
electrolyte binary system, in the former ∆gaw ) ∆gcw )
∆gacw, while in the latter ∆gaw * ∆gcw. In the present
The NRTL equation is generally expressed as study, two modifications were performed to introduce

( )
the ion-specific parameters to Chen’s electrolyte-NRTL
ln γi,NRTL ) model. First, the local electric neutralization was ex-
N N cluded. Although this exclusion results in a more
∑j zjGjiτji
N zjGij
∑k zkGkjτkj complicated calculation, it makes the model more
extensible to multielectrolyte solutions. Second, ∆gcc or
N
+ ∑j N τij -
N
(10) ∆gaa, for cation-cation or anion-anion interaction
∑k zkGki ∑k zkGkj ∑k zkGkj parameters in the multielectrolyte system, was assumed
to be zero on the basis of Lu’s assumption24 for interac-
tions between ions carrying a charge of the same sign.
In their assumption the cation-cation and anion-anion
where
interactions gcc and gaa are set to 16628 (2000 × R)
J‚mol-1 due to a large repulsive force. Hence, either ∆gcc
Gij ) exp(-Rτij)
or ∆gaa for any ion species becomes zero by the definition
∆gij gij - gjj of ∆gij () gii - gjj). This assumption is useful for
τij ) ) reducing the number of the NRTL parameters required
RT RT for activity coefficient calculation for multielectrolyte
R ) nonrandom factor () 0.2) systems. Consequently, six NRTL parameters (∆gwa,
3292 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005
Table 1. Aqueous Binary Systems for Single Electrolytes
Used to Determine the Ion-Specific NRTL Parametersa
activity
coefficient
behavior electrolytes
type I CuSO4, Pb(NO3)2, (NH4)2SO4, NH4NO3, Na2SO4,
K2SO4, KNO3, CdCl2
type II NH4Cl, Al2(SO4)3, ZnSO4, MgSO4, KCl, NiSO4,
MnSO4, CdSO4, K2CrO4, Na2CrO4, Cr2(SO4)3,
H2SO4
type III CuCl3, Cu(NO3)2, Pb(ClO3)2, Co(NO3)2, CoCl2,
AlCl3, Zn(NO3)2, Zn(ClO4)2, Ca(NO3)2, CaCl2,
Ca(ClO4)2, HClO4, HCl, HNO3, KOH, NaOH,
Mg(ClO4)2, MgCl2, Mg(NO3)2, NaNO3, NaCl,
NiCl2, MnCl2, CrCl3, Cr(NO3)3
a Data sources: Robison and Stokes,27 Mullin,29 and Majima and
Awakura30.
Figure 2. Ion-specific NRTL parameter matrix for 66 pairs.
∆gaw, ∆gwc, ∆gcw, ∆gac, and ∆gca) required for the
calculation of one binary system can be determined from
the experimental binary activity coefficient data of
aqueous electrolytes.
Results and Discussion
Correlation of Binary Activity Coefficients of
Aqueous Electrolytes. The binary activity coefficient
data for single electrolytes in water were collected from
two books27,29 and the literature30 and summarized in
Table 1. In total, 45 binary systems were available to
determine 66 pairs of the ion-specific NRTL parameters.
In Figure 2, the parameters to be determined are
categorized in a matrix, where dark, hatched, and gray
areas indicate the newly determined parameters and
parameters set to be zero, respectively. In the parameter
determination, a nonlinear mean square (Marquardt)
method was used as the optimization algorithm. To
determine a pair of the parameters between an ion and
water, the activity coefficient data for all salts with the
same ion are required. Hence, all the parameters were
simultaneously determined using all of the experimental
data to minimize the absolute deviation between ex-
perimental and calculated values. However, the use of
such a large number of parameters led to the diversion
of the objective function and a huge calculation time,
making it impossible to simultaneously correlate all of
the ion/water parameters. In this study, therefore, the
parameter determination process was divided into two
steps. First, the ion-specific parameters for 3 cations and
anions (Na+, K+, Mg2+, Cl-, NO3-, and SO42-) were
