Fluid Phase Equilibria 336 (2012) 5258

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Fluid Phase Equilibria

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Vaporliquid equilibria and excess molar volumes of N-methyl-2-pyrrolidone

with 2-alkoxyethanols
K. Rayapa Reddy a , D. Bala Karuna Kumar a , G. Srinivasa Rao b , P.B. Sandhya Sri c , C. Rambabu a,
a
b
c

Department of Chemistry, Acharya Nagarjuna University, Nagarjunanagar, Andhra Pradesh, India

Department of Physics, Andhra Loyola College, Vijayawada, Andhra Pradesh, India
Department of Physics, D.A.R College, Nuzvid, Andhra Pradesh, India

a r t i c l e

i n f o

Article history:
Received 25 May 2012
Received in revised form 19 August 2012
Accepted 22 August 2012
Available online 7 September 2012
Keywords:
Activity coefcients
Wilson model
Gibbs energy
Excess molar volume
Inter molecular hydrogen bonding

a b s t r a c t
Consistent vaporliquid equilibria (VLE) data at 95.3 kPa have been determined for the binary mixtures of
N-methyl-2-pyrrolidone (NMP) +2-methoxyethanol (2-ME), +2-ethoxyethanol (2-EE), +2-butoxyethanol
(2-BE) over the entire composition range using a Swietoslawski ebulliometer. The VLE data have been
correlated by the Wilson model. The investigated binary systems show negative deviation from Raoults
law. None of the binary systems form maximum or minimum boiling point azeotropic mixtures. Also,
densities of all three binary liquid mixtures over the entire mole fraction range are measured at 303.15,
308.15, 313.15, and 318.15 K using densimeter. Excess molar volumes are computed with variation in
composition and temperature, and are correlated by the RedlichKister polynomial equation. The results
of activity coefcients, excess Gibbs energies and excess molar volumes are correlated, and are discussed
in terms of molecular interactions. Also, the effects of temperature and chain length of alkoxyethanols
are studied and are discussed in terms of molecular interactions.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The knowledge of phase equilibrium properties of liquid mixtures is fascinating, and is of great importance both in technological
and theoretical applications. Liquid mixtures are almost ubiquitous and have a place in setting many industries like agrochemical,
pharmaceutical and petrochemical industries [1], often on a multi
scale. Moreover according to environmental restrictions, the formulation of new gasolines requires the use of ethers and alcohols
as blending agents for enhancing the octane number and a modication of the renery [2]. Knowledge of the physical and chemical
properties of liquid mixtures is required to develop physical models, and industrial design development process [3]. The rst step in
the design or optimization of any production plant is the processes
simulation. The accuracy of simulation process depends mainly on
the thermodynamic models used to describe the physical behavior
of the liquid components involved. The high quality vaporliquid
equilibria (VLE) data are essential to improve the parameters of the
predictive models that are used in the simulation process packages. Calculations of VLE in chemical engineering have traditionally
been performed with an equation of state (EOS). These EOS models
are based on pure phase properties, easy to use, and require little

Corresponding author. Fax: +91 08656 235200.

E-mail address: crbpublications@gmail.com (C. Rambabu).
0378-3812/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2012.08.030

computational effort and yield qualitative predictions of binary

mixture VLE. It is well known that the VLE data is vital for simulation and operation of the extractive distillation process and also
for determining the optimal values of parameters in the thermodynamic models [4,5].
Liquid solvents play an important role in a number of chemical
equations [6]. Reducing the use of solvents may be very difcult; for
this reason search for alternative solvents which are non-harmful,
both from toxicological and environmental point of view is very
essential. Among such solvents, N-methyl-2-pyrrolidone (NMP) is
an important solvent, as it is weakly basic, thermally and chemically stable, with a high ash point, low volatile organic solvent [7],
with low vapor pressure [8], easily biodegradable [9], widely used
in extractive distillation [10], absorption [11], gas desulphurization [12], and coal extraction [13]. Also it is nontoxic for aquatic life
and having less toxicological prole or ozone depleting ability [14].
Moreover it is highly polar ( = 4.09 D) with a strong dipolar interaction [15] and having a hydrogen bonding acceptor ability through
the >CO oxygen, and can be used to produce surface coatings [16].
Among Cellosolves, i.e. Alkoxyalkanols viz. 2-methoxyethanol
(2-ME), 2-ethoxyethanol (2-EE), 2-butoxyethanol (2-BE) are very
interesting class of compounds from a practical point of view,
as oxygenated compounds are increasingly used as additives to
gasoline due their octane enhancing and pollution-reducing properties [17,18]. Also these are non-ionic amphiphile molecules, very
effectively used as surfactants with a large number of applications

