Chinese Journal of Chemical Engineering 23 (2015) 873879

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Chinese Journal of Chemical Engineering

journal homepage: www.elsevier.com/locate/CJChE

Fluid Dynamics and Transport Phenomena

Electrical conductivities for four ternary electrolyte aqueous solutions

with one or two ionic liquid components at ambient temperatures
and pressure
Qianqing Liang 1,, Yufeng Hu 2, Wenjia Yue 3
1
2
3

School of Chemistry Engineering, Inner Mongolia University of Science & Technology, Baotou 014010, China
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
China ShenHua Coal to Liquid and Chemical Co., Ltd., Beijing 100011, China

a r t i c l e

i n f o

Article history:
Received 20 December 2013
Received in revised form 14 August 2014
Accepted 26 September 2014
Available online 3 February 2015
Keywords:
Conductivity
Young's rule
Semi-ideal solution theory
Binary system
Ternary system

a b s t r a c t
This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two
ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for the ternary
systems NaCl[C6mim][Cl] (1-hexyl-3-methylimidazolium chloride)H2O, [C6mim][BF4][C6mim][Cl]H2O,
NaNO3[C6mim][BF4](1-hexyl-3-methylimidazolium tetrauoroborate)H2O, and [C4mim][BF4] (1-butyl-3methylimidazolium tetrauoroborate)[C6mim][BF4]H2O, and their binary subsystems NaNO3H2O, NaClH2O,
[C6mim][BF4]H2O, [C6mim][Cl]H2O, and [C4mim][BF4]H2O, respectively. The conductivities of the ternary
systems were also determined using generalized Young's rule and semi-ideal solution theory in terms of the data
of their binary solutions. The comparison showed that the two simple equations provide good predictions for
conductivity of mixed electrolyte solutions and the mixed ionic liquid solutions based on the conductivity of their
binary subsystems.
2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

1. Introduction
The transport properties of mixed aqueous solutions have always
attracted considerable interest due to extensive applications in many
elds such as chemistry and chemical engineering, separation process, wastewater treatment, pollution control, and oil recovery. Electrical conductivity is admittedly one of the principal transport
properties of aqueous electrolyte systems not only for its intrinsic
interest but also for technical and industrial applications such as
batteries and plating [1].
A number of groups have reported the physical properties of binary
electrolyte solutions [26]. However, it is still a considerable measurement work for the properties of the multicomponent solutions using
the conventional testing method. Therefore, it is practically important
to develop an efcient method to obtain more useful data of the multicomponent solutions according to the available information on the

Supported by the National Natural Science Foundation of China (51066004), the

Scientic Research Project of Higher Education Institutions of Inner Mongolia (NJZY14172)
and the Innovation Fund of Inner Mongolia Science and Technology (2011NCL060).
Corresponding author.
E-mail address: liangqianqing2012@gmail.com (Q. Liang).

binary solutions [710]. Several attempts have been made using the
Young's rule [11,12] and the semi-ideal solution theory [13,14] to obtain
good predictions for the thermodynamic properties of the mixed electrolytes solutions from their binary subsystems [15,16]. Hu et al. have successfully veried and extended the applicability of the generalized
Young's rule and the semi-ideal solution theory to the conductivity
of mixed electrolytes solutions [17,18]. For example, the conductivities of the ternary systems NaClLaCl3H2O can be predicted very
well with the conductivities of its binary subsystems NaClH2 O
and LaCl3H2O at 298.15 K [17,18]. The measurement of the conductivities [1] were also made for the mixed electrolyte solution ternary systems
Y(NO3)3Ce(NO3)3H2O, Y(NO3)3Nd(NO3)3H2O, and Ce(NO3)3
Nd(NO3)3H2O, Y(NO3)3La(NO3)3H2O, La(NO3)3Ce(NO3)3H2O, and
La(NO3)Nd(NO3)3H2O, and their binary subsystems Y(NO3)3H2O,
Ce(NO3)3H2O, and Nd(NO3)3H2O and La(NO3)3H2O, at (293.15,
298.15 and 308.15) K and up to Imax 24.4 molkg1. With the equations of the generalized Young's rule and the semi-ideal solution theory,
the predictions of conductivities for ternary systems based on the data
of their binary subsystems are in good agreement with the measured
values.
Ionic liquids (ILs) have been recognized as novel designable solvents
which can be tuned/controlled by tailoring their cationic and anionic
structures to optimize their physicochemical properties [1]. Thus, they
are environmentally benign and non-ammable, and pose high thermal

