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Department of Chemistry, Jamia Millia Islamia (Central University), New Delhi 110 025
b
Laoboratory of Molecular Thermodynamics;
Instituto de Tecnologia Quimicae Biologia, Universidade de Nova De Lisboa, Oeiras, Portugal
Received 7 November 2007; revised 23 April 2008; accepted 15 May 2008
Experimental viscosities, of pure benzene, 1,2-dichloroethane (DCE), 1,1,2,2-tetrachloroethane (TCE) and those of
their binary mixtures, having benzene as a common component, have been measured over the whole composition range at
298.15, 303.15, 308.15, 313.15 and 318.15 K. The experimental data were then fitted to standard polynomial against
composition. Using values, the deviations in viscosities, , excess Gibbs free energies of activation of viscous flow,
G*E, entropies, S* and enthalpies, H* of activation of viscous flow have been calculated. The sign and magnitude of
these parameters were found to be sensitive towards interactions prevailing in the studied systems. Further, the excess molar
volumes, VE were calculated using data for both the binary mixtures. Moreover, GrunbergNissan and Isdales group
contribution methods have been used to calculate the viscosities of mixtures and the results were discussed in terms of
average percentage deviations (APD) in experimentally and theoretically calculated viscosities.
Keywords: Viscosities, Interactions, Liquid mixtures, Correlations, Group contribution
1 Introduction
Viscosity is the ratio of tangential stress and velocity
gradient and provides a measure of the internal friction
of a fluid. It is an important non-equilibrium transport
property closely related to self-aggregation in liquids1.
Viscosity data provide a valuable insight into the
structure and interactions in mixed solvents and are
needed to evaluate mass transport and heat transfer,
among others2,3. These considerations led us to
undertake the present study in continuation to our
research programme on the thermodynamic behaviour
of binary liquid mixtures4-6.
Benzene is a versatile compound and widely used
in chemical and technological processes. Benzene is a
non-polar and unassociated liquid, whereas DCE and
TCE are polar but practically unassociated7,8.
Therefore, interesting results may be obtained
regarding the molecular interactions between the
unlike molecules in these binary mixtures.
Using the experimental data, , G*E, S* and
H * have been calculated. An attempt has also been
made to calculate excess molar volumes, VE using
data. Further, the Grunberg-Nissan9 and Isdales
group contribution10 methods have been used to
obtain viscosities of binary mixtures theoretically.
_________________________
*Email: anwar_jmi@yahoo.co.in
2 Experimental Details
The chemicals used in the present study were of
AR grade. Benzene (E. Merck, Germany), DCE and
TCE (Qualigens Fine Chemicals, India) were purified
by the methods described in the literature11,12. Before
use, the chemicals were stored over 0.4 nm molecular
sieves to reduce water content, if any. Mixtures were
prepared by mass using a Precisa XB-220 A (Swiss
make) electronic balance with a precision of 0.1 mg.
The densities of the pure liquids and their mixtures
were measured pycnometrically as reported
previously in the literature4. Viscosities were
determined with an Ubbelohde type suspended level
viscometer, thermostated in an electronically
controlled water bath (Julabo, Germany), with a
temperature stability of 0.02 K, for about 30 min so
that the thermal fluctuation in the viscosity was
minimized. The uncertainties in the measured
viscosities were not more than 210-3 mPa.s. The
observed viscosities of pure benzene, DCE and TCE
at 298.15 K are 0.6080, 0.7790 and 1.4388 mPa.s,
respectively, which compare well with the literature
values 0.6038(Ref.13)/0.6025(Ref.14), 0.7790 (Ref.15)
and 1.4560 (Ref.12)/1.4554 (Ref.16), respectively.
3 Results and Discussion
The experimental values of viscosities, of pure
benzene, DCE and TCE and those of their binary
546
= i x1i
(1)
i=0
298.15
303.15
308.15
313.15
318.15
(mPa.s)
Benzene + DCE
0.0000
0.7790
0.7350
0.7010
0.6741
0.6311
0.1028
0.7503
0.7041
0.6671
0.6355
0.5902
0.1899
0.7229
0.6765
0.6396
0.6067
0.5634
0.2975
0.6929
0.6465
0.6105
0.5776
0.5359
0.3910
0.6695
