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Chinese J . Chem. Eng.

, 14(4)494-504

(2006)

Prediction of Activity Coefficients for Mixed Aqueous Electrolyte


Solutions from the Data of Their Binary Solutions*

a)",

LIU Zhkhang(2q& )", LIU Yansheng(34%%)", HU Yufeng(m E&$)",ZENG


**, Peng( $$
FAN Shuanshi($!&$RJ)~ and LIANG Deqing(%& %)b

a State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research
Laboratory, China University of Petroleum, Beijing 102200, China
Laboratory of Gas Hydrates & High-Pressure Fluids, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 5 10070, China

Abstract

The simple equation relating the activity coefficient of each solute in mixed electrolyte solution to its
value in binary solutions under isopiestic equilibrium was tested by comparison with the experimental data for the
18 electrolyte solutions consisting of 1:1, l:2, and 113 electrolytes. The isopiestic measurements were made on the
quaternary system BaC12-mBr-NaI-H20 and its ternary subsystems N a I - m B r - H 2 0 , NaI-BaC12-H20, and
N&Br-BaCl2-H2O at 298.15K. The results were used to test the applicability of the Zdanovskii's rule to the mixed
electrolyte solutions which contain no common ions, and the agreement is excellent. The activity coefficients of the
solutes in the above quaternary and ternary systems calculated from the above-mentioned simple equation are in
good agreement with the Pitzer's equation.
Keywords electrolyte solution, activity coefficient, isopiestic measurement, the Zdanovskii's rule, the Pitzer's equation

1 INTRODUCTION
The Zdanovskii's rule"' received wide and
growing attenti~n'~'~'.
his relation is the most simple
equation relating the molality of mixed electrolyte
solution to those of its binary subsystems of equal
water activity. It was first discovered empirically by
Zdanovskii for ternary unsaturated electrolyte solutions under isopiestic equilibrium and was derived
from the semi-ideal solution theoryf2].Now the rule
has been experimentally extended to unsaturated
aqueous solutions of electrolytes and nonele~trolytes'~'
and the solutions of water-soluble polymer^'^'. Up to
now extensive experimental tests of the Zdanovskii's
rule have been reported. However, these tests were in
general limited to ternary aqueous solutions or the
quaternary solutions with common ions. On the other
)
hand, the activity coefficient of either solute (
in mixed aqueous electrolyte solution MIX, -. .. MjXi-A1(H20)can be determined from those ( GlX,
)

of their binary subsystems MIX,-AI(H~O)(I=1,2;.-,i)


of equal water activity by[133.61

Eq.( 1) has been coupled either with the thermodynamic relations or with the Eyring's absdute rate theory to establish the novel predictive equations for the
of the
thermodynamic proper tie^'^-'^] and vis~osity"~'
mixed solutions, which are now among the most simple equations for prediction of the thermodynamic and
transport properties of multicomponent solutions from
the properties of their binary subsystems of equal water activity. However, up to now Eq.(l) has not been
checked by comparing with the experimental results.
Accurate and extensive thermodynamic (activity,
volumetric properties, thermal properties, and surface
tension) and transport (viscosity) properties of concentrated mixed electrolyte solutions are required for
the research and the reliable design of many industrial
processes"6-201. However, while the extensive experimental data of binary aqueous electrolyte solutions
have been reported, relatively few measurements have
been made for the mixed electrolyte solutions. It is
thus interesting and practically important to test Eq.(1)
so as to make use of the available information on the
binary electrolyte solutions and provide sufficiently
accurate predictions for the mixed electrolyte solutions.
Therefore, in this study the isopiestic measure-

Received 2005-07-04, accepted 2006-03- 17.


