Indian Journal of Pure & Applied Physics

Vol. 46, August 2008, pp. 545-551

Experimental and predicted viscosities of binary mixtures of benzene and

chloroalkanes at different temperatures using Isdales group contribution method
Anwar Ali*a, Mohammad Tariqb & Firdosa Nabia
a

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

INDIAN J PURE & APPL PHYS, VOL 46, AUGUST 2008

546

mixtures over the entire composition range expressed

as a function of mole fraction, x1 of benzene at
different temperatures ,are presented in Table 1. The
dependence of of the mixtures on x1 has been
established using a polynomial equation of the form:
4

= i x1i

(1)

i=0

The coefficients i of Eq. (1) along with the standard

deviations ( ) at each investigated temperature are
presented in Table 2. The significance of data fitting
using similar polynomial equations have also been
reported by others17,18. The values of and
Table 1Values of experimental viscosities of binary liquid
mixtures at different temperatures
x1

298.15

303.15

308.15

313.15

318.15

(mPa.s)
Benzene + DCE

G *E were calculated by using the standard relations2

and were smoothed by Redlich-Kister polynomial19.
The values of coefficients Ai of the polynomial19
together with the standard deviations (Y E ) are
given in Table 3. The variations of experimental and
calculated values, using Redlich-Kister polynomial19
of and G *E with mole fraction x1 of benzene are
graphically presented in Figs 14, respectively.
From Figs 1 and 2, it is clear that the values are
negative over the whole composition range of both
the systems investigated at each temperature.
Negative deviations in viscosity occur where
dispersion or weak dipole-dipole forces are primarily
responsible for the interaction between component
molecules20,21. Negative values may also be
observed due to the difference in the molecular size of
the component molecules22,23. The magnitude of
values (Figs 1 and 2) follows the sequence: DCE >
TCE. This is also the sequence in the difference in the
molar volume of benzene and chloroalkanes in the
present study. Furthermore, the values become
more negative as the temperature of the mixture
increases, i.e., the system shows non-ideal behaviour
with rise in temperature. This suggests that the
interactions between molecules become weaker as a
consequence of rise in temperature.
The variation of the excess Gibbs free energy of
activation of viscous flow, G *E with mole fraction,
x1 of benzene for both the binary mixtures at different

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

0.7793 -0.2860 -0.0777 0.2358 -0.0437 0.0008

0.1222

1.3256

1.3096

1.2422

1.1168

0.9902

303.15

0.7353 -0.3149 0.0345

0.0524

0.0008

0.1956

1.2588

1.2392

1.1756

1.0585

0.9401

308.15

0.7012 -0.3579 0.2225 -0.2152 0.1819

0.0008

0.3028

1.1676

1.1451

1.0851

0.9794

0.8726

313.15

0.6744 -0.4298 0.5000 -0.6259 0.3817

0.0012

0.3862

1.1000

1.0742

1.0173

0.9199

0.8222

318.15

0.6312 -0.4595 0.6907 -0.9300 0.5380

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

1.4390 -0.9730 0.3397 -0.2904 0.0927

0.0007

0.6890

0.8557

0.8188

0.7742

0.7076

0.6425

303.15

1.4303 -1.0453 0.4689 -0.4689 0.1783

0.0009

0.8079

0.7611

0.7207

0.6807

0.6268

0.5747

308.15

1.3606 -1.0291 0.5458 -0.5738 0.2298

0.0006

0.9020

0.6861

0.6434

0.6082

0.5642

0.5222

313.15

1.2255 -0.9567 0.6702 -0.7613 0.3237

0.0006

1.0000

0.6080

0.5630

0.5330

0.5011

0.4711

318.15

1.0887 -0.8804 0.7845 -0.9203 0.3990

0.0008

Table 2Coefficients of viscosities fitted to the polynomial (1)

against composition at different temperatures

Benzene + TCE

()

Benzene + DCE
0.0554

Benzene + TCE

ALI et al.: VISCOSITIES OF BINARY MIXTURES

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

Fig. 1Variation of with x1 for binary mixtures of benzene

+ DCE at different temperatures. Points show experimental values
and curves show smoothed values using Redlich-Kister equation19

