Fluid Phase Equilibria 252 (2007) 8895

Densities, viscosities and ultrasonic velocities of binary mixtures

of methylbenzene with hexan-2-ol, heptan-2-ol
and octan-2-ol at T = 298.15 and 308.15 K
Mehdi Hasan a, , Dinesh F. Shirude a,b , Apoorva P. Hiray a ,
Arun B. Sawant a , Ujjan B. Kadam a,1
a

P.G. Department of Physical Chemistry, M.S.G. College, Malegaon Camp 423105, India
b Arts, Science and Commerce College, Nampur 423204, India

Received 24 August 2006; received in revised form 1 January 2007; accepted 1 January 2007
Available online 7 January 2007

Abstract
Densities, viscosities and ultrasonic velocities of binary mixtures of methylbenzene with hexan-2-ol, heptan-2-ol and octan-2-ol have been
measured over the entire range of composition, at 298.15 and 308.15 K and at atmospheric pressure. From the experimental values of density,
viscosity and ultrasonic velocity, the excess molar volumes (VE ), deviations in viscosity () and deviations in isentropic compressibility (s ) have
been calculated. The excess molar volumes, deviations in viscosity and deviations in isentropic compressibility have been fitted to the RedlichKister
polynomial equation. The JouybanAcree model is used to correlate the experimental values of density, viscosity and ultrasonic velocity.
2007 Published by Elsevier B.V.
Keywords: Excess molar volumes; Deviations in viscosity; Deviations in isentropic compressibility; Methylbenzene; Hexan-2-ol; Heptan-2-ol; Octan-2-ol

1. Introduction

2. Experimental

Studies on thermodynamic and transport properties of binary

liquid mixtures provide information on the nature of interactions
in the constituent binaries. Literature provides extensive data on
the density and viscosity of liquid mixtures but a combined study
of density, viscosity and ultrasonic velocity is quite scarce. The
effect of molecular size, shape, chain length and degree of molecular association of normal alkanols and branched alkanols, on the
volumetric, viscometric and acoustic properties of binary mixtures containing acetonitrile, dimethylsulfoxide, ethyl acetate,
chloroform and benzonitrile have been reported earlier [18].
In continuation with our earlier study of intermolecular interactions in methylbenzenealkanol binary mixtures [911] we now
report the density, viscosity and ultrasonic velocity data for the
binary mixtures of methylbenzene with hexan-2-ol, heptan-2-ol
and octan-2-ol at 298.15 and 308.15 K.

Methylbenzene, hexan-2-ol, heptan-2-ol and octan-2-ol

(Qualigens Fine Chemicals, purity >99.5 mass%) were used
after single distillation. The densities, viscosities and ultrasonic
velocities of the pure components were compared with the corresponding literature values at 298.15 and 308.15 K (Table 1).
Binary mixtures were prepared by mass in air tight stoppered
glass bottles. The masses were recorded on an Adairdutt balance to an accuracy of 1 104 g. Care was taken to avoid
evaporation and contamination during mixing. The estimated
uncertainty in mole fraction was <1 104 .
Densities were determined by using 15 cm3 bicapillary pycnometer as described earlier [12,13]. The pycnometer was
calibrated using conductivity water with 0.99705 g cm3 as its
density [14] at 298.15 K. The pycnometer filled with air bubble free experimental liquids was kept in a transparent walled
water bath (maintained constant to 0.01 K) for 1015 min to
attain thermal equilibrium. The positions of the liquid levels in
the two arms were recorded with the help of travelling microscope, which could read to 0.01 mm. The estimated uncertainty
of density measurements of solvent and binary mixtures was

Corresponding author. Tel.: +91 2554 561544; fax: +91 2554 251705.
E-mail address: mihasan@rediffmail.com (M. Hasan).
1 Present address: Arts, Science and Commerce College, Manmad 423104,
India.
0378-3812/$ see front matter 2007 Published by Elsevier B.V.
doi:10.1016/j.fluid.2007.01.001

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

89

Table 1
Comparison of experimental density, viscosity and ultrasonic velocity of pure liquids with literature values at 298.15 K
Pure liquid

Methylbenzene
Hexan-2-ol
Heptan-2-ol
Octan-2-ol
a
b
c
d

(g cm3 )

u (m s1 )

(mPa s)

Experimental

Literature

0.86218
0.81084
0.81374
0.81708

0.86219a
0.8108c
0.8134a
0.8171a

Experimental

Literature

Experimental

Literature

0.554
4.105
5.088
6.429

0.5525a

1306
1290
1314
1328

1304b

1309d

5.06c
6.490a

Ref. [24].
Ref. [25].
Ref. [26].
Ref. [27].

