Available online at http://www.urpjournals.

com

International Journal of Research in Pure and Applied Physics

Universal Research Publications. All rights reserved

ISSN 2278 -134X

Original Article
Correlation of excess molar volumes with Redlich-Kister polynomial and
evaluation of partial molar volumes, excess partial molar volumes in some binary
mixtures at 308.15 K
M. Kondaiaha, and D Krishna Raob*
a. NM Govt. Degree College, Jogipet, Medak Dt, A.P., India
b. Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522 510, A.P., India
* Corresponding Author: krdhanekula@yahoo.co.in
Phone: +91-863-2354395 (R), +91-9440712142
Received 17 November 2013; accepted 02 December 2013
Abstract
Excess molar volumes,

E , partial molar volumes, V

Vm
m,1 , V m,2 , excess partial molar volumes, V m ,1 , V m , 2 and
E

E,

E,

partial molar volumes, excess partial molar volumes at infinite dilution, V m,1 , V m , 2 , V m,1 , V m, 2 have been calculated
using the experimentally measured density data for the prepared binary mixtures of 1,2-Dichloroethane(DE) + N,NDimethyl formamide (DMF), 1,2-Dichloroethane(DE) + Dimethyl sulphoxide(DMSO), Dichloromethane(DM) + N,NDimethyl formamide (DMF) and Dichloromethane(DM) +Dimethyl sulphoxide(DMSO) at 308.15 K. Positive
suggesting dispersion forces exist in DE+DMF and DM+DMF binary systems and negative

VmE data

VmE data in DE+DMSO and

DM+DMSO binary systems supports strong interactions exist between the liquid molecules. Redlich-Kister type
polynomial gives better fitting of

VmE data with calculated data.

2013 Universal Research Publications. All rights reserved

Keywords: Density, Molecular interactions, RedlichKister type polynomial, Excess molar volume, Partial molar volume,
Excess partial molar volume
Introduction
The study of properties of liquid mixtures and solutions
finds direct applications in chemical and biochemical
industry. Knowledge of the temperature dependence of
excess volumetric and transport properties of liquid
mixtures provides valuable information on the nature of
inter molecular interactions existing among the component
molecules [13]. Many engineering and technological
problems require quantitative data on the density and
viscosity of liquid mixtures. Volumetric properties of liquid
binary mixtures enable the important information for the
characterization of the interactions between components.
N,N-Dimethyl formamide is used as a solvent in peptide
coupling for pharmaceuticals, in the development and
production of pesticides, in the manufacture of adhesives,
synthetic leathers, fibers, films, and surface coatings and
other applications of pure solvents. It has a large dipole

43

moment = 3.82D [4] and, in view of this, dipoledipole

interactions are expected to play an important role in
molecular interactions present in the liquid mixtures.
Dimethyl sulfoxide having highly polar S=O group and two
hydrophobic CH3 groups. It is a typical aprotic highly polar
(=4.06D) self-associated solvent, is an important solvent
in chemistry, biotechnology, and medicine and it is able to
participate in hydrogen bonding [5]. Dichloromethane used
as a cleaning agent, paint remover and in extraction
technology; paraffin extraction, recovery of specialty
pharmaceuticals [6]. 1,2-Dichloroethane mostly used in the
production of vinyl chloride which is used to make a
variety of plastic and vinyl products including polyvinyl
chloride.
A survey of literature indicates that Radhamma et al.
reported the excess molar volumes of binary mixtures of
Dimethyl sulfoxide with Chloroethanes and Chloroethenes

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49

at 303.15K [7], Oana Cioclirlan and Olga Iulian [8] Harish

Kumar and Deepika [9] Vijayakumar Naidu et al. [10],
Fabio Comelli et al. [11] and others [12-16] reported the
various excess properties of the liquid mixtures containing
Dichloromethane, 1,2-Dichloroethane, Dimethyl sulfoxide
as one component. In the present paper, densities, of
binary
mixtures
of
N,N-Dimethyl
formamide
(DMF)+Dichloromethane (DM), N,N-Dimethyl formamide
(DMF)+1,2-Dichloroethane (DE), Dimethyl sulfoxide
(DMSO)+Dichloromethane (DM) and Dimethyl sulfoxide
(DMSO)+1,2-Dichloroethane (DE) besides those of pure
liquids at temperature 308.15K covering the entire
composition range have been reported. The excess molar
E , partial molar volumes, V m ,1 , V m,2 , excess
volume, Vm
partial molar volumes,
at infinite dilution,

