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J. Chem. Thermodynamics 64 (2013) 159166

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Study of thermodynamic and transport properties of binary liquid

mixtures of n-decane with hexan-2-ol, heptan-2-ol and octan-2-ol
at T = 298.15 K. Experimental results and application of the
PrigogineFloryPatterson theory
Aravind R. Mahajan , Sunil R. Mirgane 1
P.G. Department of Chemistry, J.E.S. College, Jalna, 431203 Maharastra, India

a r t i c l e

i n f o

Article history:
Received 30 September 2012
Received in revised form 25 April 2013
Accepted 9 May 2013
Available online 20 May 2013
Keywords:
n-Decane
2-Alkanols
PFP theory
McAllisters multibody interaction model

a b s t r a c t
Densities and viscosities of binary mixtures of n-decane with hexan-2-ol, heptan-2-ol and octan-2-ol
have been measured over the entire range of composition at T = 298.15 K and at atmospheric pressure.
From the experimental values of density and viscosity, the excess molar volumes (V Em ) and excess Gibbs
energy of activation of viscous ow (GE) have been calculated. These results were tted to RedlichKister
polynomial equations to estimate the binary coefcients and standard errors. JouybanAcree model is
used to correlate the experimental values of density, viscosity and ultrasonic velocity at T = 298.15 K.
The results of the viscosity-composition are discussed in the light of various viscosity semi-empirical
equations. The experimental results have been used to test the applicability of the PrigogineFloryPatterson (PFP) theory. The values of Dlng have also been analysed using Bloomeld and Dewan model. The
experimental and calculated quantities are used to study the nature of mixing behaviour between the
mixtures.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Accurate knowledge of thermodynamic properties of organic
liquid mixtures has relevance in understanding the molecular
interactions between the components of the mixture, in developing new theoretical models, and also in carrying out engineering
applications in the process industry.
In recent years, measurements of thermodynamic and transport
properties have been adequately employed in understanding the
nature of molecular systems and physico-chemical behaviour in
liquid mixtures. The non-rectilinear behaviour of above-mentioned
properties of liquid mixtures with changing mole fractions is
attributed to the difference in size of the molecules and strength
of interactions [1].
Literature surrey reveals that, the effect of molecular size,
shape, chain length and degree of molecular association of
2-alkanols, on the volumetric, viscometric and acoustic properties
of binary mixtures containing acetonitrile [2], acetophenone [3],

Corresponding author. Address: P. G. Department of Chemistry, Jalna Education

Societys R. G. Bagdia Arts, S. B. Lakhotia Commerce, R. Benzonji Science College,
Jalna 431 203, Maharashtra, India. Mobile: +91 9421650049; fax: +91 2482230566.
E-mail addresses: marvind22@yahoo.co.in (A.R. Mahajan), mirgane_chem@
yahoo.co.in (S.R. Mirgane).
1
Tel.: +91 9422722292.
0021-9614/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2013.05.014

methylbenzene [4] and methylcyclohexane [5] have been reported

earlier.
In this paper, we report accurate data on densities and viscosities for binary liquid mixtures of an n-decane with hexan-2-ol,
heptan-2-ol at T = 298.15 K over entire composition range. Using
these data, excess molar volume, V Em and excess Gibbs energy of
activation of viscous ow GE have been calculated. This work will
also provide a test of various semi-empirical equations to correlate
viscosity of binary mixtures.
The calculated results are discussed in terms of intermolecular
interactions between n-decane and alkane-2-ol at T = 298.15 K.
2. Experimental
The sources, CAS number, initial mole fraction purity, purication method, analysis method and nal mole fraction purity of
the pure chemicals are summarized in table 1.
The water content was determined by a Fischer titration. Prior
to use, all liquids were stored over 0.4 nm molecular sieves to reduce the water content and were degassed. The binary mixtures
of varying composition were prepared by mass in special air-tight
bottles. The masses were recorded on a Metler balance to an accuracy of 1  105 g. Care was taken to avoid evaporation and contamination during mixing. The estimated uncertainty in mole
fraction was < 1  104.

