Chemical Physics xxx (2016) xxxxxx

Contents lists available at ScienceDirect

Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Ultrasonic and spectral studies on charge transfer complexes of anisole

and certain aromatic amines
R. Rajesh a, R. Raj Muhamed a, A. Justin Adaikala Baskar b, V. Kannappan c,
a

Department of Physics, Jamal Mohamed College, Tiruchirappalli 621 004, India

Department of Chemistry, Loyola College, Chennai 600034, India
c
Department of Chemistry, Presidency College, Chennai 600 005, India
b

a r t i c l e

i n f o

Article history:
Available online xxxx
Keywords:
Thermodynamic properties
Anisoleamines
Hydrogen bonded complexes

a b s t r a c t
Stability constants of two complexes of anisole with aniline and N-methylaniline (NMA) are determined
from the measured ultrasonic velocity in n-hexane medium at four different temperatures. Acoustic and
excess thermo acoustic parameters [excess ultrasonic velocity (uE), excess molar volume (VE), excess
internal pressure (pEi )] are reported for these systems at four different temperatures. The trend in acoustic
and excess parameters with concentration in the two systems establishes the formation of hydrogen
bonded complexes between anisole and the two amines. Thermodynamic properties are computed for
the two complexes from the variation in K with temperature. The formation of these complexes is also
established by UV spectral method and their spectral characteristics and stability constants are determined. K values of these complexes obtained by ultrasonic and UV spectroscopic techniques agree well.
Aniline forms more stable complex than N-methylaniline with anisole in n-hexane medium.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Ultrasonic technique is widely employed in the study of intermolecular interaction and helpful in the development of molecular
sciences. The intermolecular interaction changes the structural
arrangement of the molecules [1,2]. The study of weak interactions
in liquid mixtures is helpful in understanding physical properties
[36]. The strength of these weak interactions can be assessed in
terms of the association constant and other thermodynamic
parameters. The determination of equilibrium constant of weak
interacting systems and influence of temperature on such systems
was studied by ultrasonic method by several investigators [710]
to evaluate thermodynamic parameters. Hydrogen bond plays
important role in strengthening of molecular interactions and stabilizing supra-molecular complexes and such systems [1113] play
a vital role in chemical, physical and biological processes.
Amines in pure state are self-associated through inter molecular
hydrogen bonds. They are both p-as well as n-electron donors which
allow them to have specific interactions with other electron deficient molecules. The complexes formed between esters and amines,
phenols and ketones have been attributed to the hydrogen bonding
between electron-rich carbonyl oxygen and active hydrogen.
Corresponding author.

Higuchi and his coworkers [14] have investigated the complex formation of caffeine with a number of acidic drugs. They attributed
the interaction between caffeine and drug to dipoledipole force
or hydrogen bonding between the polarized carbonyl groups of caffeine and the hydrogen atom of the acid. Similarly, in the formation
of 1:1 complex between p-benzoquinone and hydroquinone, hydrogen bond exists between the donor and acceptor components [15].
Recently, we determined the equilibrium constants for the protonation of N,N-dimethylaniline with three isomeric cresols by
ultrasonic method and correlated the hydrogen bond stabilized
protonated species with the molecular properties of proton donors
[16]. In this paper, the results obtained in the study of molecular
interaction between anisole with two amines namely aniline and
N-methylaniline in n-hexane medium are presented. Acoustic
parameters such as intermolecular free length (Lf), adiabatic compressibility (j), internal pressure (p), free volume (Vf), molar volume (Vm), molecular cohesive energy (MCE) are computed for the
three ternary systems at four different temperatures (293.15,
298.15, 303.15, 308.15 K) in n-hexane medium from the measured
ultrasound velocity, density and viscosity values. Excess properties
(uE, jE, LEf , pEi , VEf and VEm) are reported and discussed. The formation
constants and thermodynamic properties are also reported for the
two complexes. The formation of hydrogen bonded complexes in
the two systems is confirmed by UV spectral investigation.

E-mail address: venu_kannappan@rediffmail.com (V. Kannappan).

http://dx.doi.org/10.1016/j.chemphys.2016.05.028
0301-0104/ 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: R. Rajesh et al., Chem. Phys. (2016), http://dx.doi.org/10.1016/j.chemphys.2016.05.028

R. Rajesh et al. / Chemical Physics xxx (2016) xxxxxx

2. Experimental
Merck samples of anisole, aniline and N-methylaniline, were
purified by distillation before use. The solvent n-hexane used
was spectral grade Aldrich sample. The purity of these chemicals
was ascertained by comparing the measured densities and ultrasonic velocity (Table 1) at the investigated temperatures with the
reported literature values [1731]. The liquid mixtures of required
concentrations were prepared by weighing appropriate amounts of
pure liquids and mixed in airtight stopper bottles to minimize
evaporation losses. The density of the pure liquids and their ternary systems were found by using a 10 ml specific gravity bottle.
All the weighings were made with a digital balance (Shimadzu,
Japan) of accuracy 0.1 mg. The ultrasonic velocities of pure liquids
and ternary liquid mixtures were measured using a single crystal
variable path ultrasonic interferometer operating at 2 MHz frequency supplied by Mittal Enterprises, Model F81. The accuracy
in the measurement of ultrasonic velocity was 0.2 ms
1. Viscosity
measurements were made with an Ostwalds viscometer in which
the flow time for solutions was measured through a digital stop
clock of accuracy 0.01 s. The temperature of the samples was
maintained constant to an accuracy of 0.1 K by digitally controlled thermostatic water bath. The results of u, q and g summarized in Table 2 represent the average of at least five independent

measurements for each composition of the ternary liquid mixtures.