0.6225
0.5867
0.5541
0.5138
0.5003
0.6431
0.5955
0.5615
0.5291
0.4901
0.6019
0.6246
0.5775
0.5433
0.5105
0.4725
0.7018
0.6115
0.5637
0.5305
0.4965
0.4594
0.8006
0.6041
0.5555
0.5218
0.4872
0.4509
0.8955
0.6015
0.5535
0.5205
0.4845
0.4492
1.0000
0.6080
0.5630
0.5330
0.5011
0.4711
T/K
0.0000
1.4388
1.4302
1.3607
1.2258
1.0891
298.15
0.1222
1.3256
1.3096
1.2422
1.1168
0.9902
303.15
0.0524
0.0008
0.1956
1.2588
1.2392
1.1756
1.0585
0.9401
308.15
0.0008
0.3028
1.1676
1.1451
1.0851
0.9794
0.8726
313.15
0.0012
0.3862
1.1000
1.0742
1.0173
0.9199
0.8222
318.15
0.0014
0.4960
1.0105
0.9814
0.9285
0.8426
0.7567
0.5936
0.9315
0.8985
0.8504
0.7746
0.6992
298.15
0.0007
0.6890
0.8557
0.8188
0.7742
0.7076
0.6425
303.15
0.0009
0.8079
0.7611
0.7207
0.6807
0.6268
0.5747
308.15
0.0006
0.9020
0.6861
0.6434
0.6082
0.5642
0.5222
313.15
0.0006
1.0000
0.6080
0.5630
0.5330
0.5011
0.4711
318.15
0.0008
Benzene + TCE
()
Benzene + DCE
0.0554
Benzene + TCE
547
Table 3Coefficients of Redlich-Kister equation for the binary liquid mixtures along with standard deviations at different temperatures
T/K
A1
A2
A3
A4
A5
(YE)
Benzene + DCE
298.15
-0.1999
0.0682
(mPa.s)
0.0210
0.0331
-0.0092
0.0003
303.15
-0.2114
0.0714
0.0236
0.0383
-0.0552
0.0005
308.15
-0.2215
0.0640
0.0084
0.0414
-0.0875
0.0000
313.15
-0.2333
0.0544
-0.0343
0.0605
-0.1097
0.0001
318.15
-0.2435
0.0599
-0.0458
0.0539
-0.1691
0.0001
G*E (kJmol-1)
298.15
-620.7228
354.7228
52.3982
82.4031
-42.2639
1.2790
303.15
-719.2885
413.1853
73.2461
128.8229
-235.4530
1.9354
308.15
-814.6482
420.8769
23.4260
176.9581
-391.0945
0.3964
313.15
318.15
-916.9812
-1062.5453
427.0885
500.1239
-178.9781
-268.6752
329.0854
376.6488
-518.6594
-821.5198
0.6647
0.6004
0.0322
0.0004
Benzene + TCE
(mPa.s)
298.15
-0.0653
-0.0557
-0.0318
303.15
-0.0785
-0.0547
-0.0647
0.0028
0.0561
0.0002
308.15
-0.0864
-0.0526
-0.0636
-0.0158
0.0251
0.0003
313.15
-0.0939
-0.0468
-0.0915
-0.0347
0.0197
0.0002
318.15
-0.1026
-0.0474
-0.0949
-0.0475
G*E (kJmol-1)
-0.0148
0.0002
298.15
718.0968
-280.6028
18.0444
12.1205
81.6127
0.8357
303.15
845.9568
-326.8931
-68.9754
-18.3128
166.4595
0.5952
308.15
827.2768
-326.2755
-75.2511
-30.1629
79.6855
0.4822
313.15
694.2770
-275.3872
-197.0146
-26.2600
35.3841
0.7484
318.15
520.1513
-237.6426
-286.6083
-18.8703
-46.0321
0.7898
0.0182
548
G*
hN
exp
V
RT
(2)
(3)
V
against
hN
*E
1
T
1
V
by using a linear regression
RIn
against
T
hN
*E
procedure.
The values of H * and S * along with the linear
correlation factor, r of Eq. (3) are given in Table 4. A
close perusal of Table 4 indicates that for both the
binary mixtures, the values of H * and S * are
positive, showing an increase in H * values and an
opposite trend in S * values with mole fraction x1 of
benzene for the mixture benzene + DCE. In case of
benzene + TCE, both H * and S * tend to decrease
as the amount of benzene increases in the mixture. It
-1
(kJ.mol )
-1
-1
(JK mol )
Benzene + DCE
0.0000
7.169
7.532
0.995
0.1028
8.285
7.139
0.997
0.1899
8.647
6.997
0.997
0.2975
8.951
6.871
0.998
0.3910
9.218
6.762
0.998
0.5003
9.485
6.649
0.998
0.6019
9.787
6.533
0.998
0.7018
10.035
6.442
0.999
0.8006
10.339
6.338
0.999
0.8955
10.320
6.350
0.999
1.0000
8.883
6.847
0.999
Benzene + TCE
549
= KV E
(4)
0.0000
10.267
7.278
0.936
0.1222
10.800
7.012
0.945
0.1956
10.785
6.963
0.949
0.3028
10.732
6.901
0.954
0.3862
10.717
6.842
0.959
0.4960
10.591
6.795
0.967
0.5936
10.465
6.752
0.973
0.6890
10.435
6.673
0.982
0.8079
10.163
6.645
0.991
0.9020
9.776
6.669
0.996
1.0000
8.883
6.847
0.999
17
550
In = xi Ini +
i
1
xi x j Gij
2 i j
(5)
In = x1 In1 + x2 In 2 + x1 x2G12
(6)
Gij = i j + W
(7)
W=
(0.3161)( N i + N j ) 2
( Ni + N j )
(0.1188)( N i N j )
(8)
573 T
275
(9)
GrunbergNissan
APD
Isdale
APD
298.15
-0.265
-0.450
-0.662
32.95
303.15
-0.310
-0.525
-0.650
-13.19
308.15
-0.258
-0.579
-0.638
-9.88
313.15
-0.420
-0.752
-0.626
-6.93
318.15
-0.493
-0.865
-0.614
-4.08
Benzene + TCE
298.15
0.301
-6.072
-0.252
24.50
303.15
0.345
-5.247
-0.247
-79.64
308.15
0.330
-9.452
-0.243
64.33
313.15
0.263
0.268
-0.238
-70.73
318.15
0.183
15.70
-0.234
-70.83
551
4
5
6
7
8
9
10
11
12
Fig. 8Comparison of In with the calculated values using
Grunberg - Nissan and Isdales approach for the binary mixtures
of benzene + TCE at 298.15 K
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28