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A.R. Mahajan, S.R. Mirgane / J. Chem. Thermodynamics 64 (2013) 159166

TABLE 1
The provenance, CAS number, maximum water content mass%, initial mole fraction purity, purication method, .analysis method and nal mole fraction purity of the pure
chemicals.

a
b
c

Chemical name

CAS
number

Water content
(mass%)

Source

Initial mole
fraction purity

Purication
method

Analysis
method

Final mol
fraction purity

n-Decane
Hexan-2-ol
Heptan-2-ol
Octan-2-ol

124-65-9
626-93-7
543-49-7
123-96-6

0.03
0.02
0.02
0.004

S.D. Fine Chemicals

E-Merck
E-Merck
E-Merck

>0.992
>0.993
>0.991
>0.994

F.G.Da
F.G.Da
F.G.Da
F.G.Da

G.C.b
G.C.b
G.C.b
G.C.c

>0.995
>0.996
>0.994
>0.996

Fractional glass distillation.

Gasliquid chromatography, HP6980 using FID detector.
Gasliquid chromatography, DB Wax using FID detector.
1

V Em =m3  mol
TABLE 2
Comparison of experimental densities (q) and viscosities (g) of pure liquids with
literature values at T = 298.15 K.
Pure liquids

n-Decane
Hexane-2-ol
Heptane-2-ol
Octane-2-ol
a
b
c
d
e
f

3

3

g/mPa  s

q  10 /kg  m
Experimental

Literature

Experimental

Literature

0.72635
0.81084
0.81374
0.81705

0.7267a
0.8105d
0.81372e
0.81708f

0.845
4.105
5.088
6.429

0.861b,c
4.104d
5.089e
6.435f

Baraigi et al. [11].

Gonazalez et al. [12].
Gonazalez et al. [14].
Iloukhani et al. [2].
Almasi et al. [3].
Hasan et al. [4].

The densities of the solutions were measured using a single

capillary pycnometer made up of borosil glass with a bulb of 8
cm3 and capillary with internal diameter of 0.1 cm was chosen
for the present work. The detailed pertaining to calibration, experimental set up and operational procedure has been previously
described [610]. .An average of triplicate measurement was taken
into account. The reproducibility of density measurement
was 1  105 g cm3.
The dynamic viscosities were measured using an Ubbelohde
suspended level viscometer [610] calibrated with conductivity
water. An electronic digital stop watch with readability of 0.01
s was used for the ow time measurements. At least three repetitions of each data point reproducible to 0.05 s were obtained, and
the results were averaged. Since all ow times were greater than
300 s and capillary radius (0.1 mm) was far less than its length
(50 to 60) mm, the kinetic energy and end corrections, respectively,
were found to be negligible. The uncertainties in dynamic viscosities are of the order 0.003 mPa s. A thermostatically controlled,
well-stirred water bath whose temperature was controlled
to 0.01 K was used for density and viscosity measurement.
Standard uncertainties u are U(x1) = 0.0002, and the combined
expanded uncertainty Uc is Uc(q) = 1  103 kg  m3 and
Uc(g) = 0.003 mPa  s with 0.95 level of condence (k  2).
The purity of the samples and accuracy of data were checked by
comparing the measured densities and viscosities of the pure compounds with the literature values, which are given in table 2. Thus
our results obtained are in good agreement with those listed in the
literature [1114].
3. Results
Experimental values of densities (q) and viscosities (g) of mixtures at T = 298.15 K are listed as a function of mole fraction in table 3. The density values have been used to calculate excess molar
volumes (V Em ) using the following equation

x1 M1 x2 M 2 =q12  x1 M1 =q1  x2 M2 =q2 ;

1

where q12 is the density of the mixture and x1M1, q1, and x2, M2, q2
are the mole fraction, the molar mass, and the density of pure
components 1and 2, respectively.
Excess Gibbs energy of activation of viscous ow GE for binary
mixtures can be calculated as