0.00005 g cm3 . At least three to four measurements were made

which had an average deviation of 0.00005 g cm3 .
The dynamic viscosities were measured using an Ubbelohde
suspended level viscometer [68], calibrated with conductivity water. An electronic digital stop watch with readability of
0.01 s was used for the flow time measurements. At least three
repetitions of each data reproducible to 0.05 s were obtained,
and the results were averaged. Since all flow times were greater
than 200 s and capillary radius (0.5 mm) was far less than its
length (5060 mm), the kinetic energy and end corrections,
respectively, were found to be negligible. The uncertainties in
dynamic viscosities are of the order of 0.003 mPa s.
The ultrasonic velocities (u) were measured at a frequency of
2 MHz in these solutions through interferometric method (using
Mittals F-81 model) at 298.15 and 308.15 K (0.05 K). The
error in velocity measurements is 0.1%. The other experimental details are the same as reported earlier [24].
3. Results and discussion
Experimental values of densities (), viscosities () and ultrasonic velocities (u) of mixtures at 298.15 and 308.15 K are listed
as a function of mole fraction in Table 2. The density values
have been used to calculate excess molar volumes (VE ) using
the following equation:
 


x 2 M2
x1 M1 + x2 M2
x 1 M1
E

(1)
V =

12
1
2
where 12 is the density of the mixture and x1 , M1 , 1 , and
x2 , M2 , 2 are the mole fraction, the molecular weight, and the
density of pure components 1 and 2, respectively.
The viscosity deviations () were calculated using
 = 12 x1 1 x2 2

(2)

where 12 is the viscosity of the mixture and x1 , x2 and 1 , 2

are the mole fraction and the viscosity of pure components 1 and
2, respectively.
The ultrasonic velocity u was used to calculate the isentropic
compressibility s by the equation
s =

1
u2

(3)

The deviation from isentropic compressibility, (s ), was

obtained using the relation:
s = s,mix x1 s1 x2 s2

(4)

where s,mix is the experimental isentropic compressibility of the

mixture, x1 , x2 and s1 , s2 are the mole fraction and isentropic
compressibility of pure components.
The excess molar volumes and deviations in viscosity and
isentropic compressibility were fitted to RedlichKister [15]
equation of the type
Y = x1 x2

n


ai (x1 x2 )i

(5)

where Y is either VE , or , or s , and n is the degree of

polynomial. Coefficients ai were obtained by fitting Eq. (5) to
experimental results using a least-squares regression method. In
each case, the optimum number of coefficients is ascertained
from an examination of the variation in standard deviation ().
was calculated using the relation

1/2
(Yexptl Ycalcd )2
(Y ) =
(6)
N n
where N is the number of data points and n is the number of
coefficients. The calculated values of the coefficients ai along
with the standard deviations () are given in Table 3.
The variation of VE with the mole fraction x1 of methylbenzene for hexan-2-ol, heptan-2-ol and octan-2-ol at 298.15
is represented in Fig. 1. It is seen that the VE values are positive for binary mixtures of methylbenzene with hexan-2-ol,
heptan-2-ol and octan-2-ol over the entire composition range
at both the temperatures. It is well known fact that alkanols
are self-associated through hydrogen bonding. The mixing of
methylbenzene with alkanols is expected to induce changes in
hydrogen boding equilibrium and electrostatic interactions with
different resultant contributions to the volumes of mixtures.
Weakening of interactions between molecules of methylbenzene
tend to result in an increase in volume. Similarly, the disruption
of alkanol multimers through breaking of hydrogen bonds makes
a positive contribution to VE . Our VE values of binary mixtures
of methylbenzene with hexan-2-ol at x = 0.5 (0.240 cm3 mol1 )
is in good agreement with the values of Ortega et al. [16],
being 0.236 cm3 mol1 . For the alkan-2-ols the VE values fol-

