Fluid Phase Equilibria 242 (2006) 6571

A new model for the activity coefficients of individual

ions in aqueous electrolyte solutions
G.R. Pazuki a, , A.A. Rohani b
a

Department of Biotechnology Engineering, Malek ashtar University of Technology, Tehran, Iran

b Department of Chemistry, Islamic Azad University, Shahrood Branch, Shahrood, Iran

Received 15 February 2005; received in revised form 7 December 2005; accepted 9 January 2006

Abstract
In this study, the individual ion activity coefficient in an aqueous solution is modeled with a new model. This model contains two physical
significant ionic parameters regarding the ionic solvation and the closest distance of approach between ions in a solution. The present model was
evaluated by the estimation of the individual activity coefficients of the ions of thirty electrolytes in aqueous solutions. The results showed that this
model suitably predicts the individual ion activity coefficients in aqueous two-electrolyte solutions consisting of the binary pairs of electrolytes of
NaCl, KCl, KBr and CaCl2 in a temperature range from 298.15 to 243.15 K. The results by this model were compared to the literature values. The
average absolute relative deviations of vapor pressures showed acceptable agreement between experimental data and the results of this model.
2006 Elsevier B.V. All rights reserved.
Keywords: Activity coefficient; Electrolyte solution; Vapor pressure; Osmotic coefficient; Ions

1. Introduction
The phase behavior of individual ions in an aqueous solution is important for the design of particular processes involving
ion-exchange. There is a need for experimental values of the
activity of individual ions for the study of oil recovery, absorption heats pump, gas sweetening and biological systems [1]. The
DebyeHuckel model is the first model that predicts the phase
behavior of electrolyte solution but it is can be used for very
dilute solutions [2]. Pitzer [3], Pitzer and Mayorga [4], Bromley [5] and Pazuki [6] and Pazuki and Arabgol [7] predict the
models based on DebyeHuckel model. Models for the shortrange interaction term between ion and molecule based on local
composition based model such as Wilson and NRTL models,
Cruz and Renon [8], Chen and Evans [9], Zhao et al. [10], Xu
and Macedo [11] and Sadeghi [12] a combination of the Pitzar
model for the long-range interaction and NRTL model for the
short-range interaction was applied. Other models based on the
use of pair correlation functions are the mean spherical approximation (MSA) used of Harvey and Prausnitz [13], Liu et al.

[14] and Taghikhani and Vera [15]. In this Study, a new model
is used which contains two parameters proposed for ion activity coefficients. Furthermore, the vapor pressure of the aqueous
multi-electrolyte solutions were calculated by a mixing rule from
the single electrolyte solutions parameters. The results of the
new model and the literature values showed good agreement for
this model.
2. Activity coefcient of individual ions
The activity coefficient of an individual ion contains a combination of the long-range interaction and short-range interaction
as shown below
ln i = ln iLR + ln iSR

Guggenheim proposed the first model of the activity coefficient

of individual ion i from the approximation of DebyeHukel
model [12]:
ln i =

Corresponding author. Tel.: +98 215712883.

E-mail address: ghpazuki@yahoo.com (G.R. Pazuki).

0378-3812/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.01.004

(1)

Az2i I 1/2
1 + BD I 1/2

(2)

In the above equation, A is a parameter depending temperature

and BD is a parameter for the size of the ion. Based on this model

66

G.R. Pazuki, A.A. Rohani / Fluid Phase Equilibria 242 (2006) 6571

the long-range interaction of Guggenheim model for each ion

can be written as

written as shown below

Az2i I 1/2
ln i =
1 + Bi I 1/2

ln i =

(3)

Recently, Lin and Lee [17] predicted a new approach for the
short-range interaction. This model was considered the effect of
ions with water molecules in an aqueous solution. Based on the
Coulombs law, the electric potential between ion i and water
molecule calculated as below
hiw zi e
iw =
(4)
ri2
where the is the dipole moment of water, hiw a proportional
factor, and ri is the distance between ion and water molecule. Lin
and Lee [13] proposed ri inversely proportional to the inverse of
ionic strength of solution, Therefore
r i = i I

1/2

The ionic activity coefficient of the solvation effect can be calculated as follow [16]
 zi
ln iSR =
iw dz
(7)

+ Bi

1/2

1 + Ix

Ix

1/2

1 + Ix

+ Ci ln (1 + Ix2/3 )