Supported by the National Natural Science Foundation of China (No.20476059, No.20276037) and 863 Hi-Technology Research and Development Program of China (2004 AA616040).
** To whom correspondence should be addressed. E-mail: huyf@cup.edu.cn

Predictionof Activity Coeficients for Mixed Aqueous Electrolyte Solutions from the Data of Their Binary Solutions 495

ments were made on BaC12-mBr-NaI-H20 and its


ternary subsystems NaI--r-H20,
NaI-BaC12-H20,
and NHJ3r-BaC12-H20 at 298.15K. The results were
used to test the applicability of the linear isopiestic
relation to the electrolyte solutions which contain no
common ions. At the same time Eq.(l) was tested by
comparison with the experimental results reported in
the literature and then was used to provide the activity
coefficients of the solutes in the above quaternary and
ternary systems, which were also compared with the
Pitzer's e q u a t i ~ n [ ~ ' - ~ ~ ] .
2 EXPERTMENTAL
All the chemicals used in this study were reagent
grade, and were recrystallized twice from doubly distilled water. NaI and m
r were dried under vacuum
over anhydrous CaC12 for 7d at 423K. BaC12 was dehydrated in an anhydrous HC1 atmosphere at a pressure less than lOlkPa rising from 298.15K to 573K
and then treated by introducing purified argon at 573K.
Finally, all the chemicals were stored over P205 in a
vacuum desiccator before use.
The isopiestic apparatus and the sample cups
used in this study are identical to those of our previous
stUdies[2,14,24-291. The experimental procedure used for
the present systems is also similar to that used previously and is described briefly as follows.
To prepare the samples for easy equilibration, the
binary aqueous solutions of NaI, m B r , BaCl:! were
first made with approximately the same water activity
by direct weighing of water and each of these solutes.
Next, each of the ternary and quaternary solutions was
prepared by mixing these binary solutions. For each
equilibration there were duplicate cups of the samples
investigated. Before each run, 1.5 to 2.0g of the initial
solution was weighed into each sample cup. After
evacuating and degassing through two large vessels
placed between the air pump and the apparatus, the
apparatus was placed into a thermostat controlled at
T=(298.15*.01)K. These physically isolated solutions of two and more components of known initial
concentrations and known initial masses were then
allowed to equilibrate isothermally by transferring
water through a common vapor phase. During the
whole experimental process, the apparatus was rocked
once every 5s in the thermostat. At equilibrium, a lid
was slowly lowered and pressed on to all the cups
within the apparatus. The apparatus was opened and
then replaced to the bracket in the same thennostat. At

isopiestic equilibrium, all the test solutions have the


same water activity. The preliminary experiments
showed that equilibration could be achieved within 3
to 4d. The equilibration period for each run was then
chosen as 5 to 6d. The results reported in this study for
each sample were the average between the duplicate
cups for solute and the results are reproducible to
+0.05%.

3 RESULTS AND DISCUSSION


The Zdanovskii's rule"'21 for mixed solutions can
be written as
i

where a and rn denote activity and molality (mol-kg-l),


respectively. In this study the experimental deviation
from I%+( 1) is defined by

at constant activities of water and within the range


(mMfXf /mLfXf

Under

for M,X, -

and

the

boundary

where

- -.-M,x, -A, (H,O) ,

vMIXf~~fX,/(l-vMfXfx~fXf)

condition

'MIXl xLIX,

= vMfXl

%lIXl

+o

/(

vMfXf n&Xf

rill )] for

-I-

its sub-systems MIX, - A, (H,O) , there follows

where the superscript d denotes the infinite dilute behavior mentioned above. Integration of Eq.(4) from

pi, to

PA,

gives

(pA, = const.)
Chinese J. Ch. E. 14(4) 494 (2006)

Chinese J. Ch. E.(Vol. 14, No.4)

4%

It can be shown that, if the ideal system


M 1X 1
Mixi-A, (H,O) is prepared by mixing
-

its ideal sub-systems MIXI - A, (H,O)


mole

fraction

of

A,

then

of equal

xAl = xil

vM,X,x&,X,

=l-xA,

=~vMrX,xM,Xr

,and

I =1

I=l

we can obtain
-d

estimated which enables

(pAI
=const.

was tried until the relation vBrn:% =vc$qc was


satisfied.
( 3 ) Insert the rn&xi thus obtained into Eq.(9) to
&lX,(exp),

which can be inserted

into Eq.(1) or the Pitzers equation[231to provide the


activity coefficients ( yMlx,) of the solutes in the

vM,X, xM,X,

solved by Eq.(2).

Then, the values v,m;%


and vcm& were calculated by using the osmotic data (ql)in binary solutions[441,where v denotes the salt stoichiometric coefficient. If v,rn;% #vCm&pc, a new value of rn;

yield the value of


=RTIn

4 to be

(6)

From Eqs. ( 5 ) and (6), we obtain the following equations and Eq.(l).

mixed solution of given mB and % .