From the measured values of ultrasonic velocity (u), density (q)
and viscosity (g) various acoustical and excess thermo acoustical
parameters were calculated using the standard formulae as
reported in the literature [710].
3. Results and discussion
Hydrogen bonded complexes formed between a proton donor
molecule and a base (containing nitrogen or oxygen lone-pair
donors) play vital role in biological systems. The partial chargetransfer nature of such bonds is the reason for the stability of these
complexes [32]. Chowdhury investigated anilinediethyl ether and
anilinetetrahydrofuran complexes using one-color-resonant
two-photon ionization spectroscopy in combination with infrared
depletion spectroscopy and concluded that hydrogen bonded
complexes are formed in these systems [33]. They found that fast
vibrational relaxation occurs in the hydrogen-bonded aniline
tetrahydrofuran complex. Here, we used anisole, aromatic ether
in the complex formation with two aromatic primary and
secondary that can form hydrogen bond with ethereal oxygen of
anisole.
3.1. Acoustical parameters

Table 1
Ultrasonic velocity and density values of pure components at different temperatures.
Components

n-hexane

Anisole

Aniline

N-methyl
aniline

a
b
c
d
e
f
g
h
i
j
k
l
m
n
o

Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.

[17].
[18].
[19].
[20].
[21].
[22].
[23].
[24].
[25].
[26].
[27].
[28].
[29].
[30].
[31].

Temp
(K)

Velocity (ms
1)

Density (kg m
3)

Experimental
value

Literature
value

Experimental
value

Literature
value

293

1099.6

1100a

0.6603

298

1076.2

0.6549

303

1058.1

1077c
1075.8d
1077e
1058.3f
1055a
1032a

0.6597a
0.6593b
0.6551c
0.6552a
0.6548d
0.6506a
0.6505b
0.6460a

0.6508

308

1039

293
298

1424.8
1408.1

1408g
1407h

0.9922
0.9882

0.6457

303
308

1390.6
1376.1

0.9846
0.9798

293
298

1650.6
1639.2

1.0190
1.0169

303

1624.8

1651.3j
1638.6k
1635l
1619.2k
j

0.9891g
0.9891h
0.9889i

308

1606.6

1595.1

1.0089

1.0217k
1.0174k
1.0172l
1.0130k
1.0129m

293
298
303
308

1584.0
1564.1
1547.2
1532.8

1582.5n
1563.9n
1546.0o

0.9865
0.9819
0.9767
0.9703

0.9862n
0.9822n
0.9782o

1.0138

The values of ultrasonic velocity (u), density (q) and viscosity

(g) for the two ternary systems at various concentrations and at
four different temperatures are given in Table 2. Plots of ultrasonic
velocity versus concentration for the two ternary systems are
depicted in Fig. 1(a) and (b). Plots of u versus concentration are
similar in the two ternary systems indicating the presence of similar type of interaction in both the systems. It is observed that the
ultrasonic velocity increases with increase in concentration in both
the systems. However, the variation is not perfectly linear. This
non-linear variation in u with concentration suggests that there
are specific solutesolute interactions in the two systems as the
solutesolvent interaction in these ternary systems is less prominent due to chemical inertness and non-polar nature of n-hexane
[34]. This strong solutesolute interaction of unlike molecules
may be attributed to the formation of hydrogen bonded complex
between anisole and amine [35]. The formation of complex is also
supported by the significant increase in density and the viscosity
with concentration. It is found that the ultrasonic velocity
decreases with increase in temperature in a system at a given concentration. This may be due to thermal agitation which affects the
intermolecular interaction [36]. The increase in density and viscosity with concentration in both the systems suggests that the extent
of complex formation increases with the increase in concentration.
The complex formation can be established by the variation in
the adiabatic compressibility of ternary liquid mixtures. It is
observed that isentropic compressibility js decreases with
increasing concentration (Table 3) in the two systems. It is primarily the compressibility that changes with structure which leads to a
change in ultrasonic velocity. The decrease in isentropic compressibility (js) in liquid mixtures indicates that there is a definite
contraction on mixing and the significant variation is attributed
to H-bonded complex formation [37]. Intermolecular free length
(Lf) reflects similar behaviour as isentropic compressibility. The
decrease in compressibility brings the molecules to close packing,
resulting in the decrease of intermolecular free length. There is regular decrease in Lf with increase in concentration (Table 3) in both
the systems at a given temperature. This indicates that the molecules are closer in the system due to strong interaction between
solute molecules in the ternary mixtures. The disruption of molecular interactions with rise in temperature makes the molecules to

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Table 2
Measured values of ultrasonic velocity (u), density (q) and coefficient viscosity (g) of anisole-aniline and anisole-N-methylaniline systems in n-hexane at different temperatures.
Solvent: n-hexane