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

Table 1
Materials description.
Chemical name
N-Methyl-2-pyrrolidone
2-Methoxyethanol
2-Ethoxyethanol
2-Butoxyethanol

Source
Merck
SD-Fine
SD-Fine
SD-Fine

Mass fraction
purity

Purication method

>0.995
>0.995
>0.995
>0.995

distillation at low pressure

fractional distillation
fractional distillation
fractional distillation

Table 2
Comparison of the experimental density (/kg m3 ) of the pure liquids with the
literature data at 303.15 K.
Substance

[19,20]. These solvents have variety of applications in petroleum,

cosmetics, textile, pharmaceutical, and the other industries [21,22].
The formation of hydrogen bond ability of the OH group enhances
because of the presence of the etheric oxygen. Different spectroscopic techniques have been used to investigate the existence of
inter and intra molecular hydrogen bonds in these compounds
[23,24]. Dipole moments of these cellosolves are (ME = 2.23 D,
EE = 2.31 D, BE = 2.08 D) [25,26]. The effective dipole moment of
cellosolves, a useful magnitude to study the impact of polarity on
bulk properties [2729], and is found to be higher than that of the
homomorphic 1-alkanol [30]. The study of cellosolves is of great
interest due to the simultaneous presence of etheric and alcoholic
oxygen atoms on the molecular interactions.
In this paper we report the VLE data at a local atmospheric pressure of 95.3 kPa and volumetric properties of
NMP + 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol at a
temperature range 303.15 K to 318.15 K at an interval of 5 K over the
entire composition range, to characterize the nature and magnitude
of interactions present between the unlike molecules in these mixtures along with the effect of chain length of 2-cellosolves. Excess
molar volumes of the all the investigated binary mixtures have been
tted to RedlichKister equation to obtain the binary interaction
parameters and standard deviation, between the experimental and
calculated values. Even though a study on the excess properties of
binary liquid mixtures of NMP with 2-alkoxyethanols at 298.15 K
is available in the literature [31], no dedicated studies are reported
on the correlation of binary liquid mixture molar volumes and VLE
data to interpret the molecular interactions between the binary
liquid mixtures.
2. Experimental
2.1. Materials
In the present study, all the chemicals used are of analytical
grade, purchased from various commercial sources. NMP (Merck
India 0.995 mole fraction purity) is distilled at low pressure over
freshly activated 0.3 nm molecular sieves [32]. 2-Cellosolves (SD
Fine India >0.995 mole fraction purity) are puried by using the
method described in the literature [33]. All the chemicals are
degassed before measurements. Materials used in the experiments
are listed in Table 1. The purity of the chemicals is assessed by
comparing the measured density values with the reported [3436]
values in the literature as presented in Table 2.
2.2. Method
Vaporliquid equilibrium measurements are performed by a
Swietoslawski type ebulliometer described by Hala et al. [37].
The detailed procedure is explained in our previous article [38].
The binary liquid mixtures are prepared gravimetrically by using
an electronic balance (Sartorius BT224s) with an uncertainty of
1 104 g and are stored in air-tight glass bottles. The mole
fraction uncertainty is estimated to be 0.001. It is ensured that
before being transferred in to the ebulliometer, the components are
well mixed and each binary mixture is used immediately after the

53

N-Methyl-2-pyrrolidone
2-Methoxyethanol
2-Ethoxyethanol
2-Butoxyethanol
a
b
c

/kg m3
exp

lit

1023.45
955.74
921.21
892.28

1023.42a
955.74b
921.18c
892.31c

Ref. [34].
Ref. [35].
Ref. [36].