http://dx.doi.org/10.1016/j.cjche.2014.09.050
1004-9541/ 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

874

Q. Liang et al. / Chinese Journal of Chemical Engineering 23 (2015) 873879

stability and a high solvation capacity [19,20]. These unique features

suggest their potential application in a wide variety of industrial and
chemical processes, such as absorption media in gas absorption, heat
transfer uids and working uids in electrochemical processes
[2123].
In all these applications, the utilization of aqueous solutions of
ILs, especially cognition of the basic properties for these systems,
will be inevitable in a practical approach or in the design of industry
process. One of the basic properties of interest for electrochemical
applications is electrical conductivity. Moreover, the presence
of water in ILs can dramatically affect their physicochemical
properties [2426]. Therefore, several groups [2734] have studied
the physical properties of aqueous solutions of ILs for the binary
systems (waterIL). Up to now, the basic properties of aqueous solutions of IL mixtures are important not only for industrial applications, but also for the verication of the electrolyte theories
although few measurements have been made on the electrical conductivities for ternary systems such as the aqueous solutions of IL
mixtures and the mixed electrolyte solutions with IL.
Therefore, the experimental measurements of the conductivities of
ternary systems NaCl[C6mim][Cl]H2O, [C6mim][BF4][C6mim][Cl]
H2O, NaNO3[C6mim][BF4]H2O, and [C4mim][BF4][C6mim][BF4]H2O,
and their binary subsystems NaNO3H2O, NaClH2O, [C6mim][BF4]
H2O, [C6mim][Cl]H2O, and [C4mim][BF4]H2O were presented at
room temperature, respectively. The above-mentioned predictive
equations including generalized Young's rule and semi-ideal solution theory developed for the properties of mixed electrolyte solutions were extended to conductivities of mixed IL solutions and
the mixed electrolyte solutions containing IL with lower concentration. On the other hand, the measured conductivities of the above ternary
systems and their binary subsystems were also used to test the generalized Young's rule and the semi-ideal solution theory for electrical conductivity of multicomponent solutions containing ILs and electrolytes.
2. Experimental
Deionized water was distilled in a quartz still, and its conductivity
was 0.81.2 106 Scm1. All chemicals used in this study were of
reagent grade with the claimed purity N 99%. N-methylimidazole, nC4H9Cl, n-C6H13Cl, and NaBF4 were supplied by Shanghai Jiacheng
Chemical Co., Ltd. These chemicals were rened by fractional distillation
[35]. NaCl and NaNO3 were dried under vacuum over CaCl2 for 7 days at
423 K prior to their use [16]. All the ionic liquids present in this work
were prepared using well-established procedures [3638]. The chloride
salts were prepared by reacting N-methylimidazole with RCl, where, R
was n-C4H9 or n-C6H13 The products were puried by repeated extractions of the remaining starting materials with ethyl acetate. After the
last extraction, the remaining ethylacetate was removed at 343.15 K
under vacuum [39]. The resulting [1-alkyl-mim][Cl] ([C 4 mim][Cl]
and [C6mim][Cl]) were dried at 343.15 K under vacuum for 6 days.
[C4mim][Cl] and NaBF4 were dissolved in acetone separately with
equimolar amounts. Then, the two solutions gradually formed a
mixture with stirring. The precipitated sodium chloride was removed
from the liquid by ltration. The excess acetone was evaporated away
and crude product [C4mim][BF4] was dried in vacuum for 48 h. The
obtained [C4mim][Cl] was white crystals at room temperature, and
[C 6mim][Cl] and [C6 mim][BF4 ] were liquid at room temperature.
After purication, the ILs were dried under vacuum over CaCl2 for
several days at 70 C and were then further dried with 0.3 nm molecular sieves for several days immediately before use. The water content after drying, measured by Karl Fisher titration, was within
0.012% (by mass).
All the samples were prepared by syringing weighed amounts of the
pure liquids into stoppered bottles in a glove box. The binary aqueous solutions of NaNO3, NaCl, [C6mim][BF4], [C6mim][Cl] and [C4mim][BF4] were
prepared by mass from double-distilled deionized water and the ILs using