1

C mol kg

[amines] = [anisole]
Anisole + Aniline + n-hexane
293 K

Anisole + NMA + n-hexane

298 K

303 K

308 K

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

1110.0
1115.1
1119.8
1125.5
1130.5
1134.3
1140.1
1147.2
1151.3
1159.4

1089.6
1093.5
1097.3
1101.1
1106.3
1112.1
1116.5
1122.6
1130.0
1136.3

1068.5
1072.4
1077.3
1081.0
1088.8
1093.2
1098.2
1103.1
1110.0
1115.9

1044.7
1048.7
1054.2
1061.5
1067.0
1072.0
1078.1
1084.5
1089.7
1095.4

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

673.4
678.0
681.5
685.6
690.8
696.0
701.2
706.8
712.2
717.0

668.6
674.1
679.0
682.9
686.1
691.0
696.3
700.8
707.2
712.5

663.7
670.8
674.9
680.4
684.5
688.0
693.1
697.8
703.2
709.0

661.5
665.8
670.8
676.6
681.6
685.2
691.0
695.4
700.0
706.1

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

0.3937
0.3976
0.4008
0.4047
0.4123
0.4183
0.4260
0.4332
0.4401
0.4489

0.3513
0.3579
0.3639
0.3671
0.3754
0.3812
0.3882
0.3941
0.4023
0.4092

0.3339
0.3406
0.3438
0.3480
0.3539
0.3575
0.3641
0.3711
0.3791
0.3869

0.3169
0.3203
0.3217
0.3284
0.3331
0.3390
0.3467
0.3552
0.3626
0.3698

1160

293 K
u (m s
1)
1107.8
1114.9
1119.0
1126.4
1130.9
1136.6
1143.3
1150.0
1154.8
1160.2
q (kg m
3)
671.4
675.9
681.7
688.0
693.5
698.7
704.0
710.2
716.7
723.0

3
g (10 mPa s)
0.3853
0.3898
0.3949
0.4035
0.4096
0.4187
0.4250
0.4333
0.4393
0.4479

298 K

303 K

308 K

1087.6
1093.0
1097.8
1102.0
1107.1
1110.9
1116.0
1121.2
1127.4
1134.7

1062.7
1068.5
1075.9
1081.0
1085.8
1090.0
1095.1
1099.6
1105.1
1112.3

1043.7
1047.2
1055.5
1059.8
1065.1
1068.9
1074.3
1079.0
1083.5
1089.0

667.2
674.5
677.9
684.3
689.0
694.4
700.2
707.1
714.0
720.1

663.6
670.3
675.0
681.1
685.4
690.2
696.5
702.9
708.0
714.2

661.6
665.2
672.1
678.6
682.1
687.1
693.5
699.0
705.3
710.8

0.3541
0.3591
0.3631
0.3699
0.3775
0.3842
0.3922
0.4031
0.4139
0.4208

0.3315
0.3357
0.3399
0.3452
0.3532
0.3612
0.3698
0.3761
0.3840
0.3922

0.3145
0.3197
0.3241
0.3296
0.3380
0.3459
0.3523
0.3598
0.3679
0.3754

1160

Anisole-Aniline

1140

1120

1120

u/ms

-1

u/ms

-1

1140

Anisole - N-methylaniline

1100

1100

1080

1080

1060

1060

1040
0.00

0.02

1040
0.00

Conc. / mol Kg

0.04
0.06
-1
Conc. / mol Kg

(a)

(b)

0.04

0.06

0.08

0.10

-1

0.02

0.08

0.10

Fig. 1. Plot of ultrasonic velocity versus concentration (a) aniline and (b) N-methylaniline with anisole in n-hexane system at different temperatures (j) T = 293 K, (d) 298 K,
() 303 K and (.) 308 K.

move apart and the systems become more compressible. This is

well reflected with the increase in the values of Lf and js with
increase of temperature in the two systems.
The internal pressure (pi) values for two ternary systems are
calculated at different concentration and presented in Table 3.
Plots of pi against concentration are depicted in Fig. 2(a) and (b).
It is found that pi values are high in both the systems and it

increases with concentration indicating the existence of specific

solutesolute interactions. The non-linear variation of pi clearly
reveals the formation of complex. The increase in pi value increases
with concentration shows that the extent of complex formation
increases with concentration. However, the degree of complex formation decreases with increase in temperature as evident from the
decrease in pi value with temperature.

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Table 3
Computed values of adiabatic compressibility (j), intermolecular free length (Lf), acoustic impedance (Z) molar volume (Vm), internal pressure (pi), free volume (Vf) and molecular
cohesive energy (MCE) of anisoleaniline and anisole-N-methylanilinesystems in n-hexane at different temperatures.
Solvent: n-hexane
C mol kg
1