90

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

Table 2
Density (), viscosity (), ultrasonic velocity (u), isentropic compressibility (s ), excess molar volume (VE ), deviation in viscosity () and deviation in isentropic
compressibility(s ) for methylbenzene (1) + 2-alkanols (2) at 298.15 and 308.15 K
(mPa s)

 (mPa s)

u (m s1 )

s (TPa1 )

s (TPa1 )

Methylbenzene (1) + hexan-2-ol (2) 298.15 K

0.0000
0.81084
0.000
0.0497
0.81291
0.017
0.1007
0.81508
0.031
0.1588
0.81753
0.058
0.1993
0.81929
0.073
0.2520
0.82150
0.108
0.2999
0.82359
0.134
0.3495
0.82577
0.162
0.4016
0.82816
0.183
0.4468
0.83021
0.210
0.5012
0.83270
0.243
0.5502
0.83510
0.257
0.6003
0.83761
0.269
0.6492
0.84023
0.264
0.7008
0.84305
0.256
0.7476
0.84575
0.237
0.8006
0.84893
0.206
0.8502
0.85209
0.160
0.8945
0.85501
0.114
0.9407
0.85809
0.067
1.0000
0.86218
0.000

4.105
3.548
3.087
2.741
2.427
2.110
1.849
1.619
1.439
1.318
1.165
1.061
0.953
0.920
0.866
0.840
0.762
0.686
0.649
0.638
0.554

0.000
0.381
0.660
0.800
0.970
1.100
1.191
1.245
1.240
1.200
1.160
1.090
1.020
0.880
0.750
0.610
0.500
0.400
0.280
0.127
0.000

1290
1286
1284
1281
1278
1274
1270
1269
1267
1265
1265
1264
1263
1267
1268
1271
1276
1280
1286
1294
1306

741
744
744
745
747
750
753
752
752
753
750
749
748
741
738
732
723
716
707
696
680

0
6
8
12
17
23
28
30
33
37
37
39
41
37
38
35
29
25
20
12
0

Methylbenzene (1) + hexan-2-ol (2) 308.15 K

0.0000
0.80175
0.000
0.0497
0.80369
0.035
0.1007
0.80585
0.050
0.1588
0.80816
0.096
0.1993
0.80989
0.113
0.2520
0.81203
0.158
0.2999
0.81399
0.201
0.3495
0.81607
0.242
0.4016
0.81834
0.278
0.4468
0.82035
0.308
0.5012
0.82290
0.330
0.5502
0.82527
0.346
0.6003
0.82779
0.354
0.6492
0.83036
0.352
0.7008
0.83328
0.327
0.7476
0.83592
0.313
0.8006
0.83910
0.278
0.8502
0.84225
0.230
0.8945
0.84520
0.175
0.9407
0.84838
0.112
1.0000
0.85279
0.000

2.920
2.566
2.273
1.935
1.703
1.519
1.303
1.153
1.046
0.962
0.850
0.794
0.766
0.689
0.671
0.611
0.579
0.561
0.531
0.527
0.496

0.000
0.234
0.403
0.600
0.734
0.790
0.890
0.920
0.901
0.875
0.855
0.792
0.699
0.657
0.550
0.497
0.400
0.298
0.221
0.113
0.000

1255
1251
1245
1243
1240
1237
1235
1232
1230
1229
1228
1228
1228
1229
1230
1232
1237
1242
1249
1257
1270

792
795
801
801
803
805
805
807
808
807
806
804
801
797
793
788
779
770
758
746
727

0
6
15
18
22
27
30
35
40
41
44
45
45
45
44
42
37
32
23
14
0

Methylbenzene (1) + heptan-2-ol (2) 298.15 K

0.0000
0.81374
0.000
0.0514
0.81549
0.023
0.1014
0.81727
0.040
0.1469
0.81888
0.064
0.2008
0.82083
0.094
0.2519
0.82270
0.126
0.3007
0.82454
0.157
0.3480
0.82633
0.192
0.4006
0.82845
0.221
0.4526
0.83061
0.248
0.5002
0.83262
0.277
0.5501
0.83490
0.290
0.6011
0.83736
0.294
0.6574
0.84016
0.300
0.7011
0.84250
0.290
0.7560
0.84559
0.270
0.8000
0.84822
0.244

