Fluid Phase Equilibria 423 (2016) 138e145

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

The ternary and quaternary electrolyte systems: Activity coefficient of

NaCl measured and modeled for NaCl þ C2H5OH þ H2O and
NaCl þ KCl þ C2H5OH þ H2O systems
Maryam Abedi a, Maryam Alamdari Shendi b, Zohreh Karimzadeh a, *,
Rahman Salamat-Ahangari b, Farzad Deyhimi 1
a
Department of Chemistry, Shahid Beheshti University, Evin-Tehran 1983963113, Iran
b
Department of Chemistry, Faculty of Basic Sciences, Azarbaijan Shahid Madani University, Tabriz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: This work purpose is measuring and modeling of the ternary and quaternary systems consist of NaCl and
Received 19 January 2016 mixed NaClþKCl electrolyte in mixed solvents with different mass fractions (x) of C2H5OH in H2O, where
Received in revised form x ¼ 0.10, 0.20, 0.30, 0.40, and 0.50 and in the molality range of (0.0005e3.0) mol kg1. Based on
23 April 2016
potentiometric measurement technique, the experimental data are obtained. A cell consists of a Naþ-
Accepted 24 April 2016
Available online 28 April 2016
glass membrane and Ag/AgCl electrodes and series of electrolyte solutions, used to calculate the activity
coefficients at (298.15 ± 0.05) K. The quaternary system of mixed NaCl þ KCl electrolyte in mixed
C2H5OH þ H2O solvents is investigated by different molal salt ratios r (r ¼ mNaCl/mKCl ¼ 100, 150, 200 and
Keywords:
Pitzer-Merida et al.
250). Modeling is implemented by using particularly, the Pitzer (P) and modified Pitzer by Merida et al.
Ion-nonelectrolyte interaction (MP) equations. There is a good agreement between the results obtained from both models. The modified
Activity coefficient Pitzer approach by Merida et al. permitted the determination of various binary ion-solvent and ternary
Mixed solvent ion-ion-solvent interaction coefficients which represents complementary data to the usual Pitzer
Mixed electrolyte interaction parameters for modeling the named electrolyte systems.
Potentiometric technique © 2016 Elsevier B.V. All rights reserved.

1. Introduction
The knowledge of the mixed electrolyte thermodynamic prop-
erties, particularly activity coefficients, in aqueous and non-
aqueous solutions is required to investigate the nature of various
ionic interactions in many industrial and environmental processes,
such as desalination, chemical separation, marine chemistry, ge-
ology and environmental aerosol sciences [1e3].
The usual experimental techniques used for these purposes are
vapor pressure or solvent activity methods and potentiometric
measurements. The potentiometric technique using ion-selective
electrodes (ISEs) is found to be an efficient experimental method
for investigation of electrolyte systems. We have previously used in
our laboratory glass membrane [4,5] and solvent polymeric ISE
membranes for modeling different single and mixed electrolyte
systems in aqueous [6,7] and in mixed solvents [8,9]. We have
* Corresponding author.
E-mail address: z.karimzadeh@gmail.com (Z. Karimzadeh).
1
Deceased.
recently made use of the Pitzer (P) and the modified Pitzer (MP)
equations for modeling the ternary system of the NaCl single
electrolyte in mixed CH3OH þ H2O solvent [10] and the quaternary
system of mixed NaCl þ KCl electrolyte in mixed CH3OH þ H2O
solvents. The present work is a continuation of a series of works on
determining the partial properties of sodium chloride in aque-
ousealcoholic solutions through the electromotive force method
[11].
A review of literature showed that, M. A. Esteso et al. investi-
gated NaCl þ C2H5OH þ H2O. They used the Pitzer and chemical
models for modeling the activity coefficients for NaCl in ethanol-
water mixtures containing 20, 40, 60, 70, 80 and 90% ethanol
[12]. Lopes and coworkers determined the activity coefficients of
NaCl in watereethanol solvents, in the range 5e20% (w/w) ethanol,
from emf data in the temperature range 25e50  C. They imple-
mented the Pitzer and PitzereSimonson models to describe the
nonideal behavior of the electrolyte [13]. The ISE measurements in
cells with sodium chloride in watere-ethanol solvents (5e20 wt% of
C2H5OH) at 298.15e323.15 K were approximated using the Pitzer
and Pitzere Simonson (PS) models by Mamontov et al. [14].

http://dx.doi.org/10.1016/j.fluid.2016.04.023
0378-3812/© 2016 Elsevier B.V. All rights reserved.
 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145 139