GE RT lngt=g2 t2  x1 lng1 t1 =g2 t2 ;

where t is the molar volume of the mixture and ti is the molar volume of the pure component, R is the gas constant, T is the absolute
temperature, and g is the dynamic viscosity of the mixture, respectively. gi is the dynamic viscosity of the pure component i and x1 the
mole fraction in component.
The excess molar volumes and excess Gibbs energy of activation
of viscous ow were tted to a RedlichKister [15] equation of the
type

Y x1 x2

Xn
i

ai x1  x2 i ;
V Em ,

3
E

where Y is either
or G and n is the degree of polynomial.
Coefcients ai was obtained by tting equation (3) to experimental
results using a least-squares regression method. In each case, the
optimum number of coefcients is ascertained from an examination
of the variation in standard deviation (r).
r was calculated using the relation

rY

"P

Y expt  Y calc 2
Nn

#1=2
;

where N is the number of data points and n is the number of

coefcients. The calculated values of the coefcients ai along with
the standard deviations (r are given in table 4.
4. Discussion
The variation in excess molar volumes, V Em with mole fraction of
the binary mixtures of n-decane with hexan-2-ol, heptan-2-ol and
octan-2-ol T = 298.15 K are displayed in gure 1. The V Em curve for
the mixture show positive deviation over the entire composition
range.
Generally V Em can be considered as arising from three types of
interactions between component molecules of liquid mixtures
[5,1620]: (i) physical interactions consisting of mainly of dispersion forces or weak dipoledipole interaction making a positive
contribution, hereby the contraction volume, (ii) chemical or
specic interactions, which include charge transfer,forming of
H-bonds and other complex forming interactions,resulting in a
negative contribution, (iii) structural contribution due to differences in size and shape of the component molecules of the
mixtures,due to tting of component molecules into each others
structure, hereby reducing the volume of the mixtures, resulting
in a negative contribution .

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TABLE 3
Densities (q), viscosities (g), excess molar volumes (V Em ) and excess Gibbs energy of
activation of viscous ow (GE) of binary mixtures at T = 298.15 K.a
1

q 103
(kg  m3)

V Em 106
(m3  mol1)

g (mPa  s)

0.0000
0.0555
0.0999
0.1554
0.1998
0.2556
0.2999
0.3555
0.3998
0.4554
0.4998
0.5554
0.5997
0.6555
0.6999
0.7555
0.7998
0.8555
0.8999
0.9555
1.0000

0.81084
0.80294
0.79723
0.79050
0.78543
0.77942
0.77491
0.76955
0.76552
0.76072
0.75710
0.75279
0.74954
0.74566
0.74272
0.73925
0.73662
0.73348
0.73111
0.72829
0.72635

n-Decane(1) + hexane-2-ol (2)

0.000
4.105
0.135
3.569
0.197
3.170
0.267
2.725
0.317
2.410
0.372
2.062
0.410
1.821
0.448
1.561
0.471
1.384
0.490
1.198
0.499
1.076
0.499
0.952
0.491
0.875
0.470
0.802
0.445
0.760
0.402
0.725
0.359
0.708
0.292
0.699
0.230
0.698
0.138
0.703
0.000
0.845

0.0000
0.0552
0.0999
0.1555
0.1999
0.2554
0.2999
0.3554
0.3998
0.4555
0.4998
0.5555
0.5999
0.6554
0.6999
0.7553
0.8000
0.8555
0.8998
0.9553
1.0000

0.81374
0.80687
0.80155
0.79515
0.79026
0.78436
0.77983
0.77440
0.77024
0.76523
0.76141
0.75680
0.75327
0.74904
0.74579
0.74187
0.73884
0.73520
0.73239
0.72898
0.72635

n-Decane(1) + heptan-2-ol (2)