(11)

where Ax is the DebyeHuckel constant, at 298.2 K is equal to

8.766, Bi and Ci the adjustable parameter, = 9, and Ix is defined
as
Ix =

1 2
xi zi
2

(12)

where xi is the mole fraction of ion i in the mixture. The relation for the mean ionic activity coefficient of electrolyte can be
presented according to the following relation:
3/2

1/2

ln =

(5)

where i is a proportional factor and is the parameter to be

determined experimentally. Substituting Eq. (5) to Eq. (4), The
dimensionless potential, iw = e iw /kT can be calculated from

2 
e
(6)
iw = hiw zi
I
2i kT

3/2

Ax z2i Ix

Ax |z+ z |Ix
1/2

1 + Ix

+ B

Ix

1/2

1 + Ix

+ C ln(1 + Ix2/3 )
(13)

where
B =

+ B+ + B
+ +

(14)

C =

+ C+ + C
+ +

(15)

In Eqs. (14) and (15), the subscripts plus and minus denote the
parameters for the cation and anion.

By substituting Eq. (6) into Eq. (7), the activity coefficient of

species i can be determined as shown bellow



hiw e2 z2i I
Ci z2i I
SR
ln i =
=
(8)
T
T
22i k
The term (hiw e2 /22i k) is defined as the solvation parameter
of ion.
Substituting equations of ln iLR and ln iSR into Eqs. (3) and
(8) the new model for the activity coefficient of individual ion is
ln i =

Az2i I 1/2
Ci z2i I
+
1 + Bi I 1/2
T

(9)

The parameter in Eq. (9) is empirical and should be calculated

by the correlation from experimental data. This constant value
was evaluated to be 1.29 for this study. The binary parameters
of this model for anion and cation were obtained by optimizing
the objective function as seen below
 exp
2
=
(i ical )
(10)
i

3. Thermodynamic models for activity of individual ions

3.1. KhoshkbarchiVera model
Khoshkbarchi and Vera modified the Pitzer model [14] to
calculate the activity coefficients of ion [15]. This model can be

3.2. LinLee model

Lin and Lee were proposed two parameter model based on
PitzerDebyHuckel (PDH) model for long range interaction
[20]. For this model, activity coefficient is obtained as below
equation:
ln i = ln iPDH + ln iSV

(16)

where ln iPDH is calculated as follow


ln iPDH = A Zi2

I 1/2
2
+ ln(1 + Bi I 1/2 )
1 + Bi I 1/2
Bi

(17)

Also lniSV is calculated based on electrical potential law. This

is called solvation effect. Activity coefficient of individual ions
for solvation effect is shown with below equation:
ln iSV =

Ci Zi2 I
T

(18)

In the above equation = 1.29. Therefore, activity coefficient

of individual ions in aqueous electrolyte solution is calculated
from Eq. (19):


I 1/2
2
Ci Zi2 I
1/2
ln i = A Zi2
+
ln(1
+
B
I
)
+
i
1/2
1 + Bi I
Bi
T
(19)

G.R. Pazuki, A.A. Rohani / Fluid Phase Equilibria 242 (2006) 6571

67

where Bi and Ci are the adjustable parameters for anion and

cation. The mean ionic activity coefficient for LinLee model is
obtained as follows [20]:
ln

=


1/2
I
i A Zi2 1+B
+
I 1/2
i

2
1/2 )
Bi ln(1 + Bi I

+ +

Ci Zi2 I
T

(20)

3.3. Pitzer model

Pitzer model is a semi-emperical model for correlation the
activity coefficient of individual ions [18]. This model is presented based on DebyeHukel model:
AZi2 I 1/2
ln i =
+ Ci I
1 + Bi I 1/2

(21)

Fig. 1. Individual activity coefficients of ions in aqueous solution: () experimental value for ; () experimental value for ; () calculated by this model.

where in the above equation A = 1.176. Bi and Ci are adjustable

parameters for each ions. The mean ionic activity coefficient for
Pitzer model is obtained as follow



AZi2 I 1/2
i 1+B I 1/2 + Ci I
i
ln =
(22)
+ +
4. Results and discussion
4.1. Activity coefcients of ions in aqueous electrolyte
solution
The experimental ion activity coefficients of individual ions
in aqueous electrolyte solution were obtained in the literature. In
Tables 1 and 2 the binary interaction of each individual ion and
average absolute deviations (100) of ions for this model and the
KhoshkbarchiVera model are reported. The results of Table 2
show this model can accurately correlate the experimental activity coefficients of each individual ion in electrolytes aqueous
solutions. In addition, the results of this model are better than
the KhoshkbarchiVera model. Figs. 13 compare the prediction of correlation of the activity coefficients of individual ions
and this model in NaCl, KBr and BaBr2 electrolyte solutions.