There is only one published data on the salt activity coefficients the corresponding P equation is written as [1].
for NaCl þ KCl mixed electrolyte in C2H5OH þ H2O mixed solvent.
Activity coefficients of KCl and NaCl were determined in the qua- ln g±NaCl ¼ ln g0±NaCl þ cNaClEtOH mEtOH þ uNaClEtOH m2EtOH
ternary system KCl-NaCl-water-ethanol, for 10 and 20% (w/w)
þ 0:5mEtOH fmCl zEtOHNaCl þ mNa zEtOHNaCl
ethanol in the solvent, from experimental electromotive force data.
The Pitzer-Simonson equations were used to describe the nonideal þ mK zEtOHKCl þ hEtOHNaK g: (1)
behavior of the both electrolytes in the temperature range
20e50 ± C [15]. where
The purpose of this work is modeling of the ternary and qua- n  
g
ternary system of electrolytes in the mixed C2H5OH þ H2O solvent, ln g0±NaCl ¼ f g þ ðmNa þ mCl Þ ð2  y2 Þ BNaCl  B4NaCl
with different alcohol mass fractions x(C2H5OH) in H2O (where    
g g
x ¼ 0.10, 0.20, 0.30, 0.40, and 0.50), by using particularly, the Pitzer þ ð1  y2 Þ 2B4NaCl  BNaCl þ y2 BKCl  B4KCl
(P) and the modified Pitzer (MP) equations [1,16] and based on   h
g
potentiometric measurement technique. Accordingly, the experi- þ 2B4KCl  BKCl þ ðmNa þ mCl Þ 3=2Þ
mental potentiometric data are obtained in this work over the i
electrolyte molality ranging from 0.005 mol kg1 up to about  y2 ÞC4
NaCl
þ y2 C4
KCl
þ y2 ðqNaK þ ð1=2ÞðmNa
3.0 mol kg1, at 298.15 ± 0.05 K, by using a cell containing a Naþ h
þ mCl ÞjNaKCl Þ þ y2 ð1  y2 Þ ððmNa þ mCl Þ
glass membrane and an Ag/AgCl electrodes.
o
 =2ÞjNaKCl :
2. Experimental
(2)
Ethanol of analytical grade (purity >99.5%)) from Fluka is used " #
pffi
as received. The analytical grade NaCl and KCl salts (mass percent g I 2  pffiffi 
fraction >99.5%) are also obtained from Fluka (Table 1). Each time, f ¼ A4 pffi þ ln 1 þ b I : (3)
1þb I b
prior to use, the salts are dried overnight in an oven (at 110  C). All
primary stock solutions are prepared by weight using a Sartorius
CPA225d electronic balance with a resolution of 0.01 mg in doubly 2bð1Þ h pffi  pffi i
Bg ¼ 2 b 1  ea I 1 þ a I  ð1=2Þa2 ðIÞ :
ð0Þ
distilled water. Naþ glass membrane electrode (Model 6.0501.100) þ (4)
a ðIÞ
2
is obtained from Metrohm and AgjAgCl wires are prepared essen-
tially as described elsewhere by electrolysis [17]. Under normal pffi
ð0Þ ð1Þ a I
usage, in our experimental conditions, each Ag/AgCl electrode B4 ¼ b þb e : (5)
lasted about 8 weeks. The experimental cell potentials are recorded
using a Metrohm ion-meter (model 619) with a high input
Cg ¼ ð3=2ÞC4 : (6)
impedance (>1 TX) connected to a Topward multimeter equipped
with a GPIB interface Bus option (model 1304, Taiwan, Korea). The and g± is the molality-scale mean ionic activity coefficient of the
reading potential accuracy of instrumental setup is 0.1 mV A. electrolyte Mnþ Xn ; Z is the charge number of ion; n ¼ nþ þ n is
All measurements are performed under stirring conditions by the number of ions dissociated in one unit electrolyte formula; m is
employing a double-wall container enabling the circulation of the molality of electrolyte (kg mol1); y2 is the solute fraction of
thermostated water from a bath (Julabo thermostat MF12, Ger- KCl; I is the ionic strength on a molality scale; bð0Þ (kg mol1), bð1Þ
many) with temperature kept constant at 298.15 ± 0.05 K. The (kg mol1) and Cf (kg2 mol2 are the parameters of the Pitzer
electrodes and a glass thermometer are immersed in the solution equation; b ¼ 1.2 (kg1/2 mol1/2) and a ¼ 2 kg1/2 mol1/2. Moreover,
through a lid preventing from solvent evaporation. In each mixed qNaK, (kg mol1) and jNaKCl (kg2 mol2) represent the mixing ion-
solvent system and for each molality, data acquisition are per- interaction parameters for mixed electrolyte system. zEtOHNaCl,
formed every 4 s interval and during 20 (for concentrated solu- zEtOHKCl, hEtOHNaK and uEtOHMX are the interaction parameters of
tions) to 60 min (for dilute solutions). From data processing, a nonelectrolyteeioneion and nonelectrolyteenonelectrolyte-ion.
resulting final potential mean value with a standard deviation The Debye-Hückel coefficient for the osmotic coefficient (Af ) is
never exceeding 0.1 mV during 1 min is accepted for each con- defined as
centration. The techniques for reagent preparation and performing
the electrochemical measurements are identical to those described  3=2
1 e2
in Ref. [11]. A4 ¼ ð2p NA rA Þ1=2 : (7)
3 4p εo D kT

3. Method
3
uEtOHNaCl ¼ ðyM mEtOHEtOHNa þ yX mEtOHEtOHCl Þ: (8)
3.1. Pitzer equations for mixed electrolyte (P) yNaCl

For a (1:1) mixture of NaCl and KCl electrolyte in mixed solvent, cNaClEtOH ¼ yNa lEtOHNa þ yCl lEtOHCl : (9)

where constants ε◦, k, NA, D and rA are vacuum permittivity,

Table 1
Company and purity of compounds.
Boltzmann constant, Avogadro constant, dielectric constant and
density of the mixed solvent, respectively. In Eqs. 8 and 9, m and l
Compound Company Mass fraction, purity
are the ternary and binary ion-nonelectrolyte interactions.
Sodium chloride Fluka >99.5% The mixing ionic interaction parameters (qMN and jMNX) can be
Potassium chloride Fluka >99.5% determined according to the Pitzer graphical method [1], based on
Ethanol Fluka >99.5%
the following relations
140 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145

!
     g
y 1 Z  0
Dln g±NaCl ¼ qNaK þ mNa þ mCl  Na  jNaKCl : ln NaCl ¼ cNaClEtOH mEtOH þ cEtOHNaCl mEtOH mNaCl
2yNa mK 2 ZCl goNaCl
0
(10) þ cEtOHKCl mEtOH mKCl þ 0:5mEtOH fmCl zEtOHNaCl
þ mNa zEtOHNaCl þ mK zEtOHKCl þ hEtOHNaK g
y ¼ yNa þ yCl : (11) þ uNaClEtOH m2EtOH :
(16)
 
Dln g±NaCl ¼ ln g±NaCl exp
 ln g±NaCl calc : (12)
where gNaCl is the mean activity coefficient of NaCl in the mixture,
where yM and yX are the salt stoichiometric coefficients, mNa and
goNaCl is the mean activity coefficient of NaCl in the absence of
nonelectrolyte and KCl electrolyte at the same ionic strength,
mCl are the ionic molalities, ZNa and ZCl the cation and anion
charges, and ðln g±NaCl Þcalc related to the corresponding g±NaCl
zEtOHKCl and hEtOHNaK are the ioneion interaction parameter arising
from the presence of KCl, respectively.
values for which qNaK and nNaKCl are zero.