[amines] = [anisole]
Anisole + Aniline + n-hexane
293 K

298 K

Anisole + NMA + n-hexane

303 K

308 K

293 K

298 K

303 K

308 K

1.267
1.241
1.224
1.203
1.184
1.166
1.146
1.125
1.101
1.078

1.334
1.306
1.279
1.256
1.237
1.219
1.197
1.176
1.156
1.131

1.387
1.370
1.335
1.312
1.292
1.273
1.249
1.223
1.207
1.186

0.703
0.696
0.691
0.685
0.679
0.675
0.669
0.662
0.655
0.648

0.728
0.720
0.713
0.706
0.701
0.696
0.689
0.683
0.678
0.670

0.749
0.744
0.735
0.728
0.723
0.717
0.711
0.705
0.699
0.692

7.256
7.372
7.441
7.540
7.627
7.714
7.814
7.928
8.049
8.170

7.052
7.162
7.262
7.362
7.442
7.523
7.627
7.729
7.824
7.944

6.905
6.965
7.094
7.191
7.265
7.344
7.450
7.542
7.641
7.740

1.292
1.279
1.273
1.262
1.254
1.245
1.236
1.225
1.213
1.204

1.299
1.287
1.279
1.268
1.261
1.253
1.242
1.232
1.224
1.214

1.303
1.297
1.284
1.273
1.267
1.259
1.248
1.239
1.229
1.220

2.463
2.491
2.506
2.538
2.568
2.598
2.631
2.677
2.721
2.748

2.443
2.466
2.483
2.509
2.541
2.575
2.613
2.644
2.676
2.710

2.436
2.459
2.481
2.511
2.543
2.579
2.610
2.644
2.682
2.714

4.868
4.807
4.763
4.664
4.559
4.468
4.366
4.223
4.096
4.039

5.191
5.140
5.103
5.026
4.893
4.764
4.635
4.551
4.449
4.357

5.467
5.367
5.325
5.230
5.079
4.937
4.844
4.728
4.606
4.507

31.84
31.87
31.92

31.74
31.75
31.76

31.75
31.90
31.88

j (10
9 m2 N
1)
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

1.205
1.186
1.170
1.151
1.132
1.116
1.097
1.075
1.059
1.037

1.259
1.240
1.223
1.207
1.190
1.170
1.152
1.132
1.107
1.086

1.319
1.296
1.276
1.257
1.232
1.216
1.196
1.177
1.154
1.132

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

0.679
0.674
0.669
0.664
0.658
0.654
0.648
0.641
0.637
0.630

0.701
0.696
0.691
0.686
0.681
0.675
0.670
0.664
0.657
0.651

0.724
0.717
0.712
0.707
0.699
0.695
0.689
0.684
0.677
0.671

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

7.474
7.560
7.631
7.716
7.809
7.894
7.994
8.108
8.199
8.312

7.285
7.371
7.450
7.519
7.590
7.684
7.774
7.867
7.991
8.096

7.091
7.193
7.270
7.355
7.452
7.521
7.611
7.697
7.805
7.911

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

1.280
1.272
1.266
1.259
1.250
1.241
1.232
1.223
1.214
1.207

1.289
1.279
1.270
1.264
1.258
1.250
1.241
1.233
1.223
1.214

1.299
1.285
1.278
1.268
1.261
1.255
1.247
1.239
1.230
1.220

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

2.544
2.561
2.574
2.589
2.619
2.646
2.675
2.702
2.731
2.760

2.456
2.486
2.514
2.529
2.558
2.582
2.612
2.635
2.668
2.695

2.446
2.482
2.497
2.520
2.541
2.556
2.585
2.615
2.647
2.680

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

4.280
4.249
4.227
4.201
4.115
4.050
3.973
3.913
3.845
3.774

4.938
4.831
4.740
4.705
4.585
4.519
4.427
4.366
4.278
4.208

5.175
5.054
5.021
4.959
4.891
4.850
4.754
4.654
4.553
4.454

0.01
0.02
0.03

32.58
32.59
32.59

31.67
31.82
31.95

31.78
31.92
31.93

1.385
1.365
1.341
1.311
1.280
1.269
1.245
1.222
1.203
1.180

1.213
1.190
1.171
1.145
1.127
1.107
1.086
1.064
1.046
1.027
Lf ()
0.748
0.682
0.743
0.675
0.736
0.670
0.728
0.662
0.722
0.657
0.716
0.651
0.709
0.645
0.703
0.638
0.697
0.633
0.691
0.627
Z (105 kg m
2 s
2)
6.910
7.437
6.982
7.535
7.071
7.628
7.182
7.749
7.272
7.842
7.345
7.941
7.449
8.048
7.541
8.167
7.627
8.276
7.734
8.388
Vm (10
4 m3 mol
1)
1.303
1.284
1.295
1.276
1.286
1.266
1.275
1.255
1.267
1.246
1.261
1.238
1.251
1.229
1.243
1.219
1.235
1.209
1.225
1.199
pi (103 atm)
2.444
2.514
2.462
2.530
2.472
2.554
2.502
2.587
2.524
2.614
2.548
2.647
2.583
2.671
2.617
2.703
2.649
2.730
2.682
2.764

7
Vf (10 m3 mol
1)
5.411
4.409
5.360
4.379
5.370
4.322
5.264
4.230
5.197
4.165
5.101
4.064
4.977
4.013
4.845
3.936
4.735
3.883
4.636
3.802
MCE (kJ)
31.86
32.29
31.90
32.30
31.80
32.36

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Table 3 (continued)
Solvent: n-hexane
C mol kg
1