(4)Compare the predictions with the experimental data. In this article, the average absolute differences between the predicted and measured data over
the entire experimental composition range of the
mixed solutions,A T , was defined by

AT

I=,

(10)

where N is the number of experimental data. For convenience, A: and A: are used to denote the aver-

In this work, the experimental activity coefficients of the electrolytes in 18 ternary systems[ 3 0 4 3 ]
and in the binary subsystems reported in the literature
at 298.15K were used to test the predictive capabilities
of Eq.(l) and the Pitzers equation231.The test procedure is briefly described as follows:
(1) Represent the experimental data of the activity coefficients of each examined electrolyte in the
binary aqueous solutiona1 by the following polynomial:
n

k=O
b

where rnMIX,and yM,XI(exp)denote rnolality and activity coefficient of the electrolyteM,X, in MIX, - H,O .
The optimum fit was obtained by increasing k until the
resulting polynomials is accurate to a few parts in lo4.
The number of Ak needed for a binary solution usually
ranges from 3 to 6.
(2) Determine the compositions of the binary
sub-systems ( rng and rn; ) which have the same water
activity as that of a ternary solution of given molalities

m, and m c . A first approximate value of rn; was


August, 2006

age absolute deviations of Eq.(l) and the Pitzers


equation from the experimental results.
Table 1 shows AT for 18 electrolyte systems at
298.15K. The examined systems are (1) four 111
electrolyte mixtures including NaCl-KCl-H20, NaC1LiCl-HzO, NaCl-NaN03-H20, and NaC1-NaC104-H20;
(2) eleven 1:2 electrolyte mixtures including NaC1BaC12-Hz0, NaCl-CaClZ-HzO, NaC1-MgCI2-H20,
NaCl-MgC12-H20, HC1-BaClZ-HzO, HCl-CaC12-HZ0,
HCl-CoC12-H20, HCl-SrC12-HZ0, HCl-MnClZ-HzO,
HBr-CaBrlz-HzO, and HBr-MgBr2-H20; (3) two 1:3
electrolyte mixtures, i.e., HCl-LaC13-H20, and HClSmC13-H20; (4) one 1:4 electrolyte mixture HC1-ThCk
H20. It is clear that 0.0022 < A: -i 0.0176 and

0.0019 < A; d 0.0289 for all the examined systems,


indicating that Eq.( 1) agrees well with the experimental results30431 and with the Pitzers equation[231
(without use of the mixing parameters).
Table 2 shows the isopiestic results for the ternary systems NaI-NWr-HzO, NaI-BaC12-Hz0, and
N&Br-BaC12-H20 at 298.15K. It can be seen from the
last column of Table 2 that (A(d 0.0018 for all these
systems, indicating that Eq.(2) is in good agreement

Predictionof Activity Coefficients for Mixed Aqueous Electrolyte Solutionsfrom the Data of Their Binary Solutions 497
Table 1 The values of the

functions for the 18 ternary electrolyte solutions at 298.15K

NaCl-KC1-H20

0.0172

NaCI-LiCl-H20

1,

Ref.

0.0190

4.2

1301

0.0102

0.0115

3.0

1311

NaCl-NaNOS-H20

0.0043

0.0043

3.0

1321

NaCl-NaC104-H20

0.0176

0.0225

3.2

1321

NaCl-BaC12-HZO

0.0040

0.0209

5.0

NaCl-CaC12-HZO

0.0032

0.0082

1.2

NaC1-MgC12-H20

0.0041

0.0059

5.2

NaC1-SICl2-H20

0.0025

0.0090

3.0

HC1-BaCl2-H20

0.0134

0.0129

2.0

HC1-CaCl2-H20

0.0117

0.0108

4.8

HCI-CoC12-H20

0.0022

0.0107

2.0

HCl-SrC12-H20

0.0050

0.0085

4.0

HCl-MnC12-H20

0.0058

0.0081

2.5

HBr-CaBrz-HzO

0.0069

0.0156

2.0

HBr-MgBr2-H20

0.0051

0.0120

2.5

HC1-LaCl3-H20

0.0165

0.0289

3.0

I4OA11

HCI-SmCI3-H20

0.0028

0.0019

2.5

1421

System

HCl-ThCb-HZO
0.0042
0.0106
1.o
[431
Note: The superscripts H and P indicate that the activity coefficients were calculated from Eq.( 1) and the Pitzers equation, respec-

and a denote cation and anion, and the term F is defined by F = -A@

A = 0.392

. The

function Z is defined by

Z = 2 x m M Z M. The parameters Bm

and

BA

are defined by

BM, = fl;;

f( x )