Fig. 2. Individual activity coefficients of ions in aqueous solution: () experimental value for ; () experimental value for ; () calculated by this model.

4.2. Develop of the new model for mixed electrolytes

solution
This model could be used to calculate of vapor pressure and osmotic coefficient of the electrolyte solutions. The
GibbsDuhem equation for a mixture of electrolytes at constant
temperature and pressure can be written as

nw d ln aw +
ni d ln ai = 0
(23)
i

where nw = 1000/Mw and ni is the number of moles of water and

ions. By integration of Eq. (16), the activity coefficient of water
in an aqueous mixture of electrolyte solution can be obtained

Fig. 3. Individual activity coefficients of ions in aqueous solution: () experimental value for ; () experimental value for; () calculated by this model.

68

G.R. Pazuki, A.A. Rohani / Fluid Phase Equilibria 242 (2006) 6571

Table 1
Parameters and the average absolute deviation of the activity coefficient of individual ion single electrolyte solution (Bi and Ci parameters of LinLee model are
obtained from Ref. [20])
Electrolyte

Ion

This work

Lin-Lee

Bi

Ci

Bi

Ci

KhoshkbarchiVera

Pitzer

Reference

Bi

Ci

Bi

Ci

KBr

K+
Br

1.194
1.650

25.016
28.971

0.720
3.837

0.022
19.292

75.118
92.198

0.028
0.181

1.257
1.425

0.100
0.140

[17]

NaCl

Na+
Cl

3.627
0.676

28.265
12.958

4.352
1.827

26.448
19.245

95.891
60.973

0.557
0.409

2.544
0.571

0.168
0.090

[19]

NaBr

Na+
Br

2.155
1.011

44.188
10.204

2.935
2.554

43.406
17.469

205.641
48.987

0.156
0.157

1.293
0.912

0.278
0.064

[19]

KCl

K+
Cl

0.807
1.737

9.883
6.692

1.243
3.235

13.296
11.158

45.877
16.791

0.293
0.221

0.741
1.638

0.060
0.038

[19]

NaOH

Na+
OH

3.963
0.506

95.764
30.460

0.971
6.052

59.306
15.685

299.712
120.072

0.671
0.481

2.384
0.701

0.451
0.193

[22]

KOH

K+
OH

1.148
1.903

25.206
75.406

0.002
22.347

36.479
159.038

90.248
257.028

0.054
0.241

0.981
0.376

0.132
0.376

[22]

LiCl

Li+
Cl

5.204
0.784

96.363
1.635

6.768
1.887

82.778
20.090

370.584
5.911

0.558
0.274

2.101
0.773

0.518
0.01

[23]

NaF

Na+
F

1.420
0.901

9.570
18.961

2.393
1.647

18.792
18.176

1979.23
2097.220

0.053
0.089

1.431
0.812

0.032
0.093

[24]

KF

K+
F

0.831
1.710

5.905
33.986

1.316
2.763

22.634
27.917

393.531
709.075

0.133
0.045

0.792
1.252

0.034
0.198

[24]

CaBr2

Ca2+
Br

3.510
0.650

27.690
0.194

6.855
1.260

25.315
9.085

499.561
3.962

1.508
0.391

0.634
1.207

0.004
0.905

[25]

BaBr2

Ba2+
Br

2.651
0.770

14.041
5.692

4.606
1.960

13.665
9.861

213.608
25.476

1.413
0.281

0.780
2.074

0.030
0.371

[25]

MgCl2

Mg2+
Cl

2.821
0.734

23.861
7.698

4.785
1.860

22.914
12.942

438.562
40.288

1.193
0.343

0.715
1.962

0.0045
0.626

[26]

CaCl2

Ca2+
Cl

2.161
0.867

19.541
4.798

3.908
2.085

18.321
10.745

360.302
26.527

0.866
0.233

0.812
1.716

0.034
0.506

[26]

BaCl2

Ba2+
Cl

1.837
1.045

13.421
5.364

2.985
2.203

14.899
3.092

205.470
24.202

0.784
0.067

1.081
1.602

0.031
0.322

[26]

from


The osmotic coefficient for a mixture of electrolytes can be written as shown below

M w i mi
M w i mi 

xi ln i
1000
1000
i

 I
Mw i mi 
+
xi
ln i dI
1000I
0

ln aw =

(24)

where mi is the molality of electrolyte i and I is the ionic strength.