preparation. Dry nitrogen gas cylinder and a vacuum pump are connected to the ebulliometer with a closed end manometer in line for
maintenance and measurement of the required total pressure of
the system. The required pressure is maintained by adjusting the
opening of the needle valve of the gas cylinder or the bypass line
of the vacuum pump. In this set of experiments, by applying the
needed adjustment and frequently reading the mercury columns of
the manometer the total pressure is maintained within 0.05 kPa of
the required value. The equilibrium temperature is measured using
a mercury in glass thermometer with an accuracy of 0.05 K, which
is calibrated by means of point to point comparison with a standard
platinum resistance thermometer (certied by the National Institute of Standards and Technology, USA) and is calibrated by against
the ice and steam points of distilled water. The thermometer is
placed in the thermo well lled with mercury to note the steady
state temperature of the (vapor + liquid) mixture impinging on the
Cottrell tube.
After the binary mixture is introduced into the ebulliometer,
the heating rate is slowly increased and adjusted to produce the
required boil up rate so that a drop count of about 30 drops per
minute is achieved as per the suggestion of Hala et al. at a pressure
of 95.3 kPa. After the steady state is achieved, the equilibrium temperature is recorded, conrmed by the constancy of the equilibrium
temperature and uniformity of the drop rate is maintained at least
for 30 min. The composition of the mixture is veried both at the
beginning and at the end of each experiment by taking a Gas Chromatograph (GC-17A, Shimadzu), and the analysis is carried out by
using a thermal conductivity detector tted with an SE 30 column.
Densities of pure components and their binary liquid mixtures
over the entire composition range are measured using Anton Paar
DMA 4500 digital vibrating U-tube densimeter, with automatic viscosity correction. The densities of the samples are observed with
a reproducibility of 1 105 g cm3 . As reported by the instrument manufacturer uncertainty in the density measurement, is
1 105 g cm3 at 95% condence level and the accuracy in the density measurement is 5 105 g cm3 . For the period of vibration
(), the densities () of the mixtures are determined using the relationship  = a + b 2 , where a and b are the instrument constants and
are determined by calibration with degassed and bi-distilled water,
and dry air [39]. With a solid state thermostat (Peltier) the temperature in the cell is regulated to 0.01 K. All the measurements are
made in the temperature range 303.15318.15 K at atmospheric
pressure.
3. Results and discussion
Reliable and accurate vaporliquid equilibrium data are always
required for both better understanding of the behavior of liquid
mixtures and process engineering design. The boiling point temperatures (T) of all the pure liquids used in the present investigation
are measured at different pressures (P) using the same method
as that for obtaining VLE data and are presented in Table 3. The

54

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

Table 3
Experimental saturated vapor pressure (P/kPa) boiling point temperature (T/K)
data of pure components.
P/kPa

NMP

ME

EE

BE

95.3
88.7
81.2
76.4
68.6
60.5
53.7
47.9
41.3
34.2
28.1

474.01
471.15
467.66
465.29
461.17
456.48
452.13
448.05
442.88
436.50
430.09

395.78
393.75
391.28
389.59
386.66
383.30
380.17
377.22
373.48
368.84
364.15

406.33
404.22
401.65
399.90
396.86
393.37
390.12
387.06
383.18
378.36
373.48

442.49
440.20
437.42
435.52
432.22
428.43
424.90
421.57
417.35
412.10
406.80

measured vapor pressures of the pure liquids are correlated using

the Antoine equation:
ln[P/(kPa)] =

AB
[T/(K) + C]

(1)

where A, B, and C are Antoine constants and are determined by

tting the PT data using the nonlinear optimization method. The
experimentally determined Antoine constants with the literature
values along with the vapor pressures of the pure components
[40,41] are reported in Table 4. Also, in Table 4 the experimental
vapor pressures of pure components are compared with the values
calculated from the Antoine equation using the Antoine constants
taken from literature.
For the determination of optimum Wilson parameters the
following objective function is minimized with the help of
NelderMead optimization technique, the nonlinear regression
analysis method, described by Kuester and Mize [42]:

(Pcal Pexp )
Pexp

2

(Tcal Texp )
Texp

2

(y1cal y1 exp )
y1 exp

2

(2)

The total pressure of the mixture is calculated using:

Pcal = 1 (Wilson)x1 p1 + 2 (Wilson)x2 p2

(3)

where p1 and p2 are the vapor pressures of the pure components

of the binary liquid mixtures. x1 and x2 are the liquid phase mole
fractions, while  1 and  2 are the activity coefcients of the components 1 and 2 of the binary liquid mixture. Assuming ideal behavior,
the liquid-phase activity coefcients are calculated using the following equations as described by Reid and Walas [43,44].
ln 1 = ln (x1 + 12 x2 ) + x2

12
21

x1 + 12 x2
x2 + 21 x1

(4)

ln 2 = ln (x2 + 21 x1 ) + x1

21
12

x2 + 21 x1
x1 + 12 x2


(5)

where the adjustable parameters 12 and 21 are given by

12 =


21 =

V2L
V1L
V1L

   
12
11

exp

V2L

(6)

RT

   
12
22

exp

(7)

RT

where V1L and V2L are the molar volumes of the pure components
calculated from the experimental densities at 303.15 K. The Binary
interaction parameters for the Wilson equation together with the
average deviations in temperature are represented in Table 5, and
are used to determine the activity coefcients using Eqs. (4) and (5),
from which the corresponding vapor phase composition (y1 ) in the
binary liquid mixture at a particular liquid composition is obtained
by the equation:
y1 =

1 x1 p1
pcal

(8)

Data on liquid phase mole fraction (x1 ), experimental and calculated boiling point temperatures (Texp , Tcal ), experimental and
calculated vapor phase mole fractions (y1 ), deviations in boiling
point temperature ( T) and vapor phase mole fraction ( y1 ), activity coefcients ( i ) and excess Gibbs energies of the binary systems
NMP (1) + ME (2), EE (2) and BE (2) at 95.3 kPa are shown in Table 6.
It is clear that the values of activity coefcients are less than
unity for all the three binary liquid systems under study, indicating nonideal nature of these mixtures with a negative deviation
from Raoults law. The observed negative deviations from Raoults
law in all the three systems may be due to the presence of strong
intermolecular forces like hydrogen bonding between the binary
mixture components. The positive and negative deviations for nonideal solutions from vaporliquid studies are well described by
Harrison et al. [45]. The boiling point temperature versus mole fraction curves in both liquid (x1 ) and vapor phases (y1 ) are presented
in Fig. 1 for all the three binary systems under investigation and it
is observed that no azeotropic mixtures are formed.
The VLE data are checked for the thermodynamic consistency
using the Herington area test and the data are found to be thermodynamically consistent. The excess Gibbs energies of all binary
systems under investigation, over the entire composition range,
are determined from the activity coefcients obtained by Wilson
model through:
GE = RT (x1 ln 1 + x2 ln 2 )

(9)

and are presented in Fig. 2.

The experimental results of densities () and excess molar volumes (V) for all the three binary systems under investigation as
a function of mole fraction of NMP, in the temperature range
303.15318.15 K are given in Table 7. The excess molar volumes
(VE ) are calculated using the molar masses (M) from the relation:
VE =

(x1 M1 + x2 M2 )

mix

 x M   x M 
1 1
2 2
1

(10)

2

Table 4
Comparison of experimental Antoine constants used in Antoine equation: ln (P/kPa) = A B/[T/(K) + C] and experimental vapor pressures with the literature values.
Substance
NMP
ME
EE
BE
a
b

Ref. [40].
Ref. [41].

exp
lit
exp
lit
exp
lit
exp
lit

Tmin

Tmax

P at exp Tmax

14.58554
14.65738a
16.54076
16.62950e
16.71088
16.80199b
16.97841
17.07383b

4057.42
4112.28a
4098.61
4156.60b
4371.98
4434.64b
4953.49
5026.32b

69.422
66.866a
53.770
51.487b
46.606
44.165b
43.706
40.927b

430.09
380.73
364.15
188.05
373.48
183.00
406.80
203.15

474.01
475.72
395.78
564.00
406.33
569.00
442.49
600.00

95.30
95.32
95.30
95.28
95.30
95.31
95.30
95.30

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

55

Table 5
Representation of VLE measurements by Wilson model.
Substance 1

Substance 2

[(12 22 )/R]

[(12 22 )/R]

T/K

y1

NMP
NMP
NMP

ME
EE
BE

36.1961
11.2250
59.7850

15.8513
54.2571
140.9097

0.028
0.043
0.077

0.006
0.011
0.013

T = [ (Texp Tcal )2/ n]0.5 .

y = [ (y1exp y1cal )2/ n]0.5 .