determined, since these ions were the primary constitu-
ents of the salts shown in Figure 2 and the nine salts
with these ions exhibited all types of activity coefficient
behavior. If the determined parameters were not able
to accurately represent the activity coefficient behavior,
the use of the ion-specific parameters would be discred-
ited as a good approach for representing and predicting
the activity coefficients for all of the salts. The deter-
mined NRTL parameters are given in Table 2. The
initial results for the nine binary systems accurately
represented the experimental data, as shown in Figure
3. On the basis of these reliable parameters, the other
NRTL parameters for the other 15 ionic species were
determined from the binary activity coefficient data for
the 36 electrolytes. All the determined parameters are
summarized in Table 2. The two-step determination
successfully correlated the binary activity coefficient
data with the ion-specific NRTL parameters. To evalu-
ate the reliability of the obtained parameters, a com-
parison with the results obtained by Chen et al.19 was
carried out in respect to the standard deviation of the
logarithmic mean activity coefficient (σlnγ*(,i). The re-
sults are summarized in Table 3. The average σlnγ*(,i in
our calculations with 132 NRTL parameters (0.083) was
almost equal to that in Chen’s model with 90 param-
eters (0.079). This comparison demonstrated that this
study can provide reliable and reasonable ion-specific
NRTL parameter sets. Since the parameters can only
predict the activity coefficients in aqueous multielec-
trolyte solutions without any additional parameters,
this study suggests the first universal NRTL parameters
for aqueous electrolyte solutions. As further works, the
parameter values for other ions will be determined.
Future work should add the parameters of other ions,
particularly AsO43- and PO43-, to the list for the
purposes of environmental protection and resource
recovery.
Prediction of Activity Coefficients in Multielec-
trolyte Solutions. The activity coefficients for multiple
components in aqueous solutions were predicted based
on the ion-specific NRTL parameters obtained above.
Figure 4 shows the predicted and experimental mean
activity coefficients30-32 of various solutes at different
molalities of cosolutes in an aqueous solution. In terms
of the water-HCl-CuCl2 system, the predicted results
were in good agreement with the experimental data.
Similarly, in the water-MgSO4-MnSO4 system and the
water-H2SO4-(NH4)2SO4 system, the ion-specific NRTL
parameters predicted complicated behaviors of activity
coefficients in two-salt systems. The deviations between
calculated and experimental results are given in Table
4. The accuracy of the predictions was around the
deviations in the correlated results of binary systems
(Table 3). These results demonstrate that the ion-
specific NRTL parameters are useful for predicting the
multicomponent activity coefficients of different cations
and anions in water, and thus enable us to design
equilibrium separation and recovery processes dealing
with aqueous mutlielectrolyte solutions. In addition,
these results indicate that the assumption concerning
the interaction parameters between ions with the same
sign does not cause large deviations in accuracy with
respect to the prediction of multielectrolyte systems.
However, in the water-H2SO4-CuSO4 system, the
predicted curves did not quantitatively represent the
experimental behavior, despite relatively accurate re-
sults for the water-H2SO4-(NH4)2SO4 system. This
 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005 3293