V m,1 , V m,2 , partial molar volumes

V m,1 , V m , 2 and excess partial molar

E,

E,

volumesatinfinitedilution, V m,1 , V m, 2 havebeen calculated.

The variations of excess properties with composition of the

mixtures have been discussed in terms of molecular
interactions in the mixtures.
Experimental
In the present investigation, chemicals were further purified
by standard methods [17]. Binary mixtures of DMF with
DM or DE and DMSO with DM or DE were prepared so
that the entire composition range is covered (i.e. 0-100% of
DE or DM). The mixtures were prepared by mass in airtight bottles. The mass measurements were performed with
a METTLER TOLEDO (Switzerland) ABB5-S/FACT
digital balance with an accuracy 0.01mg. The uncertainty
in the mole fraction is 104. The density of pure liquids and
liquid mixture has been measured using a two stem doublewalled Parker & Parker type pyknometer [18]. The detailed
description of measurements of density was presented in
our previous papers [19-21]. The reproducibility in the
measured parameters of density is 3 in 105parts. The
experimental values of of pure liquids at 308.15 K along
with their literature [10,14,22,23] values are presented in
Table 1.

Table 1: Comparison of densities, (kg.m-3) of pure liquids with literature data at 308.15 K
(kg.m-3)
Liquid
In this work
Literature
Dichloromethane
1297.2
1297.2 [22]
1,2-Dichloroethane
1230.2
1230.8 [14]
N,N-Dimethyl formamide
935.6
935.717 [23]
Dimethyl sulphoxide
1085.2
1085.6 [10]
n
Results
(3)
YE
x1x2
Ai ( x2 x1)i
The experimental values of density have been used to
i 0
calculate the molar volume and excess molar volume data
E
where
Y
=
VmE ; the subscription i in the eq 3 takes
with the following equations.
values from 0 to 4. Ai are the adjustable parameters of the
x1M1 x2M 2
(1)
Vm
function and are determined using the least square method.

E
Vm

Vm ( x1V1

x2V2 )

(2)

The corresponding standard deviations

computed using the relation.

where , and Vm are the density and molar volume of the

mixture. M1, M2,

V1 and V2 are the molar masses and

molar volumes pure components1 (DE or DM) and 2 (DMF

or DMSO) respectively and xi represents the mole fraction
of the component i in the mixture.
The values of excess molar volume have been fitted to
Redlich-Kister type polynomial [24] equation,

(Y E )

E
Yexp
m

E
Ycal
n

(Y E ) have been

2 1/2

(4)

where m is the total number of experimental points and

n is the number of coefficients in eq 3. The coefficients Ai
in eq 3 and the standard deviations of all the binary
mixtures have been presented in Table 2.

Table 2 : Coefficients Ai of Redlich-Kister type polynomial equation eq 3 and the corresponding standard deviations () of
all the systems for VmE (x10-5) (m3.mol-1)
A0
A1
DE+DMF
0.0813
0.0084
DE+DMSO
-0.1623
0.0380
DM+DMF
0.1579
-0.0175
DM+DMSO
-0.0872
0.0844
The molecular interactions in the systems are well reflected
in the properties of partial molar volumes. The partial
molar volumes

V m,1

A3
0.0492
-0.0153
0.0571
-0.0625

VmE

V1*

x2

V m,1 of component 1(DE or DM) and

V m,2 of component 2 (DMF or DMSO) in the mixtures

over the entire composition range have been calculated by
using the following relations.