3.3. Potentiometric measurements

The following cells containing a Naþ glass membrane ion-

selective electrode (Naþ ISE) and an Ag/AgCl electrode are used
3.2. Modified Pitzer equation by Merida et al. (MP) for collecting the potentiometric data, for elimination of the
asymmetry potential [18], and for determination of the potentio-
To improve the fitting of experimental data containing polar metric selectivity coefficient (KPot þ þ
12 ) of the Na ISE toward the K
nonelectrolyte, the original Pitzer equation was modified by Merida interfering ions
et al. in order to include the dependence of the binary interaction
  
parameters (containing the nonelectrolyte) on the ionic strength   
AgAgClNaClðm1 Þ; KClðm2 Þ; C2 H5 OHðxÞ; H2 Oð1  xÞNaþ ISE
and the ion-nonelectrolyte interactions on the nonelectrolyte
concentration [16]. (I)

!    
g   
AgAgClNaCl mo1 ¼ m1 þ m2 ; C2 H5 OHðxÞ; H2 Oð1  xÞNaþ ISE
ln NaCl ¼ cNaClEtOH mEtOH þ uNaClEtOH m2EtOH
goNaCl
(II)
þ mEtOH fmx zEtOHNaCl þ mNa zEtOHNaCl g: (13)
  
  
AgAgClKClðm2 Þ; C2 H5 OHðxÞ; H2 Oð1  xÞNaþ ISE (III)
where gNaCl is the mean activity coefficient of NaCl in the presence
of water and ethanol. g0NaCl is the mean activity coefficient of NaCl in
For mixed electrolyte system, the potential of cell (I) can be
the absence of nonelectrolyte, ethanol. In addition, zEtOHNaCl and
expressed as
uNaClEtOH are the ternary interaction parameters of non-
electrolyteeioneion and nonelectrolyteenonelectrolyte-ion,  
E ¼ E0 þ k ln a1 þ KPot
12 a2 : (17)
respectively. In principle, zEtOHNaCl and uNaClEtOH depend on the
ionic strength of the solution.
In Eq. (13), the ionenonelectrolyte binary interaction parameter, a1 ¼ g± m: (18)
zeta and its derivative are expressed as [16].
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

  m¼ m1 ðm1 þ m2 Þ: (19)
ð0Þ ð1;0Þ ð1;1Þ 2
cNaClEtOH ¼ cNaClEtOH þ cNaClEtOH þ cNaClEtOH mEtOH Þ 1
a2 I where E0 represents the cell constant potential, k ¼ (RT/F) is the

ideal Nernstian slope, KPot
12 stands for the potentiometric selectivity
 ð1 þ aI0:5 Þexpð  aI0:5 Þ : coefficient of the Naþ ISE toward the Kþ interfering ions, and g± is
the mean activity coefficient of NaCl in the mixture.
(14)
Using different solutions of interfering ion in mixed solvent, the
potentiometric response of Naþ ISE can be determined by the po-
0 vc tential of cell (III)
cNaClEtOH ¼
vI  
  2  
E ¼ E0 þ k log KPot
ð1;0Þ ð1;1Þ 12 a2 : (20)
¼ cNaClEtOH þ cNaClEtOH mEtOH 1þ 1
a2 I 2
  
1 where the potentiometric selectivity coefficient of the ISE can be
þ aI0:5 þ a2 I exp  aI0:5 : expressed as
2
(15)  
  EE0
1 k
where c(0)NaClEtOH, c(1,0)NaClEtOH, and c(1,1)NaClEtOH are considered as KPot
12 ¼ 10 : (21)
a2
adjustable parameters.
For the quaternary system (NaCl þ KCl þ EtOH þ Water), the If the potentiometric selectivity coefficient of the ISE is negli-
corresponding MP equation is presented as [13]. gible, Eq. (20) is reduced to the Nernst relation
 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145 141

Table 2
Experimental mean activity coefficients (g±) of NaCl electrolyte in different mass fractions of C2H5OH (x ¼ 0.10, 0.20, 0.30, 0.40, and 0.50) in water and the corresponding
potentiometric responses (DE/mV) at Ta ¼ 298.15 K and Pb ¼ 100 kP.

10% 20% 30%

mc(NaCl) DEd/mV g±e(NaCl) m(NaCl) DE/mV g±(NaCl) m(NaCl) DE/mV g±(NaCl)