5.088
4.335
3.878
3.392
2.918
2.526
2.195
1.900
1.622
1.396
1.240
1.064
0.931
0.853
0.778
0.741
0.691

0.000
0.520
0.750
1.030
1.260
1.420
1.530
1.610
1.650
1.640
1.580
1.530
1.431
1.255
1.131
0.920
0.770

1314
1309
1303
1298
1293
1288
1283
1279
1276
1272
1271
1269
1268
1268
1269
1273
1276

712
716
721
725
729
733
737
740
741
744
743
744
743
740
737
730
724

0
5
11
17
22
27
33
37
40
44
45
47
48
47
46
40
36

x1

(g cm3 )

VE (cm3 mol1 )

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

91

Table 2 (Continued)
(g cm3 )

VE (cm3 mol1 )

(mPa s)

 (mPa s)

u (m s1 )

s (TPa1 )

s (TPa1 )

0.85169
0.85488
0.85812
0.86218

0.193
0.140
0.091
0.000

0.650
0.611
0.589
0.554

0.566
0.392
0.204
0.000

1283
1289
1296
1306

713
704
694
680

27
20
12
0

Methylbenzene (1) + heptan-2-ol (2) 308.15 K

0.0000
0.80488
0.000
0.0514
0.80649
0.045
0.1014
0.80820
0.071
0.1469
0.80975
0.102
0.2008
0.81162
0.141
0.2519
0.81337
0.190
0.3007
0.81512
0.231
0.3480
0.81685
0.273
0.4006
0.81886
0.313
0.4526
0.82097
0.344
0.5002
0.82292
0.377
0.5501
0.82513
0.395
0.6011
0.82750
0.408
0.6574
0.83022
0.418
0.7011
0.83253
0.408
0.7560
0.83562
0.380
0.8000
0.83825
0.348
0.8540
0.84171
0.290
0.9009
0.84495
0.223
0.9475
0.84850
0.127
1.0000
0.85279
0.000

3.683
3.171
2.776
2.459
2.155
1.875
1.665
1.485
1.332
1.199
1.078
0.992
0.904
0.818
0.756
0.679
0.641
0.570
0.518
0.501
0.496

0.000
0.348
0.584
0.756
0.888
1.005
1.060
1.089
1.075
1.042
1.011
0.938
0.863
0.770
0.692
0.595
0.492
0.392
0.294
0.162
0.000

1274
1267
1261
1256
1251
1246
1243
1238
1235
1232
1230
1229
1228
1229
1230
1234
1238
1243
1250
1258
1270

765
772
778
783
787
792
794
799
801
803
803
802
801
797
794
786
778
769
757
745
727

0
8
16
22
28
34
38
44
48
52
54
55
56
55
53
47
42
35
25
15
0

Methylbenzene (1) + octan-2-ol (2) 298.15 K

0.0000
0.81708
0.000
0.0494
0.81849
0.020
0.0991
0.81989
0.053
0.1497
0.82139
0.082
0.1999
0.82291
0.115
0.2511
0.82447
0.156
0.2996
0.82603
0.190
0.3540
0.82783
0.230
0.3998
0.82943
0.260
0.4469
0.83112
0.293
0.5000
0.83315
0.322
0.5509
0.83522
0.343
0.5995
0.83733
0.355
0.6486
0.83967
0.349
0.7010
0.84233
0.334
0.7477
0.84488
0.311
0.7989
0.84789
0.272
0.8513
0.85118
0.224
0.9000
0.85446
0.170
0.9511
0.85812
0.107
1.0000
0.86218
0.000

6.429
5.547
4.813
4.186
3.559
3.069
2.652
2.239
1.966
1.690
1.462
1.263
1.104
0.947
0.880
0.791
0.716
0.628
0.636
0.574
0.554

0.000
0.592
1.034
1.364
1.695
1.885
2.017
2.110
2.115
2.114
2.030
1.930
1.803
1.672
1.431
1.245
1.020
0.800
0.505
0.268
0.000

1328
1323
1317
1313
1306
1299
1294
1289
1285
1279
1277
1273
1271
1270
1270
1271
1273
1278
1286
1294
1306