Table 2. Ion-Specific NRTL Parameters ∆gij/J‚mol-1

From H2O to CO2+
H2O K+ Na+ Mg2+ H+ Ca2+ Zn2+ Al3+ NH4+ Cd2+ Co2+
H2O 0 1100 7150 8170 8950 -15000 14500 -5530 -22500 18700 -13600
K+ 13900 0 0 0 0 0 0 0 0 0 0
Na+ -10700 0 0 0 0 0 0 0 0 0 0
Mg2+ -13600 0 0 0 0 0 0 0 0 0 0
H+ -9000 0 0 0 0 0 0 0 0 0 0
Ca2+ 1850 0 0 0 0 0 0 0 0 0 0
Zn2+ -13700 0 0 0 0 0 0 0 0 0 0
Al3+ -13400 0 0 0 0 0 0 0 0 0 0
NH4+ 2820 0 0 0 0 0 0 0 0 0 0
Cd2+ -11100 0 0 0 0 0 0 0 0 0 0
Co2+ -8960 0 0 0 0 0 0 0 0 0 0
Cu2+ -10900 0 0 0 0 0 0 0 0 0 0
Pb2+ -6090 0 0 0 0 0 0 0 0 0 0
Mn2+ -13500 0 0 0 0 0 0 0 0 0 0
Ni2+ -11200 0 0 0 0 0 0 0 0 0 0
Cr3+ -14900 0 0 0 0 0 0 0 0 0 0
Cl- -9280 -10600 -12200 -19100 -11300 414 0 -25600 -23300 -10300 -33800
SO42- -5100 14100 -14400 -18500 -15700 0 -12400 -12900 -7500 194 0
NO3- -13300 -16800 -25200 -13400 -11700 -31200 -6400 0 -41500 0 -39500
OH- -11700 -11200 -13700 0 0 0 0 0 0 0 0
ClO4- -11300 0 0 -20400 -15100 1620 -13900 0 0 0 0
CrO42- -6790 36800 -12600 0 0 0 0 0 0 0 0

From Cu2+ to CrO42-

Cu2+ Pb2+ Mn2+ Ni2+ Cr3+ Cl- SO42- NO3- OH- ClO4- CrO42-
H2O 19400 -92500 2820 11400 -56400 -13200 -7990 -1540 -17100 -16300 -12500
K+ 0 0 0 0 0 -12900 -18200 -20000 -1440 0 9220
Na+ 0 0 0 0 0 -31900 -25200 9960 -39900 0 -30300
Mg2+ 0 0 0 0 0 3360 5480 -31400 0 -510 0
H+ 0 0 0 0 0 1760 5860 -24200 0 3900 0
Ca2+ 0 0 0 0 0 2310 0 -25600 0 265 0
Zn2+ 0 0 0 0 0 0 -1220 -31700 0 -1310 0
Al3+ 0 0 0 0 0 64700 -18800 0 0 0 0
NH4+ 0 0 0 0 0 -27800 -20800 -19800 0 0 0
Cd2+ 0 0 0 0 0 -36800 5640 0 0 0 0
Co2+ 0 0 0 0 0 5830 0 -22300 0 0 0
Cu2+ 0 0 0 0 0 -33700 5220 -29800 0 0 0
Pb2+ 0 0 0 0 0 0 0 -30700 0 707 0
Mn2+ 0 0 0 0 0 -31900 7750 0 0 0 0
Ni2+ 0 0 0 0 0 49700 5640 0 0 0 0
Cr3+ 0 0 0 0 0 -34500 -21200 -33100 0 0 0
Cl- 32300 0 -18900 -11300 -66400 0 0 0 0 0 0
SO42- 801 0 -24700 -11000 -66600 0 0 0 0 0 0
NO3- 4330 -114000 0 0 -76300 0 0 0 0 0 0
OH- 0 0 0 0 0 0 0 0 0 0 0
ClO4- 0 -116000 0 0 0 0 0 0 0 0 0
CrO42- 0 0 0 0 0 0 0 0 0 0 0

indicates the obtained parameters are still not perfect
for quantitative predictions of aqueous mutielectrolyte
solutions. For more accurate predictions of multlielec-
trolyte systems, the ion-specific parameters will most
likely need to be modified.
Solubility of Mixed Salts in Aqueous Solution.
A typical application of activity coefficient models is to
predict the solubility of a salt in an aqueous solution
containing other salts. The solubility is defined by the
solubility product Ks
/ /
Ks ) aν+
+ a- ) (γ+ x+) + (γ- x-)
ν- ν ν-
(12)
where a and x denote the activity and solubility in units
of mole fraction, respectively. The subscripts + and -
refer to cation and anion, respectively. In this study,
the temperature dependence is assumed to be repre-
sented by the van’t Hoff equation as follows:
B tures. Thermal parameters determined in this way for
R ln Ks ) A + (13)
T five salts with major ions and the strength of their
where R is the gas constant. The constants A and B
denote the thermal parameters of the pure salt, and are
independent of the concentration of the salt in the
aqueous solution. The relationship between the mole
fraction of the ion species and the molality of salt (m)
in solubility units is given by
υ+m υ-m
x+ ) , x- )
1000 1000
+ m(υ+ + υ-) + m(υ+ + υ-)
Ms Ms
(14)
The solubility data of mixed salts at the temperature
of interest are not easily obtained. Therefore, the
thermal parameters A and B should be determined by
correlating the experimental data29,34 with the electrolyte-
NRTL model that includes the ion-specific parameters
prior to the solubility prediction in a multielectrolyte
solution. If these constants are available, one can predict
solubilities in mixed salt systems at various tempera-
3294 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005