0.0005 148.0 0.9681 0.0005 145.3 0.9376 0.0005 143.8 0.9722
0.0008 127.5 0.9619 0.0008 124.7 0.9308 0.0008 123.7 0.9643
0.0011 113.2 0.9568 0.0011 110.9 0.9254 0.0010 109.8 0.9578
0.0027 67.9 0.9358 0.0027 66.1 0.9024 0.0026 65.4 0.9308
0.0054 33.7 0.9138 0.0054 32.9 0.8785 0.0052 32.4 0.9026
0.0081 13.9 0.8980 0.0080 13.5 0.8614 0.0079 13.3 0.8824
0.0109 0.0 0.8854 0.0107 0.1 0.8477 0.0105 0.1 0.8663
0.0271 43.9 0.8371 0.0268 42.7 0.7955 0.0262 42.1 0.8045
0.0543 76.5 0.7930 0.0536 74.3 0.7478 0.0524 73.0 0.7478
0.0814 95.4 0.7649 0.0804 92.6 0.7175 0.0786 90.7 0.7117
0.1086 108.7 0.7443 0.1073 105.4 0.6953 0.1048 103.2 0.6852
0.1358 118.9 0.7281 0.1341 115.3 0.6779 0.1310 112.8 0.6645
0.2717 150.7 0.6789 0.2683 145.9 0.6252 0.2621 142.4 0.6015
0.5441 182.8 0.6358 0.5371 176.9 0.5799 0.5247 172.2 0.5472
0.8172 202.1 0.6173 0.8066 195.6 0.5610 0.7876 190.3 0.5240
1.0910 216.1 0.6096 1.0766 209.4 0.5535 1.0508 203.7 0.5139
1.3655 227.5 0.6083 1.6183 230.0 0.5564 1.5784 224.0 0.5135
1.6407 237.1 0.6114 2.1624 246.1 0.5739 1.8428 232.3 0.5194
2.1931 253.3 0.6278 2.4353 253.1 0.5867
2.7483 266.9 0.6548 2.65398 258.431 0.5986
3.0270 273.2 0.6720

40% 50%

m(NaCl) DE/mV g±(NaCl) m(NaCl) DE/mV g±(NaCl)

0.0005 143.9 0.9581 0.0005 144.9 0.9487
0.0008 123.9 0.9492 0.0008 124.4 0.9383
0.0010 109.8 0.9418 0.0010 110.3 0.9299
0.0026 65.5 0.9114 0.0025 65.7 0.8951
0.0052 32.3 0.8795 0.0050 32.4 0.8585
0.0077 13.3 0.8568 0.0075 13.3 0.8324
0.0103 0.1 0.8385 0.0100 0.2 0.8116
0.0258 41.8 0.7692 0.0250 41.7 0.7324
0.0516 72.4 0.7059 0.0500 71.8 0.6604
0.0774 89.8 0.6658 0.0750 88.9 0.6148
0.1031 102.0 0.6365 0.1000 100.7 0.5817
0.1289 111.4 0.6136 0.1250 109.8 0.5558
0.2579 140.3 0.5445 0.2500 137.5 0.4775
0.5161 169.3 0.4851 0.5000 165.0 0.4095
0.7745 187.1 0.4597 0.7500 181.8 0.3789
0.95548 196.625 0.45073 0.8134 185.2 0.3739
0.98135 197.869 0.44984
a
The standard uncertainty in temperature is ±0.01 K.
b
The standard uncertainty in atmospheric pressure value is ±0.01 kP.
c
The standard uncertainty in molality values is ±0.0001 mol kg1.
d
The standard uncertainty in emf value is ±0.01 mV.
e
The standard uncertainty in activity coefficient value is ±0.0001.

1.1
10%
1 20%
0.9 30%

0.8 40%
50%
γ±

0.7

0.6

0.5

0.4

0.3
0 0.5 1 1.5 2 2.5 3 3.5
m / mol.kg-1

Fig. 1. Experimental mean activity coefficients of NaCl electrolyte versus molality in Fig. 2. Mean activity coefficients of NaCl obtained in this work (C), mean activity
different mass fractions (x) of C2H5OH in water, with x ¼ 0, 0.10, 0.20, 0.30, 0.40, and coefficients of NaCl taken from Esteso et al. [12] (D) and, data taken from Lopes et al.
0.50 at T ¼ 298.15 K. [13] ().
142 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145

Table 3
Experimental mean activity coefficients (g±) for NaCl and the corresponding potentiometric responses (DE/mV) at Ta ¼ 298.15 K, for the various molal salt ratio r ¼ m1/m2 of
NaCl(m1) þ KCl(m2) mixed electrolyte in different C2H5OH mass fractions (x ¼ 0.10, 0.20, 0.30, 0.40, and 0.50) in water at Pb ¼ 100 kP.

mc(NaCl)/mol kg1 DEd/mV g±e(NaCl) m(NaCl)/mol kg1 DE/mV g±(NaCl) m(NaCl)/mol kg1 DE/mV g±(NaCl) m(NaCl)/mol kg1 DE/mV g±(NaCl)
10%

r ¼ 100 r ¼ 150 r ¼ 200 r ¼ 250

0.0005 131.8 0.9710 0.0005 147.2 0.9722 0.0005 144.1 0.9722 0.0005 136.0 0.9723
0.0008 112.9 0.9647 0.0007 127.1 0.9663 0.0007 124.5 0.9663 0.0007 117.4 0.9663
0.0011 100.2 0.9597 0.0010 112.9 0.9614 0.0010 110.0 0.9612 0.0010 103.7 0.9612
0.0027 58.6 0.9385 0.0025 67.7 0.9409 0.0025 66.1 0.9409 0.0025 62.4 0.9409
0.0054 27.5 0.9163 0.0050 33.8 0.9194 0.0050 33.1 0.9194 0.0050 31.1 0.9194
0.0081 9.5 0.9005 0.0075 14.2 0.9041 0.0075 13.8 0.9040 0.0075 13.0 0.9041
0.0108 3.3 0.8878 0.0099 0.4 0.8918 0.0100 0.3 0.8917 0.0100 0.3 0.8918
0.0270 43.3 0.8393 0.0248 43.0 0.8445 0.0249 42.2 0.8445 0.0249 39.8 0.8445
0.0540 72.9 0.7951 0.0497 75.3 0.8009 0.0498 73.8 0.8009 0.0498 69.6 0.8009
0.0810 90.1 0.7668 0.0745 93.9 0.7730 0.0746 92.0 0.7730 0.0747 86.8 0.7730
0.1081 102.2 0.7461 0.0993 107.1 0.7525 0.0995 104.9 0.7524 0.0996 99.0 0.7525
0.1351 111.6 0.7299 0.1242 117.2 0.7363 0.1244 114.8 0.7363 0.1245 108.3 0.7363
0.2704 140.5 0.6805 0.2483 148.6 0.6866 0.2488 145.6 0.6865 0.2490 137.3 0.6866
0.5415 169.8 0.6373 0.4967 180.2 0.6423 0.4975 176.5 0.6422 0.4980 166.5 0.6423
0.8133 187.3 0.6189 0.7450 199.1 0.6224 0.7463 194.9 0.6223 0.7470 183.9 0.6224
1.0858 200.2 0.6112 0.9934 212.8 0.6131 0.9950 208.4 0.6130 0.9960 196.6 0.6131
1.3591 210.5 0.6101 1.4901 233.1 0.6111 1.4925 228.2 0.6111 1.4940 215.3 0.6111
1.6331 219.3 0.6135 1.9868 248.5 0.6227 1.9900 243.3 0.6226 1.9920 229.5 0.6227
2.1834 234.1 0.6304 2.4835 261.4 0.6438 2.4876 256.0 0.6436 2.4900 241.5 0.6437
2.7366 246.6 0.6585 2.7318 267.3 0.6574 2.7363 261.699 0.6572 2.7391 246.9 0.6572
3.0144 252.3 0.6762