a Sartorius CT225D balance with a precision of 5 105 g. The ternary

systems were prepared by mixing the binary solutions with known mass
concentration with uncertainty of 5 105 molkg1. All solutions
prepared in a glass ask were placed into stoppered bottles and
stirred for 2 h. The measurements were made one week after preparation to assure complete dissolution and aggregation. Due to the low solubility of the ionic liquids, all the prepared samples was in a narrow
concentration range of 0.00040.3000 molkg1.
The conductivities of prepared samples were measured with a
METLER TOLEDO SevenEasyTM conductivity meter (cell constant =
0.57 cm 1) calibrated with standard aqueous potassium chloride
solutions [18]. The temperature of the cell was kept constant to
within 0.005 K by circulating thermostated liquid and the temperature was measured with a calibrated calorimeter thermometer
( 0.006 K).
3. Predictive Equations for Conductivity
3.1. Generalized Young's rule for conductivity
The generalized Young's rule for the conductivity of the ternary
electrolyte solutions [40] can be expressed as

y1 1 y2 2

with yi = Ii /(I 1 + I2 ), where I is ionic strength. , 1 and 2 are

the conductivities of the ternary solution M 1 X 1 M 2 X 2 H 2 O
and its binary subsystems M i X i H 2 O (i = 1 or 2) of equal
ionic strength.
3.2. Semi-ideal solution theory for conductivity
The semi-ideal solution theory for the conductivity of the ternary
electrolyte solutions can be expressed as [18,41,42]

ln z1 ln 1 z2 ln 2

where i is the conductivity of the binary solution of salt i and water,

MiXi H2O (i = 1 or 2), having the same water activity as that of the
ternary solution M1X1 M2X2 H2O. zi is the ratio of the mole fraction
of i H2O(Li)(i = 1 or 2) in the ternary ideal solution 1 H2O(L1)
2 H2O(L2) H2O to the mole fraction of i H2O(Li) in the binary ideal
solution i H2O(Li) H2O i.e.,

ideal

o;ideal

zi xiH2 OLi =xiH2 OLi

with

o;ideal
o

o
o
xiH2 OLi i mi = 55:51ci i mi i mi

and

ideal

xiH2 OLi i mi =55:51c 1 m1 2 m2 1 m1 2 m2 

Q. Liang et al. / Chinese Journal of Chemical Engineering 23 (2015) 873879



where ci 55:51= i moi aH2 O = 1aH2 O and c = (c11m1 + c22m2)/

875

The measured conductivities of the binary solutions are substituted

by the following polynomial equations:

(1m1 + 2m2). is salt stoichiometric coefcient and i Mi X i 

aH2 O is water activity. mi and moi are the molalities of the ith solute in
ternary aqueous solution M1X1 M2X2 H2O and its binary subsystems
i H2O(Li) H2O of equal water activity. Furthermore, water activity
of material involved in this article was equal in the measured
concentration range, which was consistent with the theory of
equal ionic strength. Consequently, the semi-ideal solution theory could be appropriately used for predictions in this work.

ical

n
X

o l=2
Al mi

l0

o
and moi represent the conductivity and molality of the
where i(cal)
binary systems, Mi Xi H2O, respectively. The optimum t is obtained
by varying l until the values of

3.3. Comparisons with the experimental data


,


N 
X
i exp ical 

N
i exp
j1

The measured conductivities of ternary system are used to test

Eqs. (1) and (2), and the test procedure [43] is briey illustrated in the
following schematic diagram in Fig. 1.