/
Figure 3. Correlation results of mean ionic activity coefficients (γ(,i ) for nine alkali and alkaline-earth metal salts.

/
Figure 4. Prediction results of mean ionic activity coefficients (γ(,i ) for four mixed electrolyte aqueous solutions at 298 K.

correlation with experimental values are given in Table
5. Furthermore, the results for three heavy metallic
salts in Table 5 are also given in Figure 5. Strong
correlations, with the exception of K2SO4, were ob-
served. The ability to calculate the solubility of a salt
in water at various temperatures allowed for the predic-
tion of solubilities of different salts in an aqueous mixed
salt solution at various concentrations. The predicted
results of the ternary solubilities are summarized in
Table 6. The deviations for NaCl and the heavy metallic
salts were relatively high, and increased with an
increase in the concentration of the unsaturated com-
ponent. These deviations may be due to the fact that it
is difficult for the electrolyte-NRTL model to predict the
solubility at higher concentrations of the unsaturated
component if there is ion association, since molecular
association is not considered in the NRTL model.
Whereas, the concentration level of the unsaturated
component in the case of the heavy metallic salts was
much higher than that in the case of NaCl. As shown
in Figure 6, the calculated values were consistently
within 10% of the experimental values below an HCl
concentration of 6 mol kg-1. This indicates that a good
prediction can be provided at relatively concentrated
solutions for the heavy metallic salts. As a whole, the
present solubility predictions for the aqueous mixed salt
 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005 3295