0.000
5.080
0.069
4.250
0.120
3.732
0.183
3.152
0.229
2.740
0.282
2.283
0.319
1.962
0.356
1.614
0.378
1.375
0.396
1.122
0.401
0.954
0.398
0.782
0.386
0.673
0.361
0.570
0.333
0.510
0.289
0.461
0.246
0.440
0.187
0.432
0.135
0.438
0.067
0.457
0.000
0.845

0.0000
0.0554
0.0998
0.1554
0.1999
0.2554
0.2999
0.3555
0.3998
0.4554
0.4999
0.5555
0.5998
0.6555
0.7000
0.7554
0.7998
0.8554
0.8999
0.9554
1.0000

0.81705
0.81077
0.80583
0.79974
0.79499
0.7892
0.78467
0.77916
0.7749
0.76969
0.76564
0.76074
0.75694
0.7523
0.7487
0.74432
0.74091
0.73674
0.73347
0.72948
0.72635

n-Decane(1) + octan-2-ol
0
0.036
0.071
0.119
0.158
0.205
0.239
0.275
0.298
0.318
0.326
0.326
0.318
0.298
0.274
0.236
0.2
0.149
0.106
0.052
0

(2)
6.429
5.222
4.638
3.972
3.491
2.951
2.564
2.136
1.836
1.509
1.284
1.046
0.889
0.73
0.63
0.538
0.487
0.45
0.438
0.445
0.845

GE
(J  mol1)

0
112
221
367
490
650
780
939
1062
1201
1293
1381
1419
1421
1385
1291
1200
990
600
400
0
0
233
301
403
497
632
755
927
1078
1285
1461
1690
1871
2080
2223
2280
2200
2000
1250
800
0
0
188
306
471
617
818
993
1227
1426
1681
1887
2133
2309
2476
2500
2400
2362
2281
1650
1200
0

Standard uncertainties U are U(x1) = 0.0002, and the combined expanded uncertainty Uc is Uc(q) = 1  103 kg  m3 and Uc(g) = 0.003 mPa  s with 0.95 level of
condence (k  2).

The large positive V Em values (gure 1) for n of n-decane with

hexan-2-ol, heptan-2-ol and octan-2-ol mixture are attributed to

TABLE 4
Coefcients ai of equation (3) and corresponding standard deviation (r) of equation
(4).
System
V Em /(m3  mol1)
GE/(J  mol1 )
V Em /(m3  mol1)
GE/(J  mol1 )
V Em /(m3n  mol1)
GE/(J  mol1)

a3

n-Decane(1) + hexane-2-ol (2)

2.033
0.152
0.5406

1.9

0.007

1122.23

1153

7.3

n-Decane(1) + heptan-2-ol (2)

1.61
0.062
0.443

0.276

0.001

1183

516

5.4

n-Decane(1) + octan-2-ol (2)

1.129
0.1677
0.462

0.1437

0.0023

1119.18

741

9.2

a0

a1

259.1

809

30.22

a2

784

34.431

45.44

the breaking up of three-dimensional H-bonded network of alkane-2-ol due to the addition of solute, which is not compensated
by the weak interactions between unlike molecules. The V Em values
for binary mixtures of n-decane with alkane-2-ol are in the order
octan-2-ol > heptan-2-ol > hexan-2-ol.
The GE values of all binary systems are shown in table 3. Figure
2 depicts the variation of GE with mole fraction of the binary mixtures of n-decane with hexan-2-ol, heptan-2-ol and octan-2-ol
T = 298.15 K.The values of GE for all binary mixtures are negative
over entire mole fraction. The negative values of GE may be due
to (i) the mutual loss of dipolar association, and (ii) the differences
in size and shape of unlike molecules. These results support the
fact that the breaking up of three-dimensional H-bonded network
of alkane-2-ol due to the addition of solute. According to Meyer
et al. [17] negative values of GE correspond to the existence of solutesolute association.
5. Theoretical analysis
5.1. PrigogineFloryPatterson (PFP) theory
The PrigogineFloryPatterson (PFP) theory [1820] has been
commonly employed to estimate and analyse excess thermodynamic functions theoretically. This theory has been described in
details by Patterson and co-workers [21,22]. According to PFP theory, V Em can be separated into three factors: (1) an interactional
contribution, V Em int: (2) a free volume contribution, V Em fv and
(3) an internal pressure contribution, V Em P . The expression for
these three contributions are given as V Em