Represent the measured conductivities of the

binary solutions by

Mo X (calc) = Al (mMo i Xi )l 2
i i

l =0

Variation of l to obtain the value of Al and o,Mi Xi

o ,Mi Xi = j =1 Mo X
N

i i

(calc)

Mo X (expt ) Mo X (expt ) N 104

i i

i i

Determine the composition mMo,Ii Xi of the binary systems having the same ionic
strength as that of the mixed solution of given molalities mMi Xi (i = 1, 2, ..., n)

Insert the values of Mo,Ii Xi to obtain the conductivities of ternary systems of given

mMi Xi (i = 1, 2, ..., n)

Compared with measured data of ternary systems can obtain the

differences between calculation results of Eqs. 1-2 and measured
conductivities of the ternary systems

eq i = eq i exp
The average relative differences between predicted and measured
conductivities of ternary system over the entire experimental
N

,eq i =
j =1

j (exp) j (eq i )
j (exp)

Fig. 1. Test procedure diagram of comparisons with the experimental data.

876

Q. Liang et al. / Chinese Journal of Chemical Engineering 23 (2015) 873879

mi(i = 1 or 2) using the osmotic coefcients of the binary solutions

MiXi H2O(i = 1 or 2) [44] and the Zdanovskii's rule [45]

Table 1
The parameters for the binary systems MiXi H2O at different temperatures
NaNO3 + H2O

[C6mim][BF4] + H2O

[C6mim][Cl] + H2O

303.15 K

303.15 K

298.15 K

4.8478
53.8625
177.2585
574.2911
1923.5053
2860.1896
1627.2136
8.34 103

3.5786
39.5898
130.0292
391.5642
1416.8319
2328.9794
1396.8660
7.01 104

0.6791
4.6525
5.6899
149.9989
474.9026
1013.2959
822.3428
2.81 104

0
1
2
3
4
5
6
o

0
1
2
3
4
5
6
o

[C6mim][BF4] + H2O

[C4mim][BF4] + H2O

NaCl + H2O

298.15 K

298.15 K

298.15 K

6.8126
75.5857
244.0061
864.5338
3027.8867
5434.3640
3895.7232
3.30 104

2.1221
27.9582
111.04472
502.6567
2391.4944
4955.3794
3799.8876
7.99 104

7.1588
75.6244
232.4755
988.9032
2649.1213
4192.1032
2701.4780
7.20 104

m
 1 =m1 m2 =m2 1

o
aH2 O constant and 0mi =mi 1 :

The values of ci are determined using the water activities of the

o
are inserted from Eq. (6) into
binary solutions. The values of i(cal)
Eq. (2) to yield the predictions for the ternary solutions of given
mi(i = 1 and 2), which are then compared with the corresponding
experimental values.
The differences between predicted and measured conductivities are
dened by
eq i eq i exp :

The average relative differences between the predicted and measured

conductivities over the entire experimental composition range of the
ternary solution are dened by

are less than a few parts in 104. Thus, the obtained parameters for the
binary systems are shown in Table 1.
Further, the values of oi(cal) are inserted from Eq. (6) into Eq. (1) to
yield the predictions for the ternary solutions of given mi (i =
1 and 2), which are then compared with the corresponding experimental data.
Determine the compositions (moi ) of the binary systems having the
same water activity as that of the ternary solution of given molalities

;eq i

,



N 
X
j exp jeq i 
N

j exp
j1

10

with i = 1 and 2.