= -2

+&;

b-[

f (qd2) and

BLx = f l ~ f 8 ( q Z 1 / ) ) / 1

with

al = 2

f ( x ) = 2[1-(l+~)e-~]/x~ ,

and

l+x+0.5x2

with the experimental results. Therefore, the activity


coefficients of each examined electrolyte in the systems were calculated by Eq.(l).It is evident that the
results, shown in the eighth and ninth columns of
Table 2, agree well with those calculated using the
Pitzers equation and the Pitzer parameters evaluated
by Kim and F r e d e r i ~ [ ~ -(without
~~
using the mixing
parameters).
Table 3 shows the isopiestic results for the quaternary system NaI-N&Br-BaC12-H20 at 298.1%.
The results from the last column of Table 3 show that
IAI d 0.0021 over the whole experimental composi

tion range, indicating that Eq.(2) is in good agreement


with the isopiestic measurements. Therefore, the activity coefficients of each examined electrolyte in the
system were also calculated by using &.( 1) and the
values of Y;,~, of the binary subsystems NaI-H20,
NH4Br-H20,and BaC12-H20. The results, represented
in Table 3, also agree well with those calculated using
the Pitzers equation and the Pitzer parameter^[^^-^^]
evaluated using the water activities of the above binary subsystems and those of the systems NH4I-H20,
NaBr-H20, NaCl-H20, NH4Cl-H20, BaBr2-H20, and
BaIz-H20 (without using the mixing parameters).
Chinese J. Ch. E. 14(4) 494 (2006)

498

Chinese J. Ch. E. (Vol. 14, No.4)