~1=3  1t
~2=3 wh2 =4=3t
~1=3  1P1 v12 ;
V Em int t

~1  t
~2 2 14=9t
~1=3  1w1w2=14=9t
~1=3  1t
~;
V Em fv t
~1  t
~2 P1 P 2 w1 w2 =P1 w1 P2 w2:
V Em P t

6
7

Thus, the excess molar volume V Em is given as

V Em =x1 V 1 x2 V 2 V Em int  V Em f v V Em P ;

where w, h and P represent the contact energy fraction, surface site

fraction, and characteristic pressure, respectively, and are calculated as

w1 1  w2 U1 P1 =U1 P 1 U2 P2 ;




h2 1  h1 U2 = U1 V 2 =V 1 ;

10

~2 a=jT :
P T t

11

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162

FIGURE 1. Plot of excess molar volumes (V Em ) against mole fraction of n-decane with (s) hexane-2-ol; (h) heptane-2-ol; and octane-2-ol (4) at T = 298.15 K. The
corresponding dotted (- - -) curves have been derived from PFP theory. The corresponding solid curves have been derived experimental results.

FIGURE 2. Plot of excess Gibbs energy of activation of viscous ow (GE) against mole fraction of n-decane with (s) hexane-2-ol; (h) heptane-2-ol; and octane-2-ol (4) at
T = 298.15 K.

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TABLE 5
Flory parameters of the pure compounds T = 298.15 K.
Components

106V/(m3  mol1)

106P/(J  m3)

T/K

n-Decane
Hexane-2-ol
Heptane-2-ol
Octan-2-ol

155.6091
102.532
115.6
129.979

453
476
512
535

5091
5517
5415
5563

The details of the notations and terms used in equations (5)(9)

may be obtained from the literature [1824]. The other parameters
pertaining to pure liquids and the mixtures are obtained from the
Flory theory [18,25] while a and jT values are taken from the literature [2630]. Flory parameters of the pure compounds are given
in table 5.The interaction parameter v12 required for the calculation of V Em using PFP theory has been derived by tting the V Em
expression to the experimental equimolar value of V Em for each system under study.
The values of v12, h2, three PFP contributions interactional, free
volume, and P effect, and experimental and calculated (using PFP
theory) V Em values at near equimolar composition are presented in
table 6. Study of the data presented in table 6 reveals that the
interactional and free volume contributions are positive, whereas
P contributions are negative for all the three systems under investigation. For these binary mixtures, it is only the interactional contribution that dominates over the remaining two contributions
.The P contribution, which depends both on the differences of
internal pressures and differences of reduced volumes of the components has little signicance for the studied binary mixtures as
compared to other two.
Furthermore, in order to check whether v12, derived from
nearly equimolar V Em values can predict the correct composition
dependence, V Em has been calculated theoretically using v12 over
the entire composition range. The theoretically calculated values
are plotted in gure 1 for comparison with the experimental results. Figure 1 show that the PFP theory is quite successful in predicting the trend of the dependence of V Em on composition for the
present systems.
In order to perform a numerical comparison of the estimation
capability of the PFP theory, we calculated the standard percentage
deviations (r %) using the relation

r%

hX

100 Expt  Theor=Expt n  1

i1=2

12

where n represents the number of experimental data points.