Table 3. Comparison of the Standard Deviation of the Table 5. Thermal Parameters for Equation 13 for Alkali
Logarithmic Mean Activity Coefficient Data of an and Alkaline-Earth Metal Salts, and Heavy Metal Salts
Electrolyte i in Water (σlnγ*(,i) between This Study and and the Relative Average Deviations
Chen’s Work19
relative average
electrolyte this study/- Chen’s work/- electrolytes A/J mol-1 K-1 B/J mol-1 deviationa/% ref
NaCl 0.018 0.024 alkali and alkaline metal salts
Na2SO4 0.043 0.024 K2SO4 114 -6460 10.6 29
NaNO3 0.126 0.002 NaCl 90.0 15900 2.72 29
KCl 0.003 0.003 KCl 41.4 -2610 2.18 29
K2SO4 0.017 0.008 Na2SO4 179 21800 0.81 29
KNO3 0.023 0.008 MgSO4 83.2 -5060 5.79 29
MgCl2 0.159 0.202 heavy metal salts
MgSO4 0.068 0.036 CoCl2 29.2 -17200 1.65 33
Mg(NO3)2 0.106 0.125 CuCl2 -132 22500 0.52 33
CuSO4 0.087 0.037 NiCl2 -41.5 9490 2.60 33
CuCl2 0.033 0.038
a ∑|(m
Cu(NO3)2 0.082 0.113 cal - mexp)/mexp|/N × 100 (m, solubility; N, number of data;
Pb(NO3)2 0.087 0.220 the subscript cal and exp denote calculation and experimental
Pb(ClO4)2 0.083 0.147 values, respectively).
Co(NO3)2 0.098 0.108
CoCl2 0.031 0.055
NH4Cl 0.003 0.001
(NH4)2SO4 0.052 0.017
NH4NO3 0.050 0.012
AlCl3 0.084 0.115
Al2(SO4)3 0.080 0.075
Zn(NO3)2 0.123 0.148
ZnSO4 0.061 0.038
Zn(ClO4)2 0.164 0.211
Ca(NO3)2 0.051 0.060
CaCl2 0.262 0.205
Ca(ClO4)2 0.337 0.272
HClO4 0.051 0.063
HCl 0.029 0.035
HNO3 0.045 0.008
KOH 0.062 0.023 Figure 5. Correlation results of the solubility (msol) of heavy
NaOH 0.034 0.029 metallic salts in water at various temperatures.
Mg(ClO4)2 0.159 0.208
NiCl2 0.053 0.092 Table 6. Comparison of the Predicted Results with the
NiSO4 0.097 0.031 Experimental Data for the Solubilities in Mixed
MnSO4 0.074 0.037 Electrolyte Solutions
MnCl2 0.036 0.047 relative
CdCl2 0.213 0.214 maximum of average
CdSO4 0.089 0.037 electrolyte maximum of total molality deviation of
K2CrO4 0.017 0.022 systems temp/ molality of of A1 and the solubility
(A1-A2) K A1/mol kg-1 A2/mol kg-1 of A2a/% ref
Na2CrO4 0.050 0.057
Cr2(SO4)3 0.178 0.129 K2SO4-MgO4 313 0.171 3.763 2.46 34
CrCl3 0.053 0.069 MgSO4-K2SO4 313 1.861 2.742 31.3 34
Cr(NO3)3 0.080 0.054 KCl-K2SO4 313 2.146 2.41 39.2 34
H2SO4 0.233 naa K2SO4-KCl 313 0.171 5.398 1.51 34
averageb 0.083 0.079 Na2SO4-K2SO4 313 1.718 2.27 161 34
K2SO4-Na2SO4 313 0.342 3.617 4.91 34
a na: not available. b denotes the average of σ
lnγ*(,i except for Na2SO4-MgSO4 313 1.374 4.717 2.86 34
H2SO4. MgSO4-Na2SO4 313 1.489 4.603 1.94 34
NaCl-KCl 313 2.146 6.278 11.7 34
Table 4. Standard Deviation of the Predicted KCl-NaCl 313 2.492 7.032 20.8 34
Logarithmic Mean Activity Coefficient Data (σlnγ*(,i) for NaCl-Na2SO4 313 2.491 4.626 9.29 34
Mixed Electrolyte Aqueous Solutions at 298 K Na2SO4-NaCl 313 1.374 6.305 10.7 34
HCl-CuCl2 298 7.802 10.849 22.6 33
molality molality σ lnγ/(,i HCl-NiCl2 298 8.342 9.415 10.9 33
electrolyte system of A1 of A2 of A2 HCl-CoCl2 298 8.428 9.077 24.2 33
(A1-A2) /mol kg-1 /mol kg-1 /- ref
a ∑|(m
cal - mexp)/mexp|/N × 100 (m, solubility; N, number of data;
CuCl2-HCl 0.1-4.0 0.4-2.4 0.055 30 the subscript cal and exp denote calculation and experimental
HCl-CuCl2 0.1-4.0 0.4-2.4 0.021 30 values, respectively).
(NH4)2SO4-H2SO4 0.240-4.188 0.5-2.0 0.118 31
H2SO4-(NH4)2SO4 0.252-2.889 0.5-2.0 0.068 31
MgSO4-MnSO4 0.1-2.8 0.1-2.4 0.057 32 the predicted values in the Na2SO4 system were opposite
MnSO4-MgSO4 0.1-2.4 0.1-2.8 0.051 32 of the experimental values. Consideration regarding the
CuSO4-H2SO4 0-1.2 0.4-1.6 0.184 30 hydration effect, similar to Lu’s model,24 may result in
H2SO4-CuSO4 0.1-1.6 0.4-0.8 0.393 30
a more successful prediction.
systems are considered to be successful because the ion- Distribution Ratio of Cu in a Solvent Extraction.
specific NRTL parameters are universal regarding all Another application of the model developed in this study
salts and all systems. Most studies reporting good is to predict the distribution equilibrium of a metallic
solubility predictions use binary parameters that lack ion between aqueous and organic phases in a solvent
this universality. Although good results were obtained extraction process. On the basis of the fact that the ion-
for the most part, the results for K2SO4 were difficult specific parameters accurately predicted ternary activity
and problematic, as shown in Figure 7. In particular, coefficients and solubilities in the water-HCl-CuCl2
3296 Ind. Eng. Chem. Res., Vol. 44, No. 9, 2005