44

A2
0.1110
0.0787
0.0662
-0.0426

V m, 2

VmE

V2*

x1

A4
-0.1601
-0.0171
-0.0169
0.0845

VmE
x

(5)
T ,P

E
m

V
x

0.0024
0.0011
0.0004
0.0006

(6)
T ,P

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49

where

V1 and V2 are the molar volumes of pure

components of DE or DM and DMF or DMSO

respectively. The derivates V E
in eq.s (5) and (6) are
m
x

T ,P

obtained by differentiating Eq.(3) which lead to the

following equations for
V m,1
V m, 2

V1*

x22

V2*

x12

V m,1 and V m,2 .

Ai ( x2
i 0
j

Ai ( x2

2 x1 x22

x1 ) i

2 x2 x12

x1 ) i

i 0

Ai ( x2

x1 ) i

i 1
j

Ai ( x2

x1 ) i

(7)
(8)

i 1

V m,1 V1*

E
m, 2

V m, 2 V2*

E calculated from
Comparison of excess molar volume, Vm
equation (2) and (3) against mole fraction, x1 of DE/DM are
plotted in fig. 2. The deviation of physical and chemical
properties of the liquid mixture from the ideal behavior is a
measure of the interaction between molecules of the
components of liquid mixtures, and such a type of deviation
is generally attributed to dipoledipole interactions and
hydrogen bond between unlike molecules [25] respectively.
From this figure, a good correlation exist between
experimentally calculated and RK polynomial excess molar
E data
volumes. This show, experimentally calculated Vm

better fits the RK polynomial.

V m,1 , V m,2 have been calculated using the relations,

V m ,1

(9)

(10)
The experimental values of densities, excess molar
E

V m,1 , V m,2 , V m ,1 and V m , 2 are furnished in

volumes,

Table 3. Furthermore, the partial molar volumes and excess

partial molar volumes of the components at infinite dilution
E,

E,

respectively, V m ,1 , V m,2 , V m ,1 and V m ,2 were obtained by;

putting x1 = 0 in eq. 7 and x1 =1 in eq. 8.
E,

V m,1
E,

V m,2

A0

A1

A2

A3 ...... V m,1 V1 ,

(11)

A0

A1

A2

A3 ...... V m,2 V2 ,

(12)

Fig. 2 Comparison plots of excess molar volume,

E,

against mole fraction, x1 of DE/DM for binary mixtures of

DE with DMF (O), DMSO (O) or DM with DMF
( ), DMSO ( ) (solid lines: calculated, dotted lines: R-K
Polynomial)
E is the resultant of several effects such as chemical,
Vm

E,

The pertinent values of V m ,1 V m,2 V m ,1 and V m ,2 are

shown in Table 4.
Discussion
The variation of density with mole fraction, x1 of DE or
DM as shown in fig. 1. From this figure 1 and table 3
densities increased monotonically, non-linearly in all the
binary systems with increase in concentration of DE or
DM. This non-linear variation is a deviation from ideal
behavior suggests that interactions between molecules of
component liquids of the mixtures.

physical and structural. Physical contributions, which are

non-specific interactions between the liquid molecules of
E values. The
the mixture [26,27], contribute to positive Vm
E are contributed by the chemical or
negative values to Vm
specific intermolecular interactions [28] that result in the
volume decrease. The structural contributions are mostly
negative and arise from interstitial accommodation of the
mixing components because of the difference in molar

volumes [29]. In the present investigation the

Fig.1 Plots of densities, against mole fraction, x1 of

DE/DM for the binary mixtures of DE with DMF/DMSO
or DM with DMF/DMSO

46

VmE

VmE data are

positive in DE+DMF and DM+DMF binary systems

indicates dispersion forces exist between unlike molecules
of the liquid mixing components and negative in
DE+DMSO and DM+DMSO binary systems supports
strong interactions exist between the liquid molecules. The
strength of interaction follows the order DE+DMSO >
DM+DMSO > DE+DMF > DM+DMF. The above
mentioned order indicates the formation of transition
complex with formation of new hydrogen bonds between
the unlike molecules in the liquid mixtures.
When DMSO mixed with DE (=1.86 D and =10.36)
which is polar but practically unassociated, specific
interaction could be donor-acceptor type between the