20%

r ¼ 100 r ¼ 150 r ¼ 200 r ¼ 250

0.0005 145.4 0.9688 0.0005 137.3 0.9686 0.0005 137.3 0.9686 0.0005 137.8 0.9686
0.0007 125.1 0.9620 0.0007 118.4 0.9619 0.0008 118.4 0.9619 0.0008 119.0 0.9619
0.0010 111.0 0.9565 0.0010 105.1 0.9564 0.0010 105.1 0.9564 0.0010 105.6 0.9564
0.0025 66.8 0.9336 0.0025 63.1 0.9336 0.0025 63.1 0.9336 0.0025 63.3 0.9335
0.0050 33.5 0.9096 0.0050 31.6 0.9096 0.0050 31.6 0.9096 0.0050 31.7 0.9095
0.0074 14.3 0.8923 0.0074 13.3 0.8923 0.0075 13.3 0.8923 0.0075 13.4 0.8923
0.0099 0.7 0.8785 0.0099 0.5 0.8785 0.0099 0.5 0.8785 0.0100 0.4 0.8785
0.0248 41.8 0.8256 0.0248 39.9 0.8256 0.0249 39.9 0.8256 0.0249 40.2 0.8257
0.0495 73.3 0.7770 0.0497 69.8 0.7770 0.0498 69.8 0.7770 0.0498 70.2 0.7771
0.0743 91.4 0.7460 0.0745 87.1 0.7460 0.0746 87.1 0.7460 0.0747 87.5 0.7460
0.0990 104.2 0.7231 0.0993 99.2 0.7231 0.0995 99.2 0.7231 0.0996 99.7 0.7232
0.1238 114.1 0.7052 0.1242 108.6 0.7052 0.1244 108.6 0.7052 0.1245 109.1 0.7053
0.2475 144.6 0.6505 0.2483 137.5 0.6505 0.2488 137.5 0.6505 0.2490 138.2 0.6506
0.4950 175.3 0.6025 0.4967 166.6 0.6025 0.4975 166.6 0.6025 0.4980 167.5 0.6026
0.7426 193.7 0.5816 0.7450 184.2 0.5816 0.7463 184.2 0.5816 0.7470 185.1 0.5818
0.9901 207.2 0.5724 0.9934 197.0 0.5723 0.9950 197.0 0.5723 0.9960 198.0 0.5725
1.4851 227.3 0.5718 1.4901 216.1 0.5717 1.4925 216.1 0.5717 1.4940 217.2 0.5720
1.9802 242.9 0.5856 1.9868 230.8 0.5854 1.9900 230.8 0.5854 1.9920 232.0 0.5856
2.2277 249.6 0.5963 2.2351 237.2 0.5960 2.2388 237.2 0.5960 2.2410 238.5 0.5963

30%

r ¼ 100 r ¼ 150 r ¼ 200 r ¼ 250

0.0005 141.0 0.9644 0.0005 139.7 0.9644 0.0005 141.9 0.9643 0.0005 149.1 0.9644
0.0007 121.6 0.9568 0.0007 120.6 0.9568 0.0007 122.4 0.9567 0.0007 128.4 0.9567
0.0010 107.9 0.9504 0.0010 107.1 0.9505 0.0010 108.6 0.9504 0.0010 114.1 0.9505
0.0025 64.8 0.9242 0.0025 64.1 0.9242 0.0025 65.1 0.9242 0.0025 68.3 0.9242
0.0049 32.6 0.8967 0.0050 32.3 0.8968 0.0050 32.7 0.8967 0.0050 34.2 0.8967
0.0074 14.0 0.8770 0.0075 13.8 0.8770 0.0075 13.9 0.8770 0.0075 14.6 0.8770
0.0099 1.0 0.8613 0.0099 0.8 0.8612 0.0100 0.7 0.8612 0.0100 0.7 0.8613
0.0248 39.9 0.8007 0.0248 39.8 0.8007 0.0249 40.5 0.8008 0.0249 42.6 0.8008
0.0495 70.0 0.7451 0.0497 69.6 0.7451 0.0498 70.9 0.7451 0.0498 74.4 0.7451
0.0743 87.3 0.7094 0.0745 86.8 0.7095 0.0746 88.3 0.7095 0.0747 92.7 0.7095
0.0990 99.4 0.6833 0.0993 98.8 0.6833 0.0995 100.5 0.6833 0.0996 105.6 0.6834
0.1238 108.7 0.6627 0.1242 108.1 0.6628 0.1244 110.0 0.6628 0.1245 115.5 0.6628
0.2475 137.5 0.6000 0.2483 136.7 0.6000 0.2488 139.0 0.6001 0.2490 145.9 0.6002
0.4950 166.4 0.5451 0.4967 165.4 0.5452 0.4975 168.2 0.5453 0.4980 176.6 0.5453
0.7425 183.9 0.5211 0.7450 182.7 0.5212 0.7463 185.8 0.5213 0.7470 195.1 0.5214
0.9900 196.8 0.5100 0.9934 195.6 0.5102 0.9950 198.9 0.5103 0.9960 208.8 0.5103
1.4851 216.2 0.5074 1.4900 214.8 0.5075 1.4925 218.4 0.5076 1.4940 229.3 0.5076
1.7326 224.1 0.5120 1.7384 222.7 0.5121 1.7413 226.4 0.5122 1.7430 237.7 0.5122
1.8811 228.4 0.5161 1.8377 225.6 0.5148 1.8408 229.4 0.5148 1.8426 240.8 0.5148