Table 2
Measured conductivities for the binary systems MiXi H2O
mNaNO3 =mol  kg

mNaCl/mol kg1

NaNO3 =mS  cm1

303.15 K

mNaCl/mol kg1

298.15 K
exp

0.0019
0.0049
0.0299
0.0499
0.1005
0.1494
0.1997
0.2995

NaCl/mS cm1

NaCl/mS cm1
298.15 K

exp

0.387
0.785
3.570
5.550
10.620
15.320
19.980
28.600

0.0027
0.0055
0.0103
0.0301
0.0499
0.0701
0.0999
0.1499
0.1998

Ref. [14]

0.328
0.674
1.172
3.310
5.410
7.450
10.320
15.090
19.620

0.2

20.21

Table 3
Measured conductivities for the binary systems MiXi H2O
mC6 mimB F4  =
mol  kg

C6 mimB F4  =

mC6 mimB F4  =

mS  cm1

mol  kg

303.15 K

C6 mimB F4  =

mC6 mimCl =

mS  cm1

mol  kg

298.15 K
exp

0.0020
0.0050
0.0100
0.0303
0.1007
0.1509
0.2016
0.3025

0.356
0.733
1.344
3.390
9.250
12.730
15.560
20.200

C6 mimCl =

C4 mimB F4  =

C4 mimB F4  =

mS  cm1

mS  cm1

mS  cm1

298.15 K
exp

0.0019
0.0050
0.0302
0.0494
0.0687
0.0975
0.0990
0.1902

0.257
0.586
3.150
4.800
6.370
8.570
8.660
14.910

298.15 K
exp

0.0019
0.0081
0.0099
0.0298
0.0494
0.0690
0.1456
0.1920

0.205
0.726
0.886
2.530
3.970
5.330
10.260
13.010

exp
0.0019
0.0051
0.0080
0.0101
0.0302
0.0501
0.1471
0.1940

0.351
0.766
1.090
1.300
3.220
5.080
12.690
15.800

Q. Liang et al. / Chinese Journal of Chemical Engineering 23 (2015) 873879

Table 4
Comparisons of measured and predicted conductivities for aqueous solution of electrolyte
mixture NaNO3(B)[C6mim][BF4] (C)H2O at 303.15 K.
mB/molkg1

mC/molkg1

/mS cm1
exp

0.0004
0.0009
0.0014
0.0010
0.0025
0.0037
0.0016
0.0040
0.0060
0.0020
0.0049
0.0074
0.0060
0.0150
0.0225
0.0101
0.0252
0.0376
0.0139
0.0346
0.0518
0.0205
0.0511
0.0763
0.0309
0.0766
0.1141
0.0417
0.1033
0.1536
0.0639
0.1574
0.2332
Note: ;eq i

0.0016
0.0010
0.0005
0.0040
0.0025
0.0012
0.0064
0.0040
0.0020
0.0080
0.0050
0.0025
0.0244
0.0152
0.0076
0.0409
0.0255
0.0128
0.0574
0.0358
0.0178
0.0824
0.0512
0.0255
0.1248
0.0774
0.0385
0.1685
0.1043
0.0517
0.2582
0.1589
0.0785

0.375
0.349
0.357
0.774
0.790
0.772
1.176
1.186
1.188
1.433
1.382
1.384
3.540
3.560
3.570
5.510
5.530
5.560
7.065
7.300
7.520
9.750
10.080
10.380
13.510
14.210
14.740
16.670
17.960
18.970
22.200
24.700
26.600

,
N 

j exp jeq i

N:
i exp
j1

/mS cm1

Eq. (1)

Eq. (2)

Eq. (1)

Eq. (2)

0.364
0.371
0.378
0.744
0.762
0.776
1.125
1.154
1.178
1.364
1.392
1.415
3.441
3.491
3.533
5.322
5.417
5.495
7.100
7.233
7.340
9.711
10.083
10.387
13.581
14.331
14.936
16.984
18.255
19.276
22.943
25.415
27.381

0.363
0.371
0.377
0.744
0.761
0.776
1.124
1.153
1.178
1.363
1.391
1.414
3.440
3.490
3.532
5.320
5.413
5.492
7.095
7.224
7.334
9.695
10.058
10.369
13.534
14.258
14.882
16.884
18.099
19.159
22.671
24.988
27.060