[amines] = [anisole]
Anisole + Aniline + n-hexane

0.04
0.05
0.06
0.07
0.08
0.09
0.10

Anisole + NMA + n-hexane

293 K

298 K

303 K

308 K

293 K

298 K

303 K

308 K

32.60
32.75
32.84
32.98
33.06
33.18
33.31

31.97
32.20
32.28
32.43
32.51
32.64
32.74

31.98
32.07
32.11
32.25
32.41
32.57
32.72

31.93
31.99
32.14
32.32
32.54
32.73
32.87

32.50
32.58
32.78
32.84
32.96
33.02
33.16

32.05
32.23
32.37
32.53
32.80
33.03
33.10

31.83
32.06
32.28
32.48
32.59
32.76
32.91

31.97
32.24
32.47
32.59
32.77
32.96
33.13

Anisole-Aniline

2.76x10

2.70x10
i / atm

i / atm

2.70x10

2.64x10

2.58x10

2.64x10

2.58x10

2.52x10

2.52x10

2.46x10

0.00

Anisole - N-methylaniline

2.76x10

2.46x10

0.02

0.04

0.06

0.08

0.10

0.00

0.02

-1

0.04

0.06

0.08

0.10

-1

Conc. / mol kg

Conc. / mol kg

(a)

(b)

Fig. 2. Plot of internal pressure versus concentration (a) aniline and (b) N-methylaniline with anisole in n-hexane system at different temperatures (j) T = 293 K, (d) 298 K,
() 303 K and (.) 308 K.

The variations in molar volume (Vm) and free volume (Vf) are
found to be the reverse trend observed in the variation of pi with
concentration. The decrease in molar volume with concentration
shows that there are strong molecular interactions between unlike
solute molecules. The decreasing trend of Vf with concentration
(Table 3) in the two systems shows that the close packing of the
molecules inside the shield is due to greater magnitude of existing

interactions [38]. The decrease in Vf may be attributed to the formation of enormous number of component molecules due to splitting of a major component or enlargement of existing molecules
due to the added component. The contribution due to the first reason will make close packing and hence pi value increases. Also
enlargement of the molecules increases the viscous force between
the layers and reduces the available volume between the compo-

33.3

33.3

33.0

33.0

32.7
MCE / k J

MCE / k J

32.7
32.4

32.4

32.1

32.1

31.8

31.8

0.00

Anisole - N-methylaniline

Anisole-Aniline

0.02

0.04
0.06
-1
Conc. / mol kg

(a)

0.08

0.10

0.00

0.02

0.04
0.06
-1
Conc. / mol kg

0.08

0.10

(b)

Fig. 3. Plot of MCE versus concentration (a) aniline and (b) N-methylaniline with anisole in n-hexane system at different temperatures (j) T = 293 K, (d) 298 K, () 303 K and
(.) 308 K.

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-0.4

-0.4

Anisole - Aniline

-0.8
2

m N
/ 10

-1.6

-1.2

-10

-1.2

-10

m N

-1

-1

-0.8

/ 10

Anisole - N-methylaniline

-1.6

-2.0

-2.0

-2.4

-2.4

0.00

0.02

0.04
0.06
-1
Conc. / mol kg

0.08

0.00

0.10

0.02

0.04
0.06
-1
Conc. / mol kg

0.08

0.10

(b)

(a)

Fig. 4. Plot of excess adiabatic compressibility versus concentration (a) aniline and (b) N-methylaniline with anisole in n-hexane system at different temperatures (j)
T = 293 K, (d) 298 K, () 303 K and (.) 308 K.

nents which is reflected by the increased values of pi [39]. The formation of complexes in the two systems is also supported by the
increase in acoustic impedance (Table 3) with concentration. Molar
cohesive energy (MCE) values at different concentrations are given
for the two systems in Table 3 and Fig. 3(a) and (b) contains the
plots of MCE against concentration. If the intermolecular forces
are small the cohesive energy is less and the molecules have relatively flexible chains. MCE increases with concentration in the two
systems indicating the dominance of solutesolute interaction at
higher concentration. The magnitude of MCE indicates the presence of strong dipoledipole attraction, probably intermolecular
hydrogen bonding in the ternary systems. The curves obtained in
the plots of MCE versus concentration are similar for the two systems indicating the formation of similar type of complexes in the
two systems.
3.2. Excess thermo acoustic properties
The values of excess parameters (uE, jE, LEf , ZE, VEm, pEi and VEf ) are
computed for the two ternary systems and listed in Table 3. The
positive values of uE in both the systems suggest the strong association of amines and growing dipoledipole interactions among the
component molecules. The rupture of cohesion and growing adhesion leading to the formation of hydrogen bonded complexes
between anisole and amine in n-hexane may give positive deviation of uE for the two ternary systems. Plots of excess compressibility (jE) versus concentration are depicted in Fig. 4(a) and (b). The
excess compressibility is due to decrease in free length as a result

of dipoledipole interactions, hydrogen bonding association or

complex formation of unlike molecules and also due to the interstitial accommodation of unlike molecules if there is a difference in
their size [40]. Positive values of uE and negative values of jE for
the two ternary systems of amines with anisole in n-hexane in
the investigated concentration range indicate the presence of
strong interactions between unlike molecules which may result
in complex formation [41,42]. The behavior of excess free length
(LEf ) for the liquid mixtures under investigation follows the same
trend as that of jE. This establishes the formation of hydrogen
bonded complexes in both the systems. The negative deviations
in free length for the ternary systems suggest that there is a possibility of interstitial accommodation of unlike molecules.
Excess acoustic impedance values are presented for the two
ternary systems at four different temperatures (Table 4). It has
been suggested that positive deviation in uE and ZE indicate the
presence of strong interactions between component molecules in
the mixture and formation of charge transfer or hydrogen bonded
complexes [43,44]. Thus, the deviations in acoustic impedance for
the two ternary systems clearly specify the presence of strong
charge transfer complexes. It is also observed that ZE value for a
given system increases with concentration indicating the increase
in extent of complex formation with concentration. Mutual loss of
dipolar or self-association due to addition of second component
and contributions due to difference in the size and shape of the
molecules and strong interactions such as dipoledipole, hydrogen
bonding or complex formation between unlike molecules are indicated by the sign and magnitude of excess molar volume (VEm). The