Table 2 Isopiestic results for the ternary systems B-C-HzO (A1) at 298.15K

0.2252

0.4365

0.6760

0.8855

1.0006

1.4906

2.0007

2.5560

3.0680

August, 2006

0.23 12

0.4575

0.7222

0.9599

1.0928

1.6760

2.3162

3.0607

3.8043

0.0521

0.1777

0.1006

0.747

0.710

0.732

0.734

0.714

0.713

0.0002

0.1280

0.736

0.738

0.718

0.717

0.0001

0.1506

0.0767

0.740

0.742

0.722

0.722

O.OOO4

0.1985

0.0274

0.745

0.746

0.726

0.726

O.oo00

0.1225

0.3292

0.701

0.703

0.669

0.668

0.0003

0.1946

0.2536

0.706

0.708

0.675

0.674

0.0002

0.2915

0.1522

0.714

0.715

0.681

0.680

0.0005

0.3760

0.0637

0.720

0.721

0.688

0.687

0.0006

0.1436

0.5684

0.687

0.687

0.640

0.640

-0.0005

0.2918

0.4104

0.696

0.694

0.650

0.648

-0.0001

0.4260

0.2672

0.706

0.705

0.658

0.656

0.5525

0.1313

0.715

0.714

0.667

0.664

0.2012

0.7422

0.685

0.684

0.627

0.626

O.OOO4

0.3627

0.5675

0.695

0.693

0.636

0.634

O.OOO8

0.5019

0.4 160

0.704

0.702

0.644

0.641

0.0002

0.6986

0.2019

0.718

0.715

0.657

0.652

-0.0007

0.2569

0.8119

0.689

0.685

0.624

0.622

-0.0003

0.3466

0.7134

0.695

0.69 1

0.629

0.626

-0.0008

0.6012

0.4349

0.711

0.707

0.643

0.638

-0.0012

0.8187

0.1990

0.723

0.72 1

0.655

0.650

0.0003

0.3426

1.2921

0.703

0.694

0.609

0.607

0.0008

0.5865

1.0169

0.716

0.709

0.621

0.617

0.0002

0.8915

0.6748

0.733

0.728

0.635

0.630

0.0007

1.2006

0.3244

0.753

0.749

0.653

0.645

-0.0010

0.5582

1.668 1

0.738

0.724

0.611

0.607

-0.0008

1.0568

1.0921

0.764

0.756

0.632

0.626

-0.0003

1.3650

0.7380

0.781

0.776

0.647

0.639

1.7682

0.2687

0.806

0.804

0.668

0.658

-0.0002

0.7162

2.2016

0.781

0.763

0.615

0.610

-0.0005

1.2667

1S405

0.812

0.798

0.639

0.631

-0.0011

1.8259

0.8715

0.845

0.838

0.665

0.654

-0.0009

2.2218

0.3996

0.869

0.867

0.684

0.672

-0.0002

0.8988

2.6947

0.830

0.812

0.622

0.619

0.0013

1 S267

1.9146

0.867

0.855

0.649

0.643

0.OOOY

2.0009

1.3251

0.897

0.889

0.672

0.663

0.0005

0.725

0.723

0.730

0.736

0.770

0.821

0.892

0.972

0.661

0.632

0.616

0.610

0.594

0.587

0.586

0.587

0.0001
-0.OOO9

0.0009

Prediction of Activity Coefficientsfor Mixed Aqueous Electrolyte Solutions from the Data of Their Binary Solutions 499

Table 2 (Continued)

3.3658

4.2684

0.943

0.942

0.706

0.693

0.0012

0.878

0.863

0.638

0.635

0.0015

1.8376

0.921

0.910

0.669

0.662

O.OOO6

2.5012

1.1041

0.959

0.955

0.697

0.686

0.0018

3.0186

0.4433

0.999

0.997

0.726

0.710

0.0007

0.657

0.660

0.465

0.467

O.oo00

2.6862

0.4780

1.2589

2.6783

1.9188

1.027

0.588

NH.+Br(B)-BaC12(C)-H2O(A,)
0.2569

0.5122

0.8360

1.1258

1.3602

1.8180

2.5558

2.8591

0.1865

0.3632

0.5769

0.7592

0.9007

1.1628

1.5556

1.7104

0.702

0.456

0.0589

0.1438

0.1009

0.1133

0.666

0.671

0.471

0.477

O.OOO1

0.1522

0.0760

0.677

0.687

0.480

0.490

0.0002

0.1991

0.0420

0.688

0.693

0.487

0.500

o.oO05

0.1267

0.2733

0.624

0.63 1

0.421

0.425

-0.OOO1

0.2170

0.2091

0.63 1

0.637

0.426

0.434

-0.OOO6

0.3065

0.1460

0.637

0.650

0.430

0.439

0.4820

0.0213

0.65 1

0.653

0.440

0.451

0.1864

0.4487

0.606

0.619

0.401

0.405

0.0008

0.2989

0.3709

0.609

0.620

0.403

0.410

O.OOO5

0.4368

0.2755

0.613

0.623

0.406

0.415

0.0001

0.6802

0.1072

0.620

0.624

0.410

0.423

0.3136

0.5480

0.603

0.620

0.397

0.402

O.OOO4

0.5890

0.3625

0.605

0.622

0.398

0.412

0.oOCn

0.6961

0.2899

0.606

0.617

0.399

0.415

0.0002

0.9152

0.1426

0.607

0.613

0.400

0.419

O.oO08

0.3767

0.6521

0.603

0.622

0.397

0.403

0.0010

0.6025

0.5022

0.603

0.625

0.397

0.408

0.0005

0.903 1

0.3020

0.602

0.615

0.397

0.415

10.2024

0.1047

0.601

0.611

0.396

0.420

0.0002

0.4289

0.8887

0.611

0.628

0.405

0.409

0.0002

0.8129

0.6439

0.605

0.620

0.401

0.411

o.OOO9

1.2268

0.3795

0.599

0.611

0.397

0.413

0.0012

1.5896

0.1467

0.594

0.600

0.394

0.417

O.OOO5

0.6360

1.1701

0.627

0.640

0.424

0.429

0.0010

1.0259

0.9321

0.618

0.637

0.419

0.430

0.0006

1.5552

0.6114

0.606

0.622

0.410

0.434

0.0015

1.9185

0.3898

0.599

0.614

0.405

0.437

0.0012

0.8107

1.2282

0.631

0.650

0.433

0.436

0.0016

0.653

0.623

0.608

0.601

0.592

0.586

0.586

0.4 15

0.398

0.396

0.398

0.409

0.435

0.448

0.0003
-0.0002

-0.OOO6

-0.0007

Chinese J. Ch. E. 14(4) 494 (2006)