0.011
0.022
0.021
0.030
0.028
0.004
0.051
0.032
0.010
0.069
0.010
0.031
0.099
0.069
0.037
0.188
0.113
0.065
0.035
0.067
0.180
0.039
0.003
0.007
0.071
0.121
0.196
0.314
0.295
0.306
0.743
0.715
0.781

0.012
0.022
0.020
0.030
0.029
0.004
0.052
0.033
0.010
0.070
0.009
0.030
0.100
0.070
0.038
0.190
0.117
0.068
0.030
0.076
0.186
0.055
0.022
0.011
0.024
0.048
0.142
0.214
0.139
0.189
0.471
0.288
0.460

877

Table 5
Comparisons of measured and predicted conductivities for aqueous solution of electrolyte
mixture [C6mim][Cl] (B)NaCl (C)H2O at 298.15 K.
mB/molkg1

mC/molkg1

/mS cm1
exp

0.0005
0.0010
0.0015
0.0012
0.0025
0.0037
0.0020
0.0040
0.0061
0.0025
0.0050
0.0074
0.0074
0.0149
0.0224
0.0125
0.0248
0.0365
0.0173
0.0343
0.0521
0.0246
0.0479
0.0740
0.0363
0.0715
0.1105
0.0475
0.0973
0.1481
Note: ;eq i

0.0021
0.0014
0.0007
0.0041
0.0027
0.0014
0.0062
0.0041
0.0021
0.0077
0.0050
0.0026
0.0227
0.0151
0.0076
0.0375
0.0252
0.0135
0.0528
0.0357
0.0180
0.0754
0.0521
0.0260
0.1136
0.0784
0.0395
0.1523
0.1025
0.0518

0.304
0.262
0.231
0.621
0.570
0.517
0.883
0.847
0.782
1.112
1.024
0.941
3.086
2.993
2.779
4.971
4.703
4.401
6.710
6.545
6.112
9.402
8.678
8.342
13.423
13.324
12.435
17.006
15.774
14.139

,
N 


j exp
jeq i

N:
i exp
j1

/mS cm1

Eq. (1)

Eq. (2)

Eq. (1)

Eq. (2)

0.291
0.252
0.222
0.618
0.560
0.504
0.899
0.842
0.784
1.098
1.024
0.956
3.125
2.931
2.738
5.061
4.716
4.388
6.936
6.439
5.921
9.616
8.926
8.153
13.975
12.910
11.729
18.160
16.621
15.051

0.290
0.252
0.222
0.613
0.554
0.499
0.893
0.835
0.779
1.092
1.017
0.950
3.106
2.907
2.720
5.021
4.663
4.348
6.873
6.358
5.861
9.520
8.801
8.059
13.821
12.706
11.575
17.942
16.329
14.834

0.013
0.010
0.009
0.003
0.010
0.013
0.016
0.005
0.002
0.014
0.000
0.015
0.039
0.062
0.041
0.091
0.013
0.013
0.226
0.105
0.191
0.214
0.248
0.189
0.552
0.414
0.706
1.154
0.847
0.912

0.014
0.010
0.009
0.008
0.017
0.018
0.010
0.012
0.003
0.020
0.007
0.009
0.020
0.086
0.059
0.050
0.040
0.053
0.163
0.187
0.251
0.118
0.123
0.283
0.398
0.618
0.860
0.936
0.555
0.695

,eq i = 2.55 102.

,eq i = 2.65 102.

,eq i = 2.1 102.

,eq i = 2.0 102.