Table 4
Excess velocity (uE), excess compressibility (jE), excess free length (LEf ), excess acoustic impedance (ZE), excess molar volume (VEm), excess internal pressure (pEi ) and excess free
volume (VEf ) of anisoleaniline and anisoleN-methylaniline systems in n-hexane at different temperatures.
Solvent: n-hexane
C mol kg
1

[amines] = [anisole]
Anisole + Aniline + n-hexane
293 K

0.01
0.02
0.03
0.04
0.05
0.06

9.3
13.2
16.8
21.4
25.3
27.9

298 K
12.2
15.0
17.6
20.2
24.3
28.9

Anisole + NMA + n-hexane

303 K
9.2
11.9
15.7
18.2
24.8
28.1

308 K
4.4
7.2
11.5
17.6
21.9
25.8

293 K
uE (ms
1)
7.1
13.2
16.3
22.6
26.1
30.8

298 K

303 K

308 K

10.3
14.7
18.4
21.5
25.6
28.3

3.5
8.2
14.6
18.6
22.3
25.5

3.5
5.9
13.1
16.3
20.5
23.3

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Table 4 (continued)
Solvent: n-hexane
C mol kg
1

[amines] = [anisole]
Anisole + Aniline + n-hexane

Anisole + NMA + n-hexane

293 K

298 K

303 K

308 K

0.07
0.08
0.09
0.10

32.6
38.6
41.6
48.7

32.2
37.2
43.4
48.6

31.9
35.7
41.4
46.2

30.7
35.9
40.0
44.5

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

0.451

0.620

0.759

0.925

1.092

1.231

1.406

1.606

1.743

1.940

0.562

0.731

0.883

1.014

1.161

1.346

1.504

1.679

1.906

2.088

0.503

0.713

0.884

1.051

1.280

1.418

1.594

1.756

1.968

2.160

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

1.253

1.728

2.117

2.590

3.068

3.470

3.980

4.572

4.980

5.573

1.532

1.988

2.401

2.757

3.161

3.680

4.125

4.627

5.285

5.817

1.349

1.912

2.373

2.822

3.457

3.835

4.325

4.782

5.389

5.943

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

0.183
0.238
0.278
0.333
0.396
0.451
0.521
0.605
0.666
0.750

0.2061
0.2616
0.3104
0.3487
0.3893
0.4535
0.5131
0.5763
0.6709
0.7462

0.174
0.246
0.292
0.347
0.414
0.453
0.513
0.569
0.648
0.725

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

2.404

3.139

3.659

4.285

5.102

5.906

6.698

7.548

8.349

9.037

2.558

3.473

4.260

4.851

5.307

6.066

6.886

7.552

8.539

9.320

2.433

3.669

4.311

5.208

5.830

6.338

7.128

7.835

8.654

9.530

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

0.005
0.020
0.048
0.103
0.311
0.482
0.682
0.860
1.058
1.251

0.005
0.0152
0.133
0.147
0.163
0.212
0.432
0.574
0.825
1.016

0.021
0.020
0.088
0.241
0.372
0.445
0.658
0.874
1.118
1.374

0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10

1.488
1.263
1.132
0.951
0.177

0.392

1.076

1.593

2.199

2.825

5.013
4.030
3.202
2.942
1.827
1.250
0.406

0.117

0.916

1.536

3.130
2.011
1.774
1.246
0.658
0.335

0.533

1.443

2.367

3.268

293 K

36.4
42.1
45.9
50.3
jE (10
10 m2 N
1)

0.466

0.367

0.634

0.581

0.852

0.747

1.124

0.986

1.329

1.147

1.490

1.323

1.714

1.514

1.913

1.714

2.085

1.878

2.288

2.046
E
Lf (10
12 m)

1.231

1.012

1.670

1.600

2.247

2.063

2.981

2.737

3.536

3.192

3.976

3.695

4.596

4.251

5.154

4.838

5.635

5.324

6.215

5.825
ZE (105 kg m
2 s
2)
0.170
0.147
0.211
0.216
0.270
0.280
0.351
0.372
0.411
0.437
0.454
0.507
0.529
0.586
0.591
0.676
0.648
0.757
0.726
0.841
VEm (10
6 m3 mol
1)

3.045

2.018

3.744

2.734

4.568

3.683

5.531

4.708

6.328

5.569

6.855

6.364

7.777

7.164

8.433

8.108

9.116

9.085

10.05

10.01
E
pi (102 atm)
0.038

0.294
0.063

0.169
0.088
0.041
0.314
0.339
0.464
0.567
0.630
0.869
0.903
1.072
1.166
1.358
1.404
1.601
1.665
1.911
VEf (10
8 m3 mol
1)
2.369
2.761
1.948
2.526
2.150
2.026
1.186
1.174
0.606
0.586

