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, 14(4)494-504
(2006)
a)",
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,
)
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-
Predictionof Activity Coeficients for Mixed Aqueous Electrolyte Solutions from the Data of Their Binary Solutions 495
Under
for M,X, -
and
the
boundary
where
vMIXf~~fX,/(l-vMfXfx~fXf)
condition
'MIXl xLIX,
= vMfXl
%lIXl
+o
/(
vMfXf n&Xf
rill )] for
-I-
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)
4%
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
(pAI
=const.
vM,X, xM,X,
solved by Eq.(2).
4 to be
(6)
From Eqs. ( 5 ) and (6), we obtain the following equations and Eq.(l).
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
Predictionof Activity Coefficients for Mixed Aqueous Electrolyte Solutionsfrom the Data of Their Binary Solutions 497
Table 1 The values of the
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
498
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
500
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
502
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
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
REFERENCES
Zdanovskii, A.B ., Trudy Solyunoi Laboratorii Akud.
Nuuk SSSR. No. 6, 1936.
Hu, Y.F., The thermodynamics of nonelectrolyte systems at constant activities of any number of components,
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ZdanovskiiStokes-Robinson approach, I . Aerosol Sci.,
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Robinson, R.A., Stokes, R.H., Activity coefficients of
mannitol and potassium chloride in mixed ,aqueous solutions at 25 C, J. Phys. Chem., 66, 506-507(1962).
Okubo, T., Ise, N., A study of interactions between
polyelectrolyte and neutral polymer in aqueous solutions
in terms of water activity, J . Phys. Chem., 74, 42844288( 1970).
Hu, Y.F., New predictive equations for the specific and
apparent molar heat capacities of multicomponent aqueous solutions conforming to the linear isopiestic relation,
Bull. Chem. SOC.Jpn., 74,47-52(2001).
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Phase Equilib., 187-188,403--413(2001).
Hu, Y.F., Fan, S.S., A new predictive equation for depression in freezing points of multicomponent aqueous
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