5.2. Semi-empirical models for analysing viscosity of liquid mixtures
Several empirical and semi-empirical relations have been used
to represent the dependence of viscosity on concentration of components in binary liquid mixtures and these are classied according to the number of adjustable parameters used to account for
the deviation from some average [31,32].We will consider here
some of the most commonly used semi-empirical models for

analysing viscosity of liquid mixtures based on one, two and three

parameters. An attempt has been made to check the suitability of
equations for experimental data ts by taking into account the
number of empirical adjustment coefcients.
The equation of Grunberg-Nissan, Tamara and Kurata Hind
et al., and Katti and Chaudhari has one adjustable parameter.
Gruenberg-Nissan provided the following empirical equation
containing one adjustable parameter [33] .The equation is

ln g12 x1 ln g1 x2 ln g2 x1 x2 G12 ;

13

where G12 may be regarded as a parameter proportional to the

interchange energy also an approximate measure of the strength
of the interaction between the components .
The one-parameter equation due to Tamura and Kurata [34] is
gave the equation of the form

gm x1 g1 U1 x2 gU2 2x1 x2 U1 U2 1=2 T 12 ;

14

where U1 and U2 re the volume fractions of components 1 and 2,

respectively; T12 is Tamura and Kurata constant.
Hind et al. [35] proposed the following equation

gm x21 g1 x22 g2 2x1 x2 H12 ;

15

where H12 is attributed to unlike pair interactions.

Katti and Chaudhari [36] derived the following equation

ln gm x1 ln gm01 x2 ln gnu02 x1 x2 W v is =RT;

16

where Wvis is an interaction term and ti is the molar volume of pure

component i.Heric [37] expression is

ln gm x1 ln g1 x2 ln g2 x1 ln g1 x2 ln g2 lnx1 g1
x2 g2 d12 ;

17

where d2 = a12x1x2 is a term representing departure from a noninteracting system and a12 = a21 is the interaction parameter.
Either a12 or a21 can be expressed as a linear function of
composition:

a12 b012 b0012 x1  x2 :

18

From an initial guess of the values of coefcients b12 and b12

the values of a12 are computed.
Heric and Brewer [38] equation is

ln m x1 ln m1 x2 ln m2 x1 ln M 1 x2 ln M 2  lnx1 M 1
x2 M 2  x1 x2 a12 a21 x1  x2 :

19

The M1 and M2 are molar mass of components 1 and 2 and a12

and a21 are interaction parameters and other terms involved have
their usual meaning. a12 and a21 are parameters, which can be calculated from the least-squares method.
McAllisters multibody interaction model [39] was widely used
to correlate kinematic viscosity (m) data. The two-parameter
McAllister equation based on Eyrings [40] theory of absolute reaction rates taken into account interaction of both like and unlike
molecules by two dimensional three-body model. The three-body
interaction model is

TABLE 6
Calculated values of the three contributions to the excess molar volume from the PFP theory with interaction parameter at T = 298.15 K.
Component

n-Decane(1) + hexane-2-ol (2)

n-Decane(1) + hexane-2-ol (2)
n-Decane(1) + heptan-2-ol (2)
n-Decane(1) + octan-2-ol (2)

v12 106 (J  m3)

19.36
19.36
17.75
12.57

VE  106/(m3 mol1) at x = 0.5

Calculated contribution

Experimental

PEP

VE  106 (int)

VE  106 (fv)

VE  106 (p)

0.499
0.499
0.401
0.326

0.498
0.498
0.398
0.328

0.596
0.596
0.537
0.5999

0.042
0.042
0.025
0.0544

0.055
0.055
0.109
0.2183

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ln num x31 ln m1 3x21 x2 ln Z 12 3x1 x22 ln Z 21 x32 ln m2

 lnx1 x2 M2 =M 1 

3x21 x2

parameter is increased. From table 7, it is clear that McAllisters

four-body interaction model is suitable for correlating the kinematic viscosities of the binary mixtures studied.

ln2=3 M2 =3M1 

3x1 x22 ln1=3 2M 2 =3M 1 x32 lnM 2 =M 1

20

and the four body model was given by

5.3. Bloomeld and Dewan model

ln num x41 ln m1 4x31 x2 ln Z 1112 6x21 x22 ln Z 1122 4x1 x32

There are different expressions available in the literature to calculate g. Here, the Bloomeld and Dewan [43] model has been applied to compare calculated Dln g values using experimental data
for each binary mixture by the following relation

 ln Z 2221 x42 ln m2  lnx1 x2 M2 =M 1  4x31 x2

 ln3 M 2 =M1 =4 6x21 x22 ln1 M 2 =M 1 =2
4x1 x32 ln1 3M 2 =M 1 =4 x42 lnM 2 =M 1 ;