0.260

0.354

1.403

0.799

2.626

1.502

3.640

1.963

4.533

2.712

298 K

303 K

308 K

32.4
36.5
41.7
48.0

29.5
33.0
37.4
43.6

27.6
31.2
34.7
39.1

0.490

0.728

0.876

1.061

1.231

1.382

1.562

1.757

1.967

2.179

0.357

0.610

0.855

1.066

1.232

1.390

1.589

1.772

1.951

2.176

0.442

0.584

0.913

1.123

1.296

1.456

1.676

1.858

2.044

2.235

1.333

1.984

2.386

2.897

3.370

3.792

4.305

4.867

5.477

6.102

0.952

1.630

2.296

2.872

3.326

3.762

4.323

4.841

5.350

6.005

1.168

1.537

2.419

2.986

3.452

3.890

4.499

5.006

5.533

6.075

0.179
0.266
0.306
0.377
0.435
0.493
0.565
0.650
0.744
0.837

0.137
0.218
0.289
0.361
0.412
0.465
0.541
0.615
0.682
0.775

0.166
0.199
0.298
0.367
0.413
0.464
0.542
0.606
0.678
0.749

2.283

3.541

4.042

5.094

5.818

6.658

7.555

8.628

9.680

10.58

2.410

3.566

4.320

5.326

5.982

6.722

7.720

8.717

9.471

10.40

3.060

3.619

4.806

5.893

6.405

7.186

8.209

9.053

10.02

10.84

0.484

0.240

0.121
0.173
0.442
0.711
1.018
1.446
1.855
2.099

0.239

0.033
0.103
0.340
0.633
0.943
1.298
1.580
1.872
2.179

0.074
0.127
0.322
0.596
0.892
1.221
1.508
1.820
2.175
2.473

4.285
3.736
3.362
2.426
1.443
0.586

0.373

1.740

2.948

3.467

3.257
2.818
2.508
1.805
0.542

0.691

1.913

2.688

3.649

4.513

2.900
1.960
1.616
0.724

0.719

2.073

2.936

4.024

5.182

6.108

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first factor contributes to expansion in volume and second factor

contributes to decrease or contraction in volume. The experimental
results of VEm for the ternary systems in the present investigation
suggest that the factors which are responsible for contraction in
volume are dominant [45]. The low positive values of excess internal pressure is in support of stronger adhesion between the components in the mixture and formation of more stable hydrogen
bonded complexes between anisole and secondary and tertiary
aromatic amines. Excess free volume (VEf ) decreases with increase
in concentration indicating that the formation of complexes is
favoured at higher concentration. The decreasing trend of excess
free volume (VEf ) with concentration (Fig. 5(a) and (b)) in the two
systems suggests the tightly bound system of molecules inside
the shield, which may be brought about by the growing magnitude
of solutesolute interaction [46]. The trend in the values of excess
free volume with concentration also suggests that there may be
strong intermolecular hydrogen bonds between the amines and
anisole.

system are depicted in Fig. 6. The absorbance values are calculated

at the wave length of maximum absorption and used to make
BenesiHildebrand plots which are given in Fig. 7(a) and (b). The
spectra were recorded at 298 K after making baseline correction
with the solutions of amines at the respective concentration
in n-hexane.

Table 5
Absorbance values at different molality of aniline.
Molality of aniline*

Absorbance at k = 243 nm

1  10
2 M
2  10
2 M
3  10
2 M
4  10
2 M
5  10
2 M

0.299
0.399
0.525
0.735
0.824

*
The concentration of anisole was kept constant (1  10
3 m) and the concentration of aniline was taken in excess and varied.

3.3. UVvisible spectra

0.90
Anisole - Aniline
0.75

-2

5 X 10 M

0.60
Abs

In order to confirm the existence of strong hydrogen bonded

interaction in the two ternary systems, UVvisible spectral method
has been adopted. The UVvisible spectra for the n-hexane solutions of pure components are recorded at 298 K and it is observed
that anisole absorbs at 213 nm due to pp transition. The np
absorption occurs at a longer wavelength of 271 nm. The kmax values for aniline and N-methylaniline are 232 nm, 245 nm for pp
absorptions respectively. The kmax values for np transitions for
the two amines are 290 nm and 292 nm respectively. The spectrum
of ternary solution of n-hexane containing the same concentration
as in solutions of pure components has absorption peak at 243 nm
and 260 nm respectively for aniline and N-methylaniline systems
respectively. These are due to the hydrogen bonded complexes. It
may be noted that in both the systems the pp transition of amine
is shifted to longer wave length [47,48]. In order to determine the
formation constants of these complexes BenesiHildebrand (BH)
method was employed. In this method anisole concentration was
kept constant and the amine was taken in excess and its concentration was varied. The absorbance values at different concentration
of aniline are given in Table 5. The spectra for anisoleaniline

0.45
-2

1 X 10 M

0.30
0.15
230

235

255

260

265

6
Anisole - N-methylaniline
4

-1

Vf / 10 m mol

-1

250

Fig. 6. Recorded UVvis spectra for the variation of absorbance versus wavelength k
for anisoleaniline in n-hexane medium at 298.15 K. The concentration of anisole
was kept constant at 1  10
3 M and the concentration of amine varied as shown.