0.0182

Fig. 2Variation of with x1 for binary mixtures of benzene

+ TCE at different temperatures. Points show experimental values
and curves show smoothed values using Redlich-Kister equation19

INDIAN J PURE & APPL PHYS, VOL 46, AUGUST 2008

548

temperatures are shown in Figs 3 and 4. The values of

G *E are found to be negative over the whole range
of composition and temperature investigated for the
mixtures of benzene + DCE (Fig. 3), while reverse
trends are observed for benzene + TCE mixtures (Fig.
4). In general, the positive contribution to the
G *E values may be attributed to the presence of
specific interactions whereas negative contributions
may be ascribed to the dispersion forces21,24. Thus, the
observed positive G *E values for the mixtures of
benzene + TCE suggest that the specific interactions of
donor-acceptor type are prevailing in the system,
whereas in case of benzene + DCE dispersion forces

are dominant which supports trends. Thus, the

observations are in accordance with the previously
reported volumetric and ultrasonic studies4 on the
present systems.
Further, by using the temperature dependence of
viscosity data the activation parameters for viscous
flow have been investigated. The Eyring viscosity
equation 25,26 is given as:

G*
hN
exp

V
RT

(2)

where h is Plancks constant, N is Avagadros

constant and G * E is the Gibbs energy of activation
of viscous flow. Combining Eq. (2) with
G* E = H * T S * gives the equation:
*
V H
*
RIn
=
S

hN
T

(3)

where H * and S * are the enthalpy and entropy of

activation of viscous flow, respectively. The plots of

V
against
hN

the left hand side of Eq. (3), i.e., RIn

*E

Fig. 3Variation of G with x1 for binary mixtures of

benzene + DCE at different temperatures. Points show
experimental values and curves show smoothed values using
Redlich - Kister equation19

1
T

for both the binary mixtures at different

compositions were found to show a quite linear trend

for each composition of the system under study. This
indicates that H * values are almost constant in the
investigated temperature range, i.e., H * is
independent of temperature.
Thus, the values of H * and S * were obtained as
the slopes and intercepts of the linear plots of

1
V
by using a linear regression
RIn
against
T
hN

*E

Fig. 4Variation of G with x1 for binary mixtures of

benzene + TCE at different temperatures. Points show
experimental values and curves show smoothed values using
Redlich - Kister equation19

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

ALI et al.: VISCOSITIES OF BINARY MIXTURES

Table 4Values of enthalpy and entropy of activation of viscous

flow for the binary liquid mixtures at each composition along with
the linear correlation factor
x1

-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

mole fraction of benzene, which again supports our

earlier view.
3.1 Theoretical Analysis
3.1.1 Correlation of excess volumes with viscosity

The excess volumes were calculated using the

deviation in viscosity data by a correlation proposed
by Singh27.
According to the relation, the deviations in
viscosity, and excess molar volumes, V E are
related to each other as:

= KV E

(4)

where K is a fitting parameter. The values of K for the

presently investigated mixtures were evaluated by
using the and experimentally reported V E data4 at
x1 = 0.5 (equimolar fraction). The values of K for
benzene + DCE and benzene + TCE are found to be209.2 and - 353.3 Nsm-5mol, respectively. From the
experimental data, the V E values at various mole

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

3.1.2 Prediction of mixtures viscosity

0.9020

9.776

6.669

0.996

1.0000

8.883

6.847

0.999

A number of mixing rules are available in the

literature28 for prediction of viscosities of liquid

fractions were calculated. The V E values calculated

from viscosity data using Eq. (4) were compared with
our earlier reported V E
values4, obtained
experimentally for both the mixtures at 298.15 K, and
are shown in Figs 5 and 6. A reasonable good
agreement has been found between the experimentally
calculated and theoretically predicted values. Thereby,
it emphasizes the effectiveness of the present approach.