(continued on next page)

 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145 143

40%

r ¼ 100 r ¼ 150 r ¼ 200 r ¼ 250

0.0005 150.7 0.95873 0.0005 150.8 0.9587 0.0005 144.9 0.9585 0.0005 150.4 0.9588
0.0007 130.3 0.95006 0.0007 130.4 0.9501 0.0008 125.2 0.9498 0.0007 129.8 0.9501
0.0010 115.7 0.94281 0.0010 115.8 0.9428 0.0010 111.1 0.9426 0.0010 115.2 0.9428
0.0025 69.4 0.91258 0.0025 69.4 0.9126 0.0025 66.8 0.9125 0.0025 69.1 0.9126
0.0050 35.1 0.88109 0.0050 35.0 0.8810 0.0050 33.7 0.8811 0.0050 34.7 0.8811
0.0074 15.3 0.85855 0.0074 15.2 0.8586 0.0075 14.5 0.8585 0.0075 15.0 0.8586
0.0099 1.4 0.84050 0.0099 1.3 0.8405 0.0099 1.2 0.8406 0.0100 1.1 0.8406
0.0248 41.9 0.77167 0.0248 42.1 0.7717 0.0249 40.7 0.7717 0.0249 42.1 0.7717
0.0495 73.6 0.70875 0.0497 73.9 0.7088 0.0498 71.3 0.7088 0.0498 73.8 0.7088
0.0743 91.7 0.66871 0.0745 92.0 0.6687 0.0746 88.8 0.6688 0.0747 91.9 0.6688
0.0990 104.4 0.63944 0.0993 104.7 0.6394 0.0995 101.1 0.6396 0.0996 104.5 0.6396
0.1238 114.1 0.61655 0.1242 114.5 0.6165 0.1244 110.5 0.6167 0.1245 114.2 0.6167
0.2475 144.0 0.54709 0.2483 144.4 0.5471 0.2488 139.4 0.5473 0.2490 144.1 0.5473
0.4951 174.1 0.48700 0.4967 174.5 0.4870 0.4975 168.4 0.4872 0.4980 174.1 0.4872
0.7426 192.3 0.46085 0.7450 192.8 0.4609 0.7463 186.1 0.4610 0.7470 192.4 0.4611
0.9406 203.5 0.45039 0.9437 204.0 0.4504 0.9453 196.8 0.4505 0.9213 202.2 0.4516

50%

r ¼ 100 r ¼ 150 r ¼ 200 r ¼ 250

0.0005 148.0 0.9516 0.0005 148.9 0.9517 0.0005 151.1 0.9519 0.0005 146.9 146.9411
0.0007 128.3 0.9416 0.0007 128.7 0.9416 0.0007 129.9 0.9414 0.0007 126.7 126.6717
0.0010 113.4 0.9328 0.0010 113.9 0.9329 0.0010 115.1 0.9328 0.0010 112.3 112.2599
0.0025 68.3 0.8978 0.0025 68.6 0.8979 0.0025 69.4 0.8979 0.0025 67.6 67.6093
0.0049 34.9 0.8612 0.0050 34.9 0.8613 0.0050 35.2 0.8612 0.0050 34.3 34.2692
0.0074 15.5 0.8350 0.0075 15.4 0.8350 0.0075 15.6 0.8351 0.0075 15.1 15.0883
0.0099 2.0 0.8142 0.0099 1.9 0.8142 0.0100 1.8 0.8141 0.0100 1.7 1.7164
0.0247 39.9 0.7346 0.0248 40.3 0.7346 0.0249 40.9 0.7346 0.0249 39.9 39.8947
0.0495 70.3 0.6624 0.0497 70.8 0.6624 0.0497 71.8 0.6624 0.0498 70.1 70.0550
0.0743 87.5 0.6167 0.0745 88.1 0.6167 0.0746 89.3 0.6167 0.0747 87.1 87.1332
0.0990 99.5 0.5833 0.0993 100.1 0.5834 0.0995 101.4 0.5833 0.0996 99.0 99.0008
0.1238 108.6 0.5573 0.1242 109.3 0.5574 0.1244 110.8 0.5573 0.1245 108.1 108.0842
0.2475 136.5 0.4788 0.2483 137.3 0.4788 0.2488 139.1 0.4788 0.2490 135.8 135.7593
0.4950 164.3 0.4105 0.4967 165.2 0.4105 0.4975 167.4 0.4105 0.4980 163.3 163.3469
0.7425 181.2 0.3798 0.7450 180.2 0.3798 0.7463 184.6 0.3798 0.7470 180.1 180.1006
a
The standard uncertainty in temperature is ±0.01 K.
b
The standard uncertainty in atmospheric pressure value is ±0.01 kP.
c
The standard uncertainty in molality values is ±0.0001 mol kg1.
d
The standard uncertainty in emf value is ±0.01 mV.
e
The standard uncertainty in activity coefficient value is ±0.0001.