Anisole - Aniline

-8

-8

245

/ nm

Vf / 10 m mol

240

-2

-2
-4

-4
-6

0.00

0.02

0.04
0.06
-1
Conc. / mol kg

(a)

0.08

0.10

0.00

0.02

0.04
0.06
-1
Conc. / mol kg

0.08

0.10

(b)

Fig. 5. Plot of excess free volume versus concentration (a) aniline and (b) N-methylaniline with anisole in n-hexane system at different temperatures (j) T = 293 K, (d) 298 K,
() 303 K and (.) 308 K.

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0.012

ANI
NMA

[A] / Abs

0.010
0.008
0.006
0.004
0.002
15

30

45

60
1 / [D]

75

90

105

Fig. 7. BenesiHildebrand plots for anisoleaniline and anisole-N-methylaniline

systems in n-hexane at 298.15 K.

3.4. Thermodynamic parameters

Pandiyan et al. investigated binary systems containing ethers
and aromatic amines by ultrasonic method and established the
existence of specific interactions between unlike molecules
through hydrogen bonding and dipoledipole interactions
between unlike components. Further, they suggested in the
cross-association, the H-atom of the present aromatic amines
interacts with O-atom of the ether molecules [49]. In the present
investigation the values of stability constants (K) of anisoleamine
complexes were calculated for the two systems from ultrasonic

velocity using Kannappan equation and from the K values at four

different temperatures the DH values were obtained from the plots
of ln K versus 1/T (Fig. 8) for the two hydrogen bonded complexes.
These thermodynamic parameters are listed in Table 6. It may be
seen from the plots in Fig. 8 that ln K values correlate well with
the 1/T values for the two systems. Free energy (DG), enthalpy
(DH) and entropy (DS) changes for complex formation obtained
by ultrasonic method at 298.15 K are given in Table 6. The formation constant (K), free energy of formation (DG), molar extinction
coefficient (e) and the wavelength of maximum absorption (kmax)
for the two hydrogen bonded complexes obtained from spectral
data are listed in Table 7. The linear trend in BH plots is an indication for the formation of 1:1 complexes between anisole and aromatic amines. It maybe pointed out that acoustical and spectral
studies indicate that both aniline and N-methylaniline form hydrogen bonded complexes with anisole. A perusal of the values of formation constant suggests that the stability of the complex is in the
order aniline > N-methylaniline. It is found that K value decreases
with increase in temperature for both the complexes, indicating
that formation of the two complexes is exothermic. The values of
free energy of formation obtained from ultrasonic method as well
as spectral method also support this trend in stability. It is found
that substitution of hydrogen of amino group by methyl decreases
the stability of the complex. It may be due to steric effect of the
methyl group attached to the imino nitrogen. Similar trend in K
values has been reported by Santhi et al. in the study of hydrogen
bonded complexes of aromatic aldehydes with aniline and
N-methylaniline [50,51]. The formation of complexes in the two
systems is also supported by the negative entropy values and
negative free energy values for the formation of these complexes.
The structure of the hydrogen bonded complex formed between
anisole and the two aryl amines is depicted in Fig. 9.

3 .8
ANI
NMA

3 .6
3 .4

ln k

3 .2
3 .0
2 .8
2 .6

3 .2 4

3 .2 7

3 .3 0

3 .3 3

1 / T x 10

-3

3 .3 6

3 .3 9

3 .4 2

Fig. 8. Plot of ln K versus reciprocal of temperature for aniline and N-methylaniline with anisole in n-hexane solution.

Table 6
The values of stability constants K (by Kannappan equation) and correlation coefficient for various donors D at different temperatures and thermodynamic parameters such as
free energy of formation DG, enthalpy change DH and entropy change DS obtained by ultrasonic method at 298.15 K.
Solvent: n-hexane
Amine

Aniline
N-methylaniline

Acceptor: anisole
K (mol
1)
293.15 K

298.15 K

303.15 K

308.15 K

39.7
36.2

28.8
26.4

20.9
19.6

16.4
15.8

Correlation coefficient

DG (kJ mol
1)

DH (kJ mol
1)

DS (kJ mol
1)

8.325

8.109

44.646

41.836

121.8

113.1

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0.996
0.993

10

R. Rajesh et al. / Chemical Physics xxx (2016) xxxxxx

Table 7
The values of stability constant (K), free energy of complex formation (DG), wave length of maximum absorption of the complex (kmax), molar absorptivity and correlation
coefficient obtained by UV spectrometric technique for various amines at 298.15 K.
Solvent: n-hexane
Amine

K (mol
1)

DG (kJ mol
1)

kmax (nm)

Correlation coefficient

Aniline
N-methylaniline

83.7
77.0

10.968

10.762

243
260

1529.3
250.0

0.961
0.976

CH3
O

H
N
X

X = H, CH3
Fig. 9. Structure of the hydrogen bonded complex of anisole and aromatic amines.

4. Conclusion
The formation of intermolecular hydrogen bonded complexes
between anisole and two structurally different aromatic amines
(aniline, N-methylaniline) is established through ultrasonic and
spectral studies. Acoustical parameters and excess thermo acoustic
properties are calculated for these systems which establish the formation of hydrogen bonded complexes between anisole and the
two amines. Stability constants are determined for these two complexes by ultrasonic and UVvisible spectroscopic methods and the
values obtained by the two different techniques are comparable.
The stability is in the order aniline > N-methylaniline. The complexes are thermodynamically stable as evidenced from their negative free energy and entropy of formation values as well as large
molar extinction coefficients.
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