500

Chinese J. Ch. E. pol. 14, No.4)

Table 2 (Continued)

1.6250

0.7408

0.612

0.629

0.419

0.430

0.0015

2.003 1

0.5131

0.604

0.621

0.414

0.437

0.0006

2.3680

0.2953

0.596

0.606

0.409

0.442

0.0009

0.675

0.684

0.459

0.463

0.0002

NaI(B)-BaCl2(C)-H2O(A1)
0.2825

0.5086

0.7660

1.0168

1.3267

1.8922

2.3670

0.2112

0.3795

0.5689

0.7505

0.9696

1.3575

1.6809

0.0652

0.1625

0.0985

0.I377

0.683

0.691

0.465

0.472

0.0005

0.1586

0.0928

0.700

0.716

0.476

0.484

0.0009

0.2258

0.0423

0.721

0.730

0.490

0.502

-0.0005

0.1360

0.2778

0.666

0.680

0.425

0.431

-0.0006

0. I987

0.23 13

0.674

0.687

0.43 1

0.436

0.0001

0.3291

0.1343

0.693

0.707

0.443

0.453

0.0009

0.4369

0.0533

0.712

0.7 19

0.455

0.471

0.2126

0.4114

0.700

0.720

0.410

0.418

0.0007

0.3560

0.3046

0.684

0.701

0.419

0.428

0.0001

0.491 9

0.2040

0.697

0.716

0.428

0.437

0.0008

0.6022

0.1222

0.708

0.721

0.433

0.450

0.0010

0.2568

0.5613

0.682

0.701

0.406

0.414

0.0005

0.5285

0.3597

0.701

0.715

0.418

0.430

0.7760

0. I786

0.717

0.730

0.427

0.447

0.0012

0.865 1

0.1116

0.725

0.735

0.432

0.453

-0.0005

0.3160

0.7397

0.705

0.726

0.409

0.41 8

0.001 1

0.6087

0.5253

0.719

0.746

0.417

0.430

0.0006

0.8855

0.3233

0.733

0.752

0.425

0.448

0.0009

1.2036

0.0915

0.749

0.758

0.434

0.461

0.0016

0.4289

1.0510

0.763

0.780

0.427

0.440

0.0009

0.8885

0.7217

0.777

0.800

0.434

0.452

0.0012

1.0266

0.6217

0.78 1

0.802

0.437

0.460

0.0005

1S298

0.2624

0.796

0.819

0.445

0.465

0.001 8

0.5669

1.2793

0.824

0.843

0.452

0.463

0.0006

1.2852

0.7697

0.834

0.851

0.460

0.480

0.0009

1.6915

0.4826

0.848

0.864

0.465

0.482

0.0017

2.1589

0.1505

0.859

0.876

0.47 1

0.491

0.0016

0.738

0.723

0.726

0.737

0.757

0.809

0.866

0.447

0.4 13

0.399

0.396

0.40 1

0.420

0.445

-0.0006

-0.0009

Note: The superscripts H and P indicate that the activity coefficients were calculated from Eq.(1) and the Pitzer's equation, respectively

August, 2006

Prediction of Activity Coefticientsfor Mixed Aqueous Electrolyte Solutions from the Data of Their Binary Solutions 501
Table 3 Isopiestic results for the quaternary system NaI(B)-NH.@r(C)- BaCl2(D)-H20(A1) at 298.15K