asymmetry potential [18] as shown below

0
E ¼ E þ k lna1 : (22)  2
m01 g1
Using the Nernst relation (Eq. (22)), the potentiometric response DE ¼ EðIÞ  EðIIÞ ¼ klnð Þ  2k lnð Þ: (23)
m1 ðm1 þ m2 Þ go1
of the cells (I) and (II) can be combined for the elimination of

1.1 Table 4
The reported Pitzer ion-interaction parameters for the NaCl, KCl and NaCl þ KCl in
10% 20% water at 298.15 K.
1
Electrolyte þ water b(0) b(1) C4 jNaKCl QNaK Ref
0.9 30% 40%
NaCl 0.0765 0.2664 0.00127 e e [1]
0.8 KCl 0.04835 0.2122 0.00084 e e [1]
50% NaCl þ KCl e e e 0.0018 0.012 [1]
γ±

0.7

0.6
Table 5
0.5 The computed Pitzer ion-interaction parameters (b(0), b(1), C4) in the investigated
system (NaCl þ C2H5OH þ H2O) at 298.15 K.
0.4 C2H5OH b(0) b(1) C4 A4 s mMax Ref

0.3 0.1 0.0852 0.2344 0.0016 0.4337 0.0019 3.027 This work
0 0.5 1 1.5 2 2.5 3 0.0804 0.3047 0.00192 [13]
0.2 0.0968 0.0250 0.0023 0.4877 0.0018 2.653 This work
m / mol.kg-1
0.0842 0.0313 0.00361 [13]
0.0976 0.0264 0.0011 [12]
Fig. 3. Experimental mean activity coefficients of NaCl electrolyte versus molality for
0.3 0.0697 0.3420 0.02052 0.5564 0.0005 1.842 This work
different mass fractions (x) of C2H5OH in water, at T ¼ 298.15 K. The various mass
0.4 0.1341 0.1597 0.0007 0.6437 0.0004 0.981 This work
fractions (x) of C2H5OH (where x ¼ 0.10, 0.20, 0.30, 0.40, and 0.50) are represented by
0.1138 0.4239 0.0068 [12]
different curves in the figure. The lowest value of mass fraction (x ¼ 0.10) appears at
0.5 0.2119 0.0617 0.0565 0.7543 0.0017 0.813 This work
the top and increase to its highest value at the bottom of the figure.
144 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145

Table 6 solvent. We perform least squares analysis of activity coefficients.

The Pitzer mixed ion-interaction parameters (qNaK, jNaKCl) in the investigated qua- The standard deviation values of the fits (s ¼ RMSD), included in
ternary NaCl(m1) þ KCl(m2) þ C2H5OH þ H2O systems, determined according to the
Pitzer graphical method, at 298.15 K.
the Tables, are estimated using the following relation

C2H5OH JNaKCl QNaK 0 11=2

0.l 0.0360 0.0423 P
B n  2 C
i¼1 Fi;exp  Fi;calc C
0.2 0.0237 0.0304 s¼B
B C : (24)
0.3 0.0207 0.0291 @ n1 A
0.4 0.0052 0.0092
0.5 0.0069 0.0116

where Fi is the objective function (activity coefficient) and n is the

In the above relation, g1 is the mean activity coefficient of NaCl
in the mixture in the presence of the non-electrolyte (C2 H5 OH ),
whilego1 is the mean activity coefficient of NaCl in the absence of the
second electrolyte at the same ionic strength and in various mass
fractions of ethanol in mixed solvents [10], respectively.
4. Results and discussions
The obtained experimental mean activity coefficients of NaCl
electrolyte in different mass fractions (x) of C2H5OH in water and
the corresponding potentiometric responses, at T/K ¼ 298.15, are
reported in Table 2 and illustrated in Fig. 1. The comparison of
calculated and reported activity coefficient values for NaCl at mass
fractions of x ¼ 0.20 are also presented in Fig. 2. The calculated data
by Lopes et al. was ranging from 0.1 mol kg1 up to 3.0 mol kg1.
Esteso et al. reported their data from 0.004 to 2.0 mol kg1. Our
values are between 0.0005 and 2.65 mol kg1. Based on the figure,
the experimental mean activity coefficients for investigated system
are in good agreement with reported values.
Also in the case of quaternary (NaCl-KCl-water-ethanol) system,
the potentiometric selectivity coefficient of the Naþ ISE toward Kþ
ion is first determined in cell (III) using pure KCl standard solutions
in various mass fractions of ethanol in water. The results show that
the potentiometric selectivity coefficient of the Naþ ISE is negligible
and does not change significantly in different mixed solvents
4
(K12
Pot ¼ 2.2 10 ± 0.7 104 because of large r values). Therefore,
since in the above experimental conditions, the presence of the
interfering of Kþ on the response of the Naþ ISE is negligible, the
mean activity coefficients of NaCl in the mixture are determined, in
the absence of asymmetry potential [17], using equation (23).
Accordingly, the obtained results at different molal salt ratios r
(r ¼ mNaCl/mKCl ¼ 100, 150, 200 and 250) in mixed solvents and at
T ¼ 298.15 K, along with the corresponding potentiometric re-
sponses in the absence of asymmetry potential are reported in
Table 3 and illustrated in Fig. 3.
The Pitzer (P) equations and the modified Pitzer (MP) equation
by Merida et al. are used in this work for modeling the mean ac-
tivity coefficients of NaCl in NaCl þ C2H5OH þ H2O and
NaCl(m1) þ KCl(m2) þ C2H5OH þ H2O at 298.15 K. For this purpose,
various molal salt ratios r ¼ m1/m2 are used and the experimental
ionic strength range of the mixed electrolyte is varied from 0.0005
up to 3.0 mol kg1. The reference state is ethanol þ water mixed
number of experimental data points.
Firstly, we use the Pitzer equation for pure NaCl in different
C2H5OH þ H2O mixed solvents.
As we found in our previous work [11], including the interaction
parameters between neutral species and ionic species lead to
unsatisfying regression. In fact, in this case as before, we delete all
the explicit interactions parameters
(zEtOHNaCl ; zEtOHKCl ; hEtOHNaK ;uNaClEtOH ;cNaClEtOH ) between neutral
species and ionic species. The obtained ion-interaction parameters
for pure NaCl in different C2H5OH þ H2O mixed solvents are
compared with reported values [12,13] in Table 5.
Although, the Pitzer equation used to modeling of activity co-
efficients of quaternary system, NaCl-KCl-water-ethanol, for
10e50% (w/w) ethanol in the solvent. Nonetheless, different as-
pects of Pitzer formalism are checked in this work as before [11].
Obtained results confirm the previous work results, and corre-
spondingly we use the Pitzer graphical method to evaluate the
mixing ionic interaction parameters (q and j). Different possible
approaches to investigate the P equation are not discussed in fol-
lows. The mixing Pitzer parameters are computed for each per-
centage of mixed solvents.
The Pitzer ion-interaction parameters for pure NaCl in different
C2H5OH þ H2O mixed solvents which calculated in Table 5 are used
in Eq. (10). We insert the evaluated b(0), b(1) and C4 parameters for
pure NaCl in different C2H5OH þ H2O mixed solvents in Eq. (10). The
two and three particles mixing ionic interaction parameters (qNaK
and jNaKCl) for NaCl þ KCl in different used mass fractions of
C2H5OH in water are determined according to the Pitzer graphical
method [1] (see Eq. (10)). According to Table 6, the result shows an
increasing trend of mixing ion-interaction parameters (qNaK and
jNaKCl) with increasing mass fractions (x) of C2H5OH in water.
Secondly, we investigate the MP equation (Eq. 13). Modeling is
implemented for the ternary and quaternary electrolyte systems
(NaCl þ C2H5OH þ H2O and NaCl þ KCl þ C2H5OH þ H2O).
For ternary system, Eq. (13) is used to obtain the binary (c(0),
c (1,0)
and c(1,1)) and ternary (z) ion C2H5OH interaction parameters
in different mass fractions (x) of C2H5OH in water, at 298.15 K. It is
noticeable that a better fit of the experimental mean activity co-
efficients is obtained when u and c(10), put equal to zero. The
optimized parameters are presented in Table 7. As can be seen in
the table, c (1,1) and z show the decreasing trends.
In the case of the quaternary system, Eq. (16) is used to study
NaCl and KCl mixtures in different mass fractions of C2H5OH in