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49

oxygen atom of S=O group of DMSO with its unshared

pairs of electrons, acts as electron-donor towards electronacceptor chlorine atoms of DE. This might be the reason

E
for negative values of Vm . In case of DMF+DE a new

hydrogen bond between the chlorine atom of DE and

hydrogen atom of DMF (CCl ---- H), hydrogen atom of
DE and oxygen atom of carbonyl group of DMF (-H--C=O) may be formed. The strength of interaction in DMSO
is predominant compared to DMF. DMSO (4.06D) has
large dipole moment compared to DMF (3.82D and hence
dipole-dipole interactions may be expected in the binary
liquid mixtures, this might be possible reason for more
negative

VmE values in the DMSO binary mixtures.

Another important and considerable effect is geometrical

fitting of smaller molecules into the voids created by the

E
bigger molecules for interpreting negative Vm vales.
Molar volumes of DM, DE, DMF and DMSO at 308.15K
are 65.472 80.442, 48.14, 72 cm3.mol-1 respectively.
Therefore, the large

VmE values are attributed to the

dipole-dipole interactions, favorable fitting of smaller

molecules into bigger molecules and hydrogen bond
formation between the unlike molecules in the liquid
molecules. The similar results were also reported by several
authors [7,9,10,12].

negative and positive values of

VmE in all the binary

systems. Fig. 3 shows excess partial molar volumes of

E

DE/DM, V m ,1 and DMF/DMSO, V m , 2 .. Examination of

figure 3 reveals that, indicating strong interactions exist
between the unlike molecules in the DE+DMSO and
DM+DMSO binary mixtures and weak forces between
DE+DMF and DM+DMF. These figures support the

VmE values. From table 4 the

conclusions drawn from

E,

E,

values of V m ,1 V m,2 V m ,1 and V m ,2 values are negative

and positive concluded that strong and weak interactions
exist in the unlike molecules of the components.
Table 4
Partial molar volumes, excess partial molar volumes at
infinite dilutions, V m,1 ,
systems at 308.15 K
Binary system
DE+DMF
DE+DMSO
DM+DMF
DM+DMSO

E,

E,

V m , 2 , V m,1 , V m, 2 for binary

V m,1

V m, 2

8.134
7.9662
6.794
6.5238

E,

E,

V m,1

V m, 2

(x10-5) ( m3.mol-1)
4.7886
0.0898
7.0766
-0.078
4.9816
0.2468
7.1328
-0.0234

-0.0254
-0.1234
0.1676
-0.0672

Fig. 3 Plots of excess partial molar volumes of DE/DM,

E

V m ,1 and DMF/DMSO, V m , 2 for the binary mixtures of

DE with DMF/DMSO or DM with DMF/DMSO (solid
E

The existing molecular interactions in the systems are well

reflected in the properties of partial molar volumes. From
table 3, the values of V m ,1 and V m,2 for both the
components in the DE+DMSO and DM+DMSO binary
mixtures are less than their respective molar volumes in the
pure state i.e contraction of volume takes place on mixing
DE/DM with DMSO. In case of DE+DMF and DM+DMF
binary mixtures V m ,1 and V m,2 for both the components
are higher than their respective molar volumes in the pure
state i.e expansion of volume takes place in the liquid
mixtures. This data are also supporting the observed

47

lines: V m ,1 , dotted lines: V m , 2 )

Conclusions
The densities, of binary mixtures of 1,2-Dichloroethane+
N,N-Dimethyl formamide, 1,2-Dichloroethane+Dimethyl
sulphoxide, Dichloromethane+ N,N-Dimethyl formamide
and Dichloromethane+Dimethyl sulphoxide at 308.15 K.
From this experimental data, excess molar volume has been
determined. A good correlation exist between
experimentally calculated and RK polynomial excess molar
volumes. This show, experimentally calculated

VmE data

better fits the RK polynomial. Hydrogen bond formation

between the unlike molecules, dipole-dipole interactions
and interstitial accommodation of unlike molecules are the

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49

favorable factors for the responsible of

VmE data in the

E

present binary mixtures. The V m ,1 , V m,2 , V m ,1 , and V m,2

have been computed from the experimental results. The
calculated values of partial molar volumes and excess
partial molar volumes at infinite dilution data supports the

conclusions drawn from Vm .