0.3160

0.734

0.3275

0.684

0.2362

0.440

0.05 12

0.0481

0.1633

0.673

0.682

0.651

0.642

0.452

0.45 1

0.0005

0.0613

0.1060

0.1140

0.685

0.694

0.663

0.655

0.460

0.456

0.0002

0.1506

0.0582

0.08 18

0.700

0.710

0.676

0.668

0.470

0.476

0.0005

0.4265

0.726

0.4466

0.663

0.3186

0.423

0.0993

0.1106

0.1656

0.676

0.690

0.646

0.637

0.440

0.437

0.0001

0.1265

0.1927

0.0866

0.689

0.699

0.659

0.650

0.449

0.442

-0.0002

0.2122

0.0856

0.0988

0.694

0.702

0.663

0.652

0.452

0.461

-0.OOO6

0.6522

0.723

0.6956

0.6.34

0.4855

0.403

0.1509

0.1492

0.2690

0.670

0.680

0.627

0.620

0.417

0.412

O.oo00

0.1706

0.3165

0.1378

0.680

0.691

0.636

0.627

0.423

0.409

O.OOO4

0.3410

0.1250

0.1440

0.691

0.703

0.647

0.638

0.430

0.44 1

-0.0008

0.7680

0.726

0.8259

0.624

0.5704

0.399

0.2316

0.2007

0.2598

0.678

0.690

0.627

0.615

0.4 15

0.410

o.oO01

0.2568

0.4270

0.0853

0.687

0.696

0.635

0.626

0.420

0.409

0.0009

0.3688

0.2115

0.1509

0.691

0.700

0.639

0.632

0.423

0.427

0.0008

1.0028

0.736

1.0953

0.610

0.7405

0.396

0.2819

0.2501

0.3627

0.686

0.699

0.621

0.618

0.409

0.400

-0.0007

0.2762

0.5255

0.1814

0.687

0.697

0.622

0.610

0.410

0.396

0.0002

0.5360

0.2006

0.2094

0.702

0.716

0.636

0.623

0.419

0.428

o.oO05

1.4858

0.770

1.6701

0.594

1.0800

0.405

0.4485

0.4300

0.4770

0.718

0.736

0.622

0.637

0.411

0.396

0.0010

0.4063

0.8182

0.2550

0.712

0.728

0.617

0.596

0.408

0.394

-0.0005

0.7716

0.4603

0.2218

0.73 1

0.743

0.634

0.615

0.419

0.417

0.0003

Chinese J. Ch. E. 14(4) 494 (2006)

502

Chinese J. Ch. E. (Vol. 14, No.4)

Table 3 (Continued)

2.0007

0.821

2.3162

0.587

1.4311

0.425

0.6198

0.5812

0.6305

0.765

0.781

0.634

0.625

0.425

0.418

0.00 13

0.5460

1.0023

0.4230

0.752

0.768

0.623

0.640

0.418

0.427

0.0012

1.1628

0.5766

0.2439

0.780

0.796

0.646

0.658

0.434

0.440

0.0006

2.4860

0.882

2.9637

0.586

1.7632

0.452

0.8264

0.8037

0.7016

0.8 17

0.834

0.647

0.633

0.446

0.425

0.0015

0.8591

1.5829

0.2136

0.796

0.803

0.629

0.643

0.433

0.448

0.0008

1.6259

0.5167

0.3060

0.843

0.861

0.667

0.687

0.460

0.48 1

0.0021

Note: The superscripts H and P indicate that the activity coefficients were calculated from Eq.( 1) and the Pitzers equation, respectively.

4 CONCLUSIONS
Based on the results shown in Tables 1-3, the
following conclusions are obtained:
(1) The simple equation symbolized by Eq.(l)
can provide good predictions for activity coefficients
of the electrolytes in mixed electrolyte solutions in
terms of the data of binary constituent solutions.
(2) The Zdanovskiis rule is applicable to the
present ternary and quaternary aqueous electrolyte
solutions which contain no common ions.

NOMENCLATURE
G
Imax
m
N
Vi
X

Y
A

A,
P

coefficient in Eq. (9)


Gibbs free energy
maximum ionic strength
molality, mobkg-
the number of experimental data
salt stoichiometric coefficient
mole fraction
activity coefficient
function defined by Eq.(3)
function defined by Eq.(lO)
chemical potential
osmotic coefficient

v
Superscripts
b
0

pred

binary solution
quantity in binary solutions at the same water activity as that of a mixed solution
predicted quantity

Subscripts
B,C,D

components

August, 2006

exp
i
W

experimental quantity
component index
water

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