21

where Z12, Z21, Z1112, Z1122 and Z2221 are interaction parameters and
Mi and mi are the molar mass and kinematic viscosity of pure component i, respectively.
The correlating ability of each of equations (13)(21) was tested
and their adjustable parameters and standard deviations (r):

h
i1=2
X
r 1=n  k 100gexptl  gcalcd =gexptl 2 ;

22

where n represents the number of data points and k is the number

of numerical coefcients is given in table 7. According to Fort and
Moore [41] and Ramamurthy [42], system exhibits strong interaction if the G12 is positive; if it is negative they show weak interaction. On this basis we can say that there is weak interaction in
the system studied.
Interaction parameter Wvis shows almost same trend as that of
G12.In fact one could say that the parameter G12 and Wvis exhibit almost similar behaviour, which is not unlikely in view of logarithmic nature of both equation.
Tamara and Kurata and Hind et al., represent the binary mixture
satisfactory as compared to Gruenberg-Nissan and Katti and
Chaudhari. Use of a three parameter equation reduces the r values
signicantly below that of two parameters equation. From this
study, it can be concluded that the correlating ability signicantly
improves for these non-ideal systems as number of adjustable

D ln g ln g  x1 ln g1 x2 ln g2 :

23

Bloomeld and Dewan [43] developed the expression from the

combination of the theories of free volumes and absolute reaction
rate

D ln g f m  DGR =RT;

24

where f(t) is the characteristic function of the free volume dened

by

~ 1=t
~  1x1=t
~1  1  x2=t
~2  1
f t

25

and DGR is the residual energy of mixing, calculated with the following expression

DGR DGE RTfx1 lnx1 =U1 x2 lnx2 =U2 g;

26

where U1 and U2 are segment fraction dened by

U2 1  U1 x2 =x2 x1 r 1 =r 2 ;

27

where r1 and r2 are in the ratio of respective molar core volumes V1

and V2.
The excess energy can be obtained from the statistical theory of
liquid mixtures proposed by Flory and co-workers [18,19] and is
given by

~1=3  1g
DGE x1 P1 V 1 1=t~1  x1 lnft~1=3
 1=t
1
TABLE 7
Adjustable parameters of equations (13)(21) and standard deviations of binary
mixture viscosities for {x1 n-decane + (1  x1) alkane-2-ol} at T = 298.15 K.
Equation

System including n-decane + alkane-2-ol

Hexane-2-ol

G12

R
T12

R
H12

R
Wvis

a12
a21
R
Z12
Z21

R
Z1112
Z1122
Z2221

Heptane-2-ol

Octane-2-ol

GrunbergNissan
3.724
3.597

3.226
2.904

0.005
0.355

Tamura and Kurata

0.925
1.766

1.117
1.884

3.75
0.964

Hind et al.
1.266
1.956

1.409
1.145

2.173
1.134

Katti and Chaudhari

3.665
2.602

3.198
3.905

2.26
2.912
0.461

Herc and Brewer

4.248
5.406
2.001

3.936
5.529
2.449

2.253
1.124

0.467
2.272
0.463

McAllisters three-body
0.081
5.225
1.03

0.094
4.068
1.449

0.481
2.157
2.591
0.325

McAllisters four-body
0.059
8.543
1.976
0.397

0.511
1.897
1.998
1.865

1=3

~2  x2 lnft
~2  1=t
~1=3  1g
x2 P2 V 2 1=t
~;
x1 h2 V 1 v12 =t

28

where the various symbols used have their usual meanings.