Table 7 Table 8
Binary (c (0)NaClEtOH and c (1,1) NaClEtOH) and ternary (zEtOHNaCl) ion. C2H5OH inter- Binary (c(1,1)EtOHKCl) and ternary (hEtOHNaK and zEtOHKCl) ion. C2H5OH interaction
action parameters of the modified Pitzer (MP) equation for NaCl in different mass parameters of the MP equation for NaCl and KCl mixtures in different mass fractions
fractions (x) of C2H5OH in water, at 298.15 K. (x) of C2H5OH in water, at 298.15 K.

C2H5OH zEtOHNaCl c(0)NaClEtOH c(1,1)NaClEtOH s C2H5OH c(1,1)EtOHKCl hEtOHNaK zEtOHKCl s

0.l 0.0016 0.0381 0.0174 0.002 0.l 0.5456 0.0024 0.1036 0.001
0.2 0.0032 0.0459 0.0090 0.002 0.2 0.1664 0.0142 0.0836 0.001
0.3 0.0003 0.0425 0.0068 0.002 0.3 0.0143 0.0027 0.1102 0.002
0.4 0.0031 0.0477 0.0055 0.001 0.4 0.0303 0.0001 0.1169 0.001
0.5 0.0087 0.0552 0.0051 0.002 0.5 0.0203 0.0003 0.1649 0.001
 M. Abedi et al. / Fluid Phase Equilibria 423 (2016) 138e145
water. The resulted parameters in Tables 4 and 7 for ion-interaction
parameters in the investigated systems (NaCl, KCl and NaCl þ KCl)
in water and ion-neutral interaction parameters of the MP equation
(Eq. 13 of [12]) for NaCl in different mass fractions of C2H5OH in
water (C4, b(1), b(0), jNaKCl, QNaK, c(0)NaClEtOH, c(1,0)NaClEtOH and
c(1,1)NaClEtOH and zEtOHNaCl) are inserted in Eq. (16). c(1,0)KClEtOH is not
taken into account. The optimized parameters are presented in
Table 8. The results show also that the ternary ioneioneCH3OH
interactions (hEtOHNaK and xEtOHKCl), in the presence of the second
electrolyte KCl are not negligible.
Briefly, the modified Pitzer approach by Merida et al. permitted
the determination of various binary ion-solvent and ternary ion-
ion-solvent interaction coefficients which represents complemen-
tary data to the usual Pitzer interaction parameters for modeling
the above electrolyte system.
It might remarkable to note that, due to appearance of ionic
association, bigger mass fraction of C2H5OH in water (x > 50%) are
released.
5. Conclusions
In this work, the ternary and quaternary electrolyte systems
including NaCl þ C2H5OH þ H2O and NaCl þ KCl þ C2H5OH þ H2O
are investigated. The activity coefficient measuring is performed in
mixed solvent with different alcohol mass fractions x (x ¼ 0.10,
0.20, 0.30, 0.40, and 0.50) in water. The mean activity coefficients
modeling for The Pitzer (P) and the modified Pitzer (MP) equations
are both used in this work for NaCl þ C2H5OH þ H2O and
NaCl þ KCl þ C2H5OH þ H2O at 298.15 K. The MP equation and
Pitzer graphical method are generally well presented by the model.
145
Acknowledgements
Dedicated to the memory of Professor Farzad Deyhimi.
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