17

has been suggested earlier that the enthalpy of

activation of viscous flow may be regarded as a
measure of the degree of cooperation between the
species taking part in viscous flow. In a highly
structured liquid, there will be considerable degree of
order and, hence, for cooperative movement of
entities, a large heat of activation, with relatively high
value of entropy of activation is needed for the flow
process. Therefore, a perusal of Table 4 indicates that
the formation of activated species necessary for
viscous flow seems to be easy in the DCE rich region,
owing to the low values of H * , and become
difficult as the mole fraction of benzene in the
mixture increases, whereas, a reverse trend is
observed in case of benzene + TCE mixtures. The
S * values are positive and decrease with increase in

Fig. 5Comparison of V between reported values ()4 and

the calculated values obtained by using viscosity data (----) of
binary mixtures of benzene + DCE at 298.15 K

INDIAN J PURE & APPL PHYS, VOL 46, AUGUST 2008

550

where N i and N j are the number of carbon atoms in

component i and j, respectively. If either of the
component (i, j) contains atom other than carbon and
hydrogen, W = 0 (as in our case). Now,
can be

calculated for i and j from the group contributions

given elsewhere28 at 298.15 K. For benzene, DCE and
TCE,
comes out to be 0.192, 0.854 and 0.444,

respectively. For mixtures of benzene + DCE/TCE,

Gij at 298.15 K can be calculated from Eq. (7).

Gij is supposed to be a mild function of

E

Fig. 6Comparison of V between reported values ()4 and the

calculated values obtained by using viscosity data (----) of binary
mixtures of benzene + TCE at 298.15 K

mixtures theoretically. Among them probably the

most extensively examined relation is the Grunberg Nissan (G-N) method.
According to this procedure, the liquid mixtures
viscosity is given as:

In = xi Ini +
i

1
xi x j Gij
2 i j

(5)

for a binary mixture of component 1 and 2, the

equation takes the form:

In = x1 In1 + x2 In 2 + x1 x2G12

(6)

where x is the mole fraction and G12 is an interaction

parameter, which is a function of the components as
well as temperature. The interaction parameter Gij can
be calculated by using a linear regression procedure.
Isdale et al.10 proposed a group contribution
method to estimate the binary interaction parameter
Gij at 298.15 K. According to them:

Gij = i j + W

(7)

By following the priority rules, first of all, assign the

number viz., i and j to the components. We have
assigned benzene and chloroalkanes as i and j,
respectively (as per the priority rule). Then, the
parameter W can be determined using:

W=

(0.3161)( N i + N j ) 2
( Ni + N j )

(0.1188)( N i N j )
(8)

temperature. Isdale et al10. suggested that if this is the

case then at subsequent temperatures G could be
calculated as:

Gij (T ) = 1 1 Gij (298.15)

573 T
275

(9)

Adopting the above two methods, viz., linear

regression analysis and group contribution method,
the interaction parameters, Gij have been obtained for
both the liquid systems at each investigated
temperature and presented in Table 5. Using the
Gij obtained from both methods, the viscosities of the
binary mixtures were calculated at each investigated
temperature and the results were given in terms of
average percentage deviations (APD) between
Table 5Interaction parameters of Grunberg - Nissan equation
and Isdales group contribution approach for the binary liquid
mixtures at different temperatures along with the average
percentage deviations (APD) from the experimental logarithmic
viscosity
Benzene + DCE
T/K

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

ALI et al.: VISCOSITIES OF BINARY MIXTURES

551

from Figs. 7 and 8 that In values calculated from GN

approach are in excellent agreement with the
experimental values, whereas, Isdales approach shows
significant deviations between theoretical and
experimental In values for both the systems studied.
Thus, the present study further supports the effectiveness
of a simple, yet accurate, GN method over the Isdales
group contribution approach.
References
1
2
3
Fig. 7Comparison of In with the calculated values using
Grunberg - Nissan and Isdales approach for the binary mixtures
of benzene + DCE at 298.15 K

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

experimentally reported and theoretically calculated

viscosities (Table 5). It is clear from Table 5 that the
APD in case of both the mixtures is quite low, when
Gij is taken from GN method, while large deviations
are observed when Gij is taken from Isdales group
contribution method. It is interesting to note that for
benzene + DCE mixtures both Gij and APD obtained
by GN method decrease with increase in
temperature, while they show an opposite trend when
obtained by using Isdales method. Whereas in case of
benzene + TCE no definite trends are observed with
variation of temperature.
Further, for the sake of comparison, logarithmic
viscosities, ln In obtained experimentally and from
GN and Isdales approaches are plotted against x1
(Figs 7 and 8) for both the mixtures studied. It is evident

16
17
18
19
20
21
22
23
24
25
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