694
698
703
706
712
719
723
727
730
736
736
739
739
738
736
733
728
719
708
696
680

0
5
10
14
20
27
32
37
40
46
48
51
52
52
51
48
44
36
26
15
0

Methylbenzene (1) + octan-2-ol (2) 308.15 K

0.0000
0.80989
0.000
0.0494
0.81113
0.040
0.0991
0.81240
0.084
0.1497
0.81376
0.124
0.1999
0.81511
0.173
0.2511
0.81648
0.233
0.2996
0.81785
0.285
0.3540
0.81946
0.340
0.3998
0.82091
0.379
0.4469
0.82249
0.414
0.5000
0.82435
0.451
0.5509
0.82629
0.473
0.5995
0.82832
0.478
0.6486
0.83043
0.487

4.365
3.837
3.373
2.975
2.563
2.264
1.986
1.685
1.488
1.276
1.121
1.004
0.912
0.836

0.000
0.337
0.608
0.811
1.029
1.129
1.220
1.310
1.330
1.360
1.310
1.230
1.134
1.020

1292
1285
1280
1274
1268
1261
1257
1250
1247
1243
1239
1235
1234
1232

740
747
751
757
763
770
774
781
783
787
790
793
793
793

0
7
12
19
25
33
37
45
48
52
56
60
59
61

x1
0.8540
0.9009
0.9475
1.0000

92

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

Table 2 (Continued)
x1
0.7010
0.7477
0.7989
0.8513
0.9000
0.9511
1.0000

(g cm3 )

VE (cm3 mol1 )

(mPa s)

 (mPa s)

u (m s1 )

s (TPa1 )

s (TPa1 )

0.83294
0.83537
0.83832
0.84160
0.84493
0.84866
0.85279

0.472
0.445
0.391
0.320
0.236
0.140
0.000

0.770
0.707
0.649
0.569
0.573
0.506
0.496

0.883
0.765
0.626
0.502
0.310
0.179
0.000

1233
1234
1237
1241
1247
1255
1270

790
786
780
772
761
748
727

58
55
49
42
32
20
0

Table 3
Parameters and standard deviations of Eqs. (5) and (6) for methylbenzene + 2-alkanols
Temperature (K)
Toluene + hexan-2-ol
VE (cm3 mol1 )

a0

a1

a2

a3

298.15
308.15

0.960
1.286

0.821
0.784

0.246
0.014

0.444

0.004
0.008

 (mPa s)

298.15
308.15

4.548
3.402

2.698
1.827

0.615
0.091

0.429

0.036
0.018

s (TPa1 )

298.15
308.15

150.407
173.879

68.571
75.246

5.210
36.023

298.15
308.15

1.071
1.477

0.798
1.024

0.005
0.2615

 (mPa s)

298.15
308.15

6.244
3.956

1.901
2.081

0.7205
1.4075

s (TPa1 )

298.15
308.15

186.021
214.196

72.990
80.501

18.785
23.973

298.15
308.15

1.252
1.778

0.748
1.124

0.034
0.079

0.253

0.001
0.006

 (mPa s)

298.15
308.15

8.102
5.087

1.051
0.276

0.689

0.021
0.024

s (TPa1 )

298.15
308.15

193.014
217.858

18.867
68.226

50.906

0.691
1.495

Toluene + heptan-2-ol
VE (cm3 mol1 )

Toluene + octan-2-ol
VE (cm3 mol1 )

3.1864
1.947
117.703
108.349

0.928
0.550

0.092

0.005
0.006

1.7132

0.038
0.014

8.7292
12.4082

0.656
0.658

Table 4
Correlated results of McAllisters multi-body models
Mixture

T (K)

Three-body model

Four-body model

12

21

1112

1122

2221

Methylbenzene + hexan-2-ol

298.15
308.15

1.120
0.718

1.760
1.381

3.91
2.65

1.109
0.748

0.970
0.747

2.603
1.933

0.126
0.097

Methylbenzene + heptan-2-ol

298.15
308.15

0.822
0.756

2.361
1.841

3.05
3.10

0.828
0.627

1.043
1.412

3.230
2.051

0.133
0.147

Methylbenzene + octan-2-ol

298.15
308.15

0.836
0.766

3.054
2.265

1.62
2.34

0.778
0.723

1.360
1.074

3.846
2.844

0.097
0.135

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

93

and the four-body McAllister model is defined by

ln = x14 ln 1 + 4 x13 x2 ln 1112 + 6 x12 x22 ln 1122



x 2 M2
3
4
+4 x1 x2 ln 2221 + x2 ln 2 ln x1 +
M1


3 + (M2 /M1 )
+ 4 x13 x2 ln
+ 6 x12 x22 ln
4




1 + (M2 /M1 )
1 + (3M2 /M1 )