h Cu C
C h CuR2
D) ) (16)
CCu C 2+
Cu

where CCu and C h Cu are the concentration of Cu2+ in the

aqueous phase (CCu2+) and the concentration of the
copper-extractant complex (CuR2) in the organic phase
h CuR2), respectively. If the activity coefficients of all
(C
components in the organic phase can be approximated
to unity, the distribution equilibrium constant Ke is
simplified as follows:

h CuR2 × (γH+ × CH+)2

C
Figure 6. Predicted solubility (msol) of heavy metallic electrolytes
in hydrogen chloride solution for the ternary systems at 298 K.
Ke ) (17)
h HR2
(γCu2+ × CCu2+) × C

Consequently, substituting eq 16 into eq 17, the distri-

bution was calculated using

Figure 7. Predicted solubility (mK2SO4) of K2SO4 in mixed elec-
trolyte solutions at 313 K. Added electrolyte (A1): MgSO4, Na2-
SO4, and KCl.
system, a solvent extraction system consisting of HCl
and CuCl2 was selected. The complete system used was
the water-xylene(-β-hydroxyoxime)-HCl-CuCl2 two-
phase system,35 and the distribution ratio of Cu between
the two phases was predicted. The extraction equilib-
rium of Cu with β-hydroyoxime as the extractant (HR)
is described by the following equation:
CCuR2 γCu2+
log ) log + 2log CHR + log Ke
CCu2+ (γH+ × CH+)2
(18)
The literature value for Ke determined by Tanaka35 was
used in this calculation. By substituting the electrolyte-
NRTL model for activity coefficients in eq 18, the
distribution ratios of Cu were accurately predicted. The
predicted ratios are plotted as a function of pH in Figure
8. As shown in Figure 8, the predicted distribution ratios
decreased with a decrease in pH in good quantitative
agreement with the experimental data.35 Comparing
these results with those of the Davies equation in Figure
8 indicates that the present electrolyte-NRTL model is
more useful at relatively high concentrations of HCl.
This level of accuracy is attributed to the reasonable
values of the activity coefficients in aqueous multielec-
trolyte solutions achieved using this model.

Cu2+ + 2HR ) CuR2 + 2H+
where the bar above the compounds denotes the xylene
phase. The distribution ratio D for Cu between both
phases is defined by
Conclusion
(15)
The introduction of ion-specific NRTL parameters into
the conventional electrolyte NRTL model proposed by
Chen et al. led to the accurate prediction of activity
coefficients in aqueous multielectrolyte solutions with-

Figure 8. Measured and predicted distribution ratio (D) of Cu in solvent extractions (HCl-CuCl2-water-xylene-β-hydroxyoxime systems)
as a function of pH in aqueous phase. Symbols, measured values; solid lines, predicted values. (a) Prediction by the electrolyte-NRTL
model with ion specific parameters. (b) Prediction by the Davies equation.

out any additional parameters. This electrolyte-NRTL
model was also used to predict the solubilities of
inorganic salts including heavy metals in multielectro-
lyte solutions and the distribution ratio of copper
between aqueous and organic phases with a high level
of accuracy. These predictions demonstrated that the
obtained parameters have the potential to be very useful
in the design of processes involving the removal and
recovery of hazardous heavy metallic salts and other
industrial inorganic compounds. This model can also
significantly contribute not only to the solution of many
environmental and resource problems, but also to the
development of recycling technologies. The parameters
for other important ions such as PO43- should be
determined in future work.
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Received for review July 16, 2004
Revised manuscript received January 19, 2005
Accepted February 9, 2005
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