Using the v12 values from tting values of V Em and the values of
the parameters for the pure liquid components, we have calculated
DGR and f(t) and nally Dln g, according to the Bloomeld and Dewan relationship, which is compared with the experimental values.
Figure 3 shows that the good agreement between the estimated
and experimental curves occurs for given binary systems.
5.3.1. The Jouyban and Acree model
The JouybanAcree model [44,45] was introduced to correlate
the physicochemical properties of the solution in mixed solvents
including the dielectric constants, viscosity solvatochromic parameter, and density, speed of sound and more recently molar volumes. The model uses the physicochemical properties of the
mono-solvents as input data and a number of curve-tting parameters representing the effects of solventsolvent interactions in the
solution. It is basically derived for representing the solvent effects
on the solubility of non-polar solutes in nearly ideal binary solvent
mixtures at isothermal conditions. The proposed equation is

ln ym;T f1 ln y1;T f2 ln y2;T f1 f2 RAj f1  f2 j =T;

29

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 volume fractions of solvents in case of density, and mole fraction in
case of viscosity, and Aj are the model constants.

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FIGURE 3. Plot of Dln g against mole fraction of n-decane with (s) hexane-2-ol; (h) heptane-2-ol; and octane-2-ol (4) at T = 298.15 K. The corresponding dotted (- - -) curves
have been derived from Bloomeld and Dewan model. The corresponding solid curves have been derived experimental results.

TABLE 8
Parameters of JouybanAcree model and average percentage deviation for densities
and viscosities at of binary mixtures at T = 298.15 K.
System

A0

A1

A2

APD

n-Decane(1) + hexane-2-ol (2)

n-Decane(1) + heptan-2-ol (2)
n-Decane(1) + octan-2-ol (2)

Density
16.812
11.498
9.0926

1.275
2.104
1.0266

4.12
1.91
0.6448

0.175
0.154
0.1183

n-Decane(1) + hexane-2-ol (2)

n-Decane(1) + heptan-2-ol (2)
n-Decane(1) + octan-2-ol (2)

Viscosity
5.123
6.321
4.2926

9.236
8.123
11.2857

3.125
2.158
2.7614

0.812
0.913
0.7668

The correlating ability of the JouybanAcree model was tested

by calculating the average percentage deviation (APD) between
the experimental and calculated density and speed of sound as

APD 100=NRjyexptl  ycalcd j=yexptl ;

heptan-2-ol and octan-2-ol mixtures suggest that the rupture of

hydrogen bonded chain of the dipolar interaction between solute
and alkan-2-ol exceed the intermolecular interaction through
dipoledipole and hydrogen bonding between n-decane and
alkan-2-ol molecules. This behaviour is characteristic for systems
containing an associated component.
All of the selected correlative models are capable of representing the volumetric and the viscometric behaviour of the mixture
with a higher or lower degree of accuracy. McAllisters four-body
interaction model is suitable for correlating the kinematic
viscosities of the binary mixtures studied. Also the Prigogine
FloryPatterson (PFP) theory shows that the good agreement
between the estimated and experimental curves occurs for given
binary systems. The JouybanAcree model and the Bloomeld and
Dewan relationship show that the good agreement between the
estimated and experimental values occurs for given binary
systems.

30
Acknowledgments

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 constants Aj calculated from the least squares analysis are
presented in table 8 along with the average percentage deviation
(APD). The proposed model provides reasonably accurate calculations for the density and viscosity of binary liquid mixtures at
T = 298.15 K and the model could be used in data modelling.
6. Conclusions
Densities and viscosities for the binary liquid mixture of n-decane with hexan-2-ol, heptan-2-ol and octan-2-ol were measured at
the temperature of 288.15 K over the whole range of compositions.
The positive V Em and negative GE for n-decane with hexan-2-ol,

Authors are thankful to Prof. B.R. Arbad, Dr. B.A.M. University

for their valuable suggestions and discussion. Authors are also
thankful to Principal Dr. R.S. Agarwal, J.E.S. College, Jalna for the
facilities provided.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jct.2013.05.014.
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JCT 13-95