4. Results and Discussions

4.1. Comparisons of the measured conductivities with the values reported in
the literature
Table 2 compares the measured conductivities of the binary solutions
NaClH2O at 298.15 K with the reported values [2]. It could be seen that
the agreements are good. The measured conductivities of the binary
solutions [C6mim][BF4]H2O at 303.15 K, and [C6mim][Cl]H2O,
[C4mim][BF4]H2O,[C6mim][BF4]H2O at 298.15 K are shown in Table 3,
respectively.
4.2. Verications of equations
Table 4 shows the comparisons of predicted and measured conductivities for aqueous solutions of (1:1 + 1:1), electrolyte
mixtures of NaNO 3 [C 6 mim][BF 4 ]H 2 O. It could be seen that the
agreements are good for all the examined cases where mixing
occurs at constant ionic strength and at constant water activity.
The average relative differences between the predicted and the
measured conductivities are ,eq 1 = 2.2 10 2 and ,eq 2 =
2.0 10 2 for NaNO3[C6mim][BF4]H2O at 303.15 K.
Tables 5, 6 and 7 compare predicted and measured conductivities for
the ternary solutions [C6mim][Cl]NaClH2O, [C4mim][BF4][C6mim]
[BF4]H2O and [C6mim][Cl][C6mim][BF4]H2O at 298.15 K. The average
relative differences between the predicted and measured conductivities,

,eq 1, are 2.55 10 2 for [C6mim][Cl]NaClH2O, 2.54 102 for

[C4mim][BF4][C6mim][BF4]H2O, and 1.50 10 2 for [C6mim][Cl]
[C6mim][BF4]H2O, respectively, which indicate that the predictions
are almost in agreement with the measured values. Meanwhile, the average relative differences between the predicted and measured conductivities, ,eq 2, are 2.65 102 for [C6mim][Cl]NaClH2O, 2.70 102
for [C4mim][BF4][C6mim][BF4]H2O and 1.40 102 for [C6mim][Cl]
[C6mim][BF4]H2O, respectively, indicating that the predictions are
almost in agreement with the measured values, which are also
consistent with the predication results of Eq. (1). It is noted that
the prediction of Eq. (1) is simpler since it only requires the conductivities of the binary subsystems MiXi H2O(i = 1 or 2) of equal ionic
strength. The prediction of Eq. (2) requires both the conductivity and
water activity of the binary subsystems. For all the examined cases, the
above results indicated that, as for predicted results of [C6mim][Cl]
NaClH2O and [C4mim][BF4][C6mim][BF4]H2O, Eqs. (1) and (2) are especially in good agreement with the measured values for the ternary system of [C6mim][Cl][C6mim][BF4]H2O at 298.15 K.
5. Conclusions
The conductivities were measured for the ternary systems NaNO3
[C 6 mim][BF 4 ]H 2 O at 303.15 K, and [C 6 mim][Cl]NaClH 2 O,
[C 4 mim][BF 4 ][C 6 mim][BF 4 ]H 2 O and [C 6 mim][Cl][C 6 mim][BF 4 ]
at 298.15 K, and their binary subsystems NaNO3H2O, [C6mim][BF4]
H2O at 303.15 K, and NaClH2O, [C6mim][BF4]H2O, [C6mim][Cl]H2O,
and [C4mim][BF4]H2O at 298.15 K. The measured conductivities for
the ternary solutions were used to verify the applicability of the
generalized Young's rule and the semi-ideal solution theory for

878

Q. Liang et al. / Chinese Journal of Chemical Engineering 23 (2015) 873879

Table 6
Comparisons of measured and predicted conductivities for aqueous solution of electrolyte
mixture [C4mim][BF4] (B)[C6mim][BF4] (C)H2O at 298.15 K.
mB/molkg1

0.0005
0.0010
0.0013
0.0026
0.0038
0.0020
0.0040
0.0060
0.0025
0.0051
0.0076
0.0076
0.0151
0.0228
0.0127
0.0254
0.0380
0.0254
0.0508
0.0763
0.0381
0.0762
0.1143
0.0508
0.1017
0.1528

mC/molkg1

0.0015
0.0010
0.0038
0.0026
0.0013
0.0062
0.0042
0.0021
0.0075
0.0050
0.0025
0.0228
0.0153
0.0076
0.0379
0.0253
0.0127
0.0760
0.0507
0.0254
0.1138
0.0759
0.0382
0.1517
0.1012
0.0507