+ 4 x1 x23 ln
2
4


M2
+ x24 ln
(8)
M1
Fig. 1. Excess molar volumes (VE ) at 298.15 K for x1 methylbenzene + (1 x1 )
alkanols: () hexan-2-ol, () heptan -2-ol, and () octan-2-ol.

low the order hexan-2-ol < heptan-2-ol < octan-2-ol. This may
be due to the fact that the extent of hydrogen bonding and selfassociation decreases with increasing chain length of alkan-2ols.
Fig. 2 depicts the variation of  with the mole fraction x1 of
methylbenzene.  values are negative for binary mixtures of
methylbenzene with hexan-2-ol, heptan-2-ol and octan-2-ol over
the entire composition range at both the temperatures. The 
values become more negative with an increase in chain length
of alkan-2-ols, suggesting a decrease in hetero association of
molecules with an increase in molar mass of alkanols.
McAllisters multi-body interaction models [17] have been
used to correlate the kinematic viscosities of binary liquid mixtures. The three-body McAllister model is defined by
ln = x13 ln 1 + x23 ln 2 + 3 x12 x2 ln 12 + 3 x1 x22 ln 21




  
M2
x 2 M2
2
2
+3 x1 x2 ln
+
ln x1 +
M1
3
3M1


  

1
M2
2M2
+3x1 x22 ln
+ x23 ln
(7)
+
3
3M1
M1

Fig. 2. Deviations in viscosity () at 298.15 K for x1 methylbenzene + (1 x1 )

alkanols: () hexan-2-ol, () heptan-2-ol, and () octan-2-ol.

where 12 , 21 , 1122 , 1122 , 2221 , are interaction parameters

and M1 and M2 are molecular weights of components 1 and 2.
The correlating ability of Eqs. (7) and (8) was tested by calculating the percentage standard deviation (%) between the
experimental and calculated viscosity as

1/2

  100(exptl calcd ) 2
1

% =
(9)
exptl
nm
where n represents the number of experimental points and m
represents the number of coefficients. Table 4 includes the different parameters for McAllisters three-body and four body
models. From Table 4, it is clear that McAllisters four-body
interaction model gives a better result than the three-body model
for correlating the kinematic viscosities of the binary mixtures
studied.
The variation of s with composition of mixture (x1 of
methylbenzene) is represented in Fig. 3. Kiyohara and Benson
[18] have suggested that s is the resultant of several opposing
effects. A strong molecular interaction through charge transfer,
dipole induced dipole and dipoledipole [19] interactions, interstitial accommodation and orientational ordering lead to a more
compact structure makes s negative and break up of the alkanol structures tend to make s positive. The positive values of
s for mixtures of methylbenzene with hexan-2-ol, heptan-2ol, and octan-2-ol signify decreasing dipoledipole interactions

Fig. 3. Deviations in isentropic compressibility (s ) at 298.15 K for x1

methylbenzene + (1 x1 ) alkanols: () hexan-2-ol, () heptan-2-ol, and ()
octan-2-ol.

94

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

show OH at 3347 and 3348 cm1 . When methylbenzene is

mixed with reported alkanols, a frequency shift of OH is
observed at higher wavelength, i.e. 3357 and 3363 cm1 , respectively. A representative figure of FTIR of methylbenzene with
heptan-2-ol is shown in Fig. 4. This we can ascribe as due to the
breaking of homo associated hydrogen bond i.e. OH OH
and formation of complex between the hetero components of
the liquid mixtures.
NMR is a powerful tool for identifying and characterizing
hydrogen bonds and dipoledipole interactions. In the case of
weak hydrogen bonding, diamagnetic anisotropy of the donor
atom or group may become dominant. The PMR spectrum of
pure liquids and liquid mixtures has been recoded in CDCl3 at
room temperature. It is seen that there is shifting of aromatic
protons in the liquid mixtures, i.e. methylbenzene (77.38),
methylbenzene + heptan-2-ol (7.097.23), shown in Fig. 5, and
methylbenzene + 2-octanol (7.157.22). This is evidently the
case of H interaction between electron rich phenyl ring of
methylbenzene, as CH3 group enhances the electron density of
the ring, and H- atom of OH group of 2-alkanol.
Recently Jouyban and Acree [22,23] proposed a model for
correlating the density and viscosity of liquid mixtures at various
temperatures. The proposed equation is