The activity of water is given in terms of the osmotic coefficient
of multi-electrolyte is defined as
=

1000

ln aw
M w i mi

Then the osmotic coefficient can be written from



1 I
ln i dI
=1+
xi ln i
I 0

(25)

(26)

2
1

2 I 1/2
B
(1
+
Bi I 1/2 )
B
i
i
i

2
mI m  2
1/2
3 ln(1 + Bi I ) +
xi zi Ci
(m + 1)T
Bi I

= 1A

xi z2i

(27)

where A in this equation is equal to 1.176 and Bi, Ci are the

adjustable parameters of ions and can be calculated by fitting
the activity coefficients of individual ions in single electrolyte
solution xi is the mole fraction of ion i. in the mixture. In Eq. (20),
Bi and Ci are the two parameters for ion i, which are calculated
from the following mixing rules [21]:
Bi =


l

Xl B i,l

(28)

G.R. Pazuki, A.A. Rohani / Fluid Phase Equilibria 242 (2006) 6571
Table 2
The average absolute deviation of activity coefficients of individual ions for the
new model and other models (average absolute deviation of LinLee model are
obtained from Ref. [20])
Electrolyte

Ion

100

lated as below
Bc1 = Xa1 B c1 ,a1 + Xa2 B c1 ,a2

(32)

Bc2 = Xa1 B c1 ,a2 + Xa2 B c2 ,a2

(33)

Also above parameter for a1 , a2 anions are obtained as follow

This work

LinLee

KhoshkbarchiVera

K+
Br

0.68
0.70

1.4
1.5

0.7
0.7

0.7
0.8

NaCl

Na+
Cl

1.18
0.83

1.3
1.0

1.8
1.0

1.3
0.9

NaBr

Na+
Br

2.30
1.63

1.7
1.4

1.7
2.0

1.6
1.9

KCl

K+
Cl

2.37
0.43

1.9
1.0

2.8
0.2

2.6
0.3

NaOH

Na+

OH

2.82
1.82

1.0
0.7

1.8
2.1

1.8
1.7

KOH

K+
OH

0.76
0.91

2.0
3.5

0.6
1.1

0.7
1.2

LiCl

Li+
Cl

4.18
0.14

2.0
0.6

2.1
0.4

2.1
0.2

NaF

Na+
F

1.75
0.85

1.6
0.7

1.1
0.8

1.8
0.8

Now, we consider a multi-electrolyte solution with a1 common

ion and c1 , c2 cations. B parameter for cations are obtained from
Eqs. (40) and (41):

KF

K+
F

1.24
2.09

0.9
2.0

1.1
1.8

1.2
1.9

Bc1 = Xa1 B c1 ,a1 = B c1 ,a1

(40)

CaBr2

Ca2+
Br

1.15
0.133

6.9
0.8

4.7
0.1

1.5
20.7

Bc2 = Xa1 B c1 ,a2 = B c1 ,a2

(41)

BaBr2

Ba2+
Br

7.18
1.14

6.9
1.0

4.7
1.6

1.5
4.4

MgCl2

Mg2+
Cl

5.53
1.09

5.7
1.2

8.7
2.0

1.5
5.3

CaCl2

Ca2+
Cl

5.61
1.04

4.9
1.4

7.6
1.4

1.2
5.2

BaCl2

Ba2+
Cl

4.05
0.68

4.3
0.6

3.4
0.6

0.6
2.7

Average

Cation
Anion

2.91
0.97

3.03
1.24

3.53
1.14

3.45
1.38

KBr

1
N

 | exp cal |
i

exp

Pitzer

69

Ba2 = Xc1 B

a2 ,c1

+ Xc2 B

(34)
(35)

a2 ,c2

Ci parameter for c1 , c2 cations in electrolyte solution are calculated as below

Cc1 = Xa1 C c1 ,a1 + Xa2 C c1 ,a2

(36)

Cc2 = Xa1 C c1 ,a2 + Xa2 C c2 ,a2

(37)

The above parameters for a1 , a2 anions are obtained as follow

Ca1 = Xc1 C a1 ,c1 + Xc2 C a2 ,c1

(38)

Ca2 = Xc1 C a2 ,c1 + Xc2 C a2 ,c2

(39)