/mS cm1

/mS cm1

exp

Eq. (1)

Eq. (2)

Eq. (1)

Eq. (2)

0.310
0.330
0.661
0.711
0.747
0.999
1.033
1.068
1.176
1.232
1.285
3.215
3.259
3.294
4.967
5.062
5.097
9.081
9.249
9.388
13.166
13.54
13.812
16.371
16.52
16.687

0.287
0.311
0.642
0.684
0.726
1.017
1.041
1.065
1.224
1.252
1.280
3.188
3.204
3.220
4.958
5.019
5.079
8.993
9.153
9.313
12.479
12.674
12.868
15.948
16.132
16.316

0.284
0.307
0.638
0.679
0.723
1.016
1.039
1.064
1.223
1.251
1.279
3.188
3.204
3.220
4.957
5.017
5.078
8.989
9.148
9.310
12.475
12.669
12.865
15.946
16.130
16.314

0.023
0.019
0.019
0.027
0.021
0.018
0.008
0.003
0.048
0.020
0.005
0.027
0.055
0.074
0.009
0.043
0.018
0.088
0.096
0.075
0.687
0.866
0.944
0.423
0.388
0.371

0.026
0.023
0.023
0.032
0.024
0.017
0.006
0.004
0.047
0.019
0.006
0.027
0.055
0.074
0.010
0.045
0.019
0.092
0.101
0.078
0.691
0.871
0.947
0.425
0.390
0.373


,
 j exp jeq i 
N:
i exp
j1
N

;eq i

,eq i = 2.54 102.

,eq i = 2.70 102.

Table 7
Comparisons of measured and predicted conductivities for aqueous solution of electrolyte
mixture [C6mim][Cl] (B)[C6mim][BF4] (C)H2O at 298.15 K.
mB/molkg1

0.0005
0.0010
0.0015
0.0012
0.0025
0.0037
0.0020
0.0041
0.0061
0.0025
0.0049
0.0074
0.0071
0.0150
0.0225
0.0125
0.0250
0.0375
0.0175
0.0351
0.0526
0.0251
0.0502
0.0751
0.0376
0.0753
0.1132
0.0502
0.1004
0.1511

0.0015
0.0010
0.0005
0.0038
0.0025
0.0013
0.0060
0.0040
0.0020
0.0075
0.0050
0.0025
0.0229
0.0150
0.0075
0.0374
0.0250
0.0125
0.0523
0.0349
0.0175
0.0747
0.0498
0.0252
0.1119
0.0748
0.0375
0.1488
0.0996
0.0499
N

;eq i
j1

the conductivity of the special ternary system in this work. The

predicted results were almost in agreement with the measured
values, indicating that the generalized Young's rule and the semiideal solution theory were suitable to predict the conductivities
of the ternary electrolyte solutions from the data of their binary
subsystems, especially for the ternary system of [C 6 mim][Cl]
[C6mim][BF4]H2O.
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,
 j exp jeq i 
i exp

/mS cm1

/mS cm1

exp

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Eq. (2)

Eq. (1)

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2.983
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7.719
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10.958
14.972
14.490
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0.002
0.002
0.004
0.002
0.002
0.007
0.027
0.025
0.014
0.026
0.031
0.014
0.006
0.020
0.007
0.075
0.100
0.005
0.089
0.128
0.006
0.159
0.161
0.050
0.027
0.087
0.211
0.333
0.400
0.509

0.001
0.000
0.003
0.001
0.006
0.010
0.020
0.016
0.007
0.018
0.021
0.007
0.017
0.036
0.018
0.090
0.119
0.019
0.108
0.152
0.024
0.181
0.190
0.071
0.049
0.057
0.188
0.302
0.360
0.479

N:

,eq i = 1.50 102.

,eq i = 1.40 102.

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