 Aj (f1 f2 )j
ln ym,T = f1 ln y1,T + f2 ln y2,T + f1 f2
T
(12)
where ym,T , y1,T and y2,T is density, or viscosity of the mixture
and solvents 1 and 2 at temperature T, respectively, f1 and f2 are
the mole fraction, and Aj are the model constants.
The correlating ability of the JouybanAcree model was
tested by calculating the average percentage deviation (APD)
Fig. 4. An FTIR spectra of methylbenzene + heptan-2-ol at 0.6 mol fraction of
methylbenzene.

due to decreasing proton donating abilities with increasing chain

length of alkan-2-ols. De-clustering of alkan-2-ols in the presence of methylbenzene may also lead to positive s values. It
is seen that the maximum in VE and s occur at about the same
mole fraction of methylbenzene for all the three binary mixtures
suggesting the formation of a similar type of complex in all the
three binary mixtures.
Conclusions drawn from density, viscosity and ultrasonic
velocity measurements could be well supported by spectroscopic
techniques [20,21].
The FTIR spectrum of a substance is affected by the influence by the medium in which it is phased due to presence of
specific interactions between the proton donors (e.g. ROH)
and acceptors (e.g. aromatic rings). In present case an IR of
the two mixtures, namely, methylbenzene (x1 ) + heptan-2-ol
(1 x1 ) and methylbenzene + 2-octanol at x1 = 0.6 have been
recorded at room temperature and then it is compared with the
spectra of the corresponding pure components of the liquid mixtures. Neat IR of self-associated 2-heptan-2-ol and 2-octanol

Fig. 5. Varian mercury YH-300 PMR spectra of methylbenzene + heptan-2-ol

at 0.6 mol fraction of methylbenzene.

M. Hasan et al. / Fluid Phase Equilibria 252 (2007) 8895

95

Table 5
Parameters of JouybanAcree model and average percentage deviation for densities, viscosities and ultrasonic velocities
System

A0

A1

A2

APD

Density
Methylbenzene + hexan-2-ol
Methylbenzene + heptan-2-ol
Methylbenzene + octan-2-ol

5.439
7.655
9.328

2.191
3.249
4.15

0.146
0.766
0.954

0.0298
0.0354
0.0331

Viscosity
Methylbenzene + hexan-2-ol
Methylbenzene + heptan-2-ol
Methylbenzene + octan-2-ol

351.142
306.14
299.454

42.231
115.914
185.986

193.508
47.1
0.583

3.3377
2.7267
1.5262

Ultrasonic velocity
Methylbenzene + hexan-2-ol
Methylbenzene + heptan-2-ol
Methylbenzene + octan-2-ol

31.869
38.96
38.759

14.503
14.18
24.783

4.486
1.962
9.814

0.1333
0.1416
0.1222

between the experimental and calculated density and viscosity

as


|yexptl ycalcd |
100 
APD =
(13)
N
yexptl
where N is the number of data points in each set. The optimum
numbers of constants Aj , in each case, were determined from the
examination of the average percentage deviation value.
The JouybanAcree model was not previously applied to
ultrasonic velocity measurements, we extend the Jouyban
Acree model (Eq. (12)) to ultrasonic velocity of the liquid mixtures with f as the mole fraction and again apply Eq. (13) for
correlating ability of the model.
The constant Aj calculated from the least squares analysis,
are presented in Table 5 along with the average percentage deviation (APD). The proposed model provides reasonably accurate
calculations for the density, viscosity and ultrasonic velocity of
binary liquid mixtures at various temperatures and the model
could be used in data modeling.
Acknowledgment
Authors thank Principal M.S.G. College for the facilities provided.
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