For common ion Bi coefficient is calculated from Eq. (42):

Ba1 = Xc1 B a1 ,c1 + Xc2 B a1 ,c2

(42)

Also Ci parameter for cations is obtained as below

Cc1 = Xa1 C c1 ,a1 = C c1 ,a1

(43)

Cc2 = Xa1 C c1 ,a2 = C c1 ,a2

(44)

And Ci common ion is calculated as below

Ca1 = Xc1 C a1 ,c1 + Xc2 C a1 ,c2

(45)

B and C parameters are the adjustable parameters for individual ion in one electrolyte solution. At low pressure, the vapor
pressure of water is calculated by

, N: number of experimental data point.

Pw = aw P w

and
Ci =

Ba1 = Xc1 B a1 ,c1 + Xc2 B a1 ,c2

Xl C i,l

(29)

where the summation runs over all centurions present in the

solution. Note that the fraction Xl , xl in the above equation is
defined as
ml
xl = 
(30)
k mk
xl
Xl = 
k xk

(31)

A multi-electrolyte solution without a common ion is considered

with a1 , c1 for first electrolyte and a2 , c2 for second electrolyte.
Bi parameter for c1 , c2 cations in electrolyte solution are calcu-

(46)

where Pw and P w are the vapor pressures of the aqueous

solutions and pure water at the same temperature, respectively.
Table 3 shows the average absolute deviation (100) of the predicted vapor pressure in a temperature range from 298.15 to
Table 3
Prediction of vapor pressures of aqueous two-electrolyte solutions systems
System

I (mol/kg)

T ( C)

100

Reference

NaClKCl
NaBrKBr
CaCl2 NaCl

0.9670.315
1.3624.033
1.1132.358

2570
2570
2570

40
40
40

4.543
5.092
5.651

[27]
[27]
[27]

1
N

 |pexp pcal |
i

exp

pi

, N: number of experimental data point.

70

G.R. Pazuki, A.A. Rohani / Fluid Phase Equilibria 242 (2006) 6571

P w
ri
T
Xi
zi

Fig. 4. Experimental and calculated vapor pressures of aqueous two-electrolyte

solutions.

343.15 K. The accurate estimation of the vapor pressures of mixture of electrolyte solutions explains that the activity coefficients
of individual ions estimated by this model were reliable. Fig. 4
shows that there is good agreement between experimental and
calculated vapor pressure of water in multi-electrolyte solutions.
5. Conclusion
A new model for calculating the activity coefficients of individual ions in the single electrolyte was proposed. The binary
interactions of this model for each ion were calculated by fitting the experimental activity coefficient data in literature. This
model could accurately correlate the activity coefficients of individual ions. Using these parameters for activity coefficients, the
vapor pressure of water in a mixture of electrolytes can be predicted. The predictions are acceptable with in a wide range of
temperatures.
List of symbols
A
DebyeHuckel constant in molality base
Ax
DebyeHuckel constant in mole fraction base
ai
activity of ion i
aw
activity of water
BD
DebyeHuckel constant in molality base
Bi
adjustable parameter
Ci
adjustable parameter
e
unit charge (1.602 1019 C)
hiw
interaction parameter between ion i and solvent
molecule
I
ionic strength on molality scale
Ix
ionic strength on mole fraction scale
k
Boltzmann constant (1.3805 1023 J K1 )
m
molality of solution (mol kg1 )
mi
molality of ion i (mol kg1 )
Mw
molecular weight of water (g mol1 )
N
number of experimental data point
ni
moles of ion i (mol)
nw
moles of water (mol)
Pw
vapor pressure of aqueous solution (Torr)

vapor pressure of pure water (Torr)

distance between ion and water
temperature (K and C)
mole fraction of ion i
absolute charge number of ion i

Greek symbols

proportional factor

activity coefficient
iw
electrical potential between ion i and solvent molecule

average absolute deviation

average absolute relative deviation

parameter of Eq. (6)

dipole moment

parameter of Eq. (5)

stoichiometric number of ions

+
stoichiometric number of cations

stoichiometric number of anions

size parameter

objective function

osmotic coefficient
iw
dimensionless electrical potential between ion i and
solvent molecule
Subscripts
i
ionic species
(x)
value pertaining to a mole fraction scale of composition
w
water or solvent
+
cation

anion

mean ionic
Superscripts
reference state
cal
calculated
exp
experimental
LR
long-range
SR
short-range

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