References
1. B. Giner, S. Martin, H. Artigas, M.C. Lopez, C.
Lafuente, Study of weak molecular interactions
through thermodynamic mixing properties, J. Phys.
Chem. B. 30 (2006) 1768317690.
2. C.M. Kinart, W.J. Kinart, D. Checinska-Majak, A.
Cwiklinska, Volumetric behaviour of binary liquid
mixtures of 2-methoxyethanol with n-butylamine, secbutylamine and tert-butylamine, J. Mol. Liq. 109
(2004) 1922.
3. H. Iloukhani, Z. Zoorasna, R. Soleimani, Excess molar
volumes and speeds of sound of tetrahydrofuran with
chloroethanes or chloroethenes at 298.15 K, Phys.
Chem. Liq. 43 (2005) 391401.
4. C. Reichardt, Solvents Effects in Organic Chemistry,
3rd edn. Wiley, Weinheim, (2003).
5. P.S. Rao, M.C.S. Subha, N.G. Swamy, Excess
thermodynamic properties of binary liquid mixtures
containing dimethylsulfoxide at 30C J. Sol.
Chem.1993, 22(5), 483-487.
6. Ullmanns, Encyclopedia of Industrial Chemistry, 5th,
Completely Revised Edition, Vol. A6, VCH
Verlagsgesellschaft, Weinheim, Federal Republic of
Germany, 1986, p. 256.
7. M. Radhamma, K. Sivakumar, M.V.P. Rao, Molecular
interactions
in
binary
liquid
mixtures
of
dimethylsulphoxide
with
chloroethanes
and
chloroethenes, Indian J. Chem. Technol. 11 (2004)
710-713.
8. O. Ciocirlan, O. Iulian, Density, viscosity and
refractive index of the dimethyl sulfoxide +o-xylene
system, J. Serb. Chem. Soc. 74 (2009) 317-329.
9. H. Kumar, Deepika, Thermodynamic study of binary
liquid mixtures of water +DMSO at T=308.15K,
International Journal of Chemical Science and
Technology. 2(1) (2012) 1-8.
10. B. Vijaya Kunar Naidu, K. Clhowdoji Rao, M.C.S.
Subha, Densities and Viscosities of Mixtures of Some
Glycols and Polyglycols in Dimethyl Sulfoxide at
308.15 K J. Chem. Eng. Data. 47 (2002) 379-382.
11. F. Comelli, R. Francesconi, A. Bigi, K. Rubini, Excess
Molar Enthalpies, Molar Heat Capacities, Densities,
Viscosities, and Refractive Indices of Dimethyl
Sulfoxide + Esters of Carbonic Acid at 308.15 K and
Atmospheric Pressure J. Chem. Eng. Data. 51 (2006)
665-670.
12. R.S. Sah, M.N. Roy, Volumetric, viscometric,
interferrometric and refractometric properties of 2methoxyethanol+diethylether+dichloromethane ternary
system and its corresponding binaries at 298.15K.
Phy. Chem. Liq. 49 (2011) 133144.

48

13. L. Su, H. Wang, Volumetric properties of

dichloromethane with aniline or nitrobenzene at
different temperatures: A theoretical and experimental
study, J. Chem. Thermodynamics. 41 (2009) 315322.
14. B. Sathyanarayana, B. Ranjithkumar, T. Savitha
Jyostna, N. Satyanarayana, Densities and viscosities of
binary liquid mixtures of N-methylacetamide with
some chloroethanes and chloroethenes at T = 308.15
K, J. Chem. Thermodynamics. 39 (2007) 1621.
15. A. Ali, M. Tariq, Temperature dependence of excess
VE
molar volumes,
and deviation in isentropic
T

16.

17.

18.
19.

20.

21.

22.

23.

24.
25.

compresibilities of binary liquid mixtures of benzene

with chloroalkanes, J. Mol. Liq. 137 (2008) 6473.
S.C. Bhatia, R. Bhatia, G.P. Dubey, Refractive
properties and internal pressures of binary mixtures of
octan-1-ol with chloroform, 1,2-dichloroethane
and 1,1,2,2-tetrachloroethane at 298.15 and 308.15 K,
J. Mol. Liq. 145 (2009) 88102.
J.A. Riddick, W.B. Bunger, T. Sakano, Organic
solvents:physical properties and methods of
purification, 4th ed. Wiley-Interscience, New York
1986.
H.C. Parker, E.W. Parker, Densities of certain aqueous
potassium chloride solutions as determined with a new
pyknometer, J. Phys. Chem. 29 (1925) 130137.
M. Kondaiah, D.S. Kumar, K. Sreekanth, D.K. Rao,
Densities and viscosities of binary mixtures of
propanoic acid with N,N-dimethylaniline and N,Ndiethylaniline at T = (303.15, 313.15, and 323.15) K, J.
Chem. Eng. Data 57 (2012) 352357.
M. Kondaiah, D.S. Kumar, K. Sreekanth, D.K. Rao,
Ultrasonic velocities, densities, and excess molar
volumes of binary mixtures of N,N-dimethyl
formamide with methyl acrylate, or ethyl acrylate, or
butyl acrylate, or 2-ethyl hexyl acrylate at T = 308.15
K, J. Chem. Thermodynamics. 43 (2011) 18441850.
M. Kondaiah, K. Sreekanth, D.S. Kumar, D.K. Rao,
Volumetric and viscometric properties of propanoic
acid in equimolar mixtures of N,N-dimethyl
formamide + alkanols at T/K 5 303.15, 313.15, and
323.15, J. Sol. Chem, 42 (2013) 494-515.
T.M. Aminabhavi, K. Banerjee, Density, viscosity,
refractive index, and speed of sound in binary mixtures
of dimethyl carbonate with methanol, chloroform,
carbon
tetrachloride,
cyclohexane,
and
dichloromethane in the temperature interval (298.15308.15) K, J. Chem. Eng. Data. 43 (1998) 1096-1101.
L. Marcheselli, A. Marchetti, M. Tagliazucchi, L.
Tassi,
G.
Tosi,
N,N-Dimethylformamide2methoxyethanol solvent system. Densities and excess
molar volumes at various temperatures J. Chem. Soc.
Faraday Trans. 88 (1992) 31593163.
O. Redlich, A.T. Kister, Algebric representation of
thermodynamic properties and the classification
solutions, Ind. Eng. Chem. 40 (1948) 345-348.
K.C. Reddy, S.V. Subramanyam, J. Bhimasenachar,
Thermodynamics of binary liquid mixtures containing
cyclohexane part 1, J. Phys. Soc. Jpn. 19 (1964)
559566.

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49

26. M.N. Roy, A. Sinha, B. Sinha, Excess molar volume

and viscosity deviation and isentropic compressibility
of binary mixtures containing 1,3-dioxolane with mono
alcohols at 303.15 K, J. Sol. Chem. 34 (2005) 13111325.
27. K. Hsu-Chen, T. Chein-Hsiun, Densities and
viscosities of binary and ternary mixtures of ethanol, 2butanone, and 2,2,4-trimethylpentane at T) (298.15,
308.15, and 318.15) K, J. Chem. Eng. Data. 50 (2005)
608-615.

28. P.S. Nikam, S.J. Kharat, Density and viscosity studies

of binary mixtures of N,N-dimethylformamide with
toluene and methyl benzoate at (298.15, 303.15,
308.15, and 313.15) K, J. Chem. Eng. Data. 50 (2005)
455-459.
29. S.J. Kharat, P.S. Nikam, Density and viscosity studies
of binary mixtures of aniline +benzene and ternary
mixtures of (aniline + benzene + N,N-dimethylformamide) at 298.15, 303.15, 308.15, and 313.15 K,
J. Mol. Liq. 131132 (2007) 81-86.

Source of support: Nil; Conflict of interest: None declared

49

International Journal of Research in Pure and Applied Physics 2013; 3(4):43-49