The excess molar volumes for each binary mixture, at each

investigated temperature are tted to RedlichKister type polynomial equation [46]:

weighed equally and the standard deviations (

) are calculated
using:

V =

V E = x1 x2 Aj1 (x2 x1 )j1

(11)

where Aj1 are adjustable parameters. The values of coefcient

Aj1 are evaluated by the method of least squares with all points

E VE )
(Vexp
cal

0.5
(12)

(m n)

where m is the number of experimental data points and n is the

number of coefcients considered (n = 5 in the present study). The
tting coefcients (Aj1 ) of the RedlichKister polynomial along

Table 6
Data on liquid phase mole fraction (x1 ), boiling point temperature (T/K), vapor phase mole fraction (y1 ), deviations in boiling point temperature ( T/K) and vapor phase mole
fraction ( y1 ), activity coefcients ( i ) and excess Gibbs energies (GE /J mol1 ) of the binary systems N-methyl-2-pyrrolidone (1) + 2-Alkoxyalkanols (2) at 95.3 kPa.
Tcal

y1exp

y1cal

y1

NMP (1) + 2-ME (2)

395.78
0.000
0.084
398.19
0.171
401.04
404.39
0.261
0.354
408.36
413.09
0.451
418.87
0.552
0.657
426.12
0.767
435.78
0.881
449.75
0.916
455.43
459.83
0.940
466.21
0.970
470.71
0.988
1.000
474.01

395.44
397.85
400.79
404.27
408.33
413.00
418.87
426.02
435.78
449.74
455.46
459.35
466.01
470.10
473.56

0.34
0.34
0.25
0.12
0.03
0.09
0.00
0.10
0.00
0.01
0.03
0.48
0.20
0.61
0.45

0.000
0.008
0.019
0.032
0.049
0.072
0.106
0.158
0.248
0.432
0.532
0.621
0.773
0.897
1.000

0.000
0.009
0.017
0.031
0.046
0.071
0.107
0.161
0.253
0.442
0.543
0.632
0.781
0.902
1.000

0.000
0.001
0.002
0.001
0.003
0.001
0.001
0.003
0.006
0.010
0.011
0.011
0.008
0.004
0.000

0.9488
0.9590
0.9682
0.9764
0.9835
0.9893
0.9940
0.9973
0.9993
0.9997
0.9998
1.0000
1.0000
1.0000

1.0000
0.9995
0.9980
0.9955
0.9919
0.9873
0.9817
0.9751
0.9676
0.9596
0.9571
0.9554
0.9534
0.9522

0.00
16.06
29.34
39.60
46.57
49.97
49.47
44.69
35.23
20.57
15.06
11.08
5.76
2.34
0.00

NMP (1) + 2-EE (2)

406.33
0.000
0.101
409.46
413.20
0.202
417.44
0.302
0.402
422.19
427.50
0.503
433.52
0.602
440.50
0.702
448.86
0.802
453.79
0.851
459.43
0.901
462.59
0.926
466.03
0.951
470.95
0.982
474.01
1.000

406.60
409.61
412.68
417.36
422.14
427.04
433.74
440.66
449.62
453.30
458.94
462.78
466.68
470.65
474.68

0.27
0.15
0.52
0.08
0.05
0.46
0.22
0.16
0.76
0.49
0.49
0.19
0.65
0.30
0.67

0.000
0.015
0.033
0.056
0.084
0.122
0.174
0.248
0.364
0.449
0.566
0.642
0.735
0.889
1.000

0.000
0.014
0.031
0.054
0.083
0.123
0.178
0.257
0.379
0.467
0.585
0.661
0.752
0.898
1.000

0.000
0.001
0.002
0.002
0.001
0.001
0.004
0.009
0.015
0.018
0.019
0.019
0.016
0.009
0.000

0.9140
0.9331
0.9497
0.9638
0.9754
0.9846
0.9916
0.9964
0.9980
0.9991
0.9995
0.9998
1.0000
1.0000

1.0000
0.9988
0.9953
0.9897
0.9823
0.9732
0.9628
0.9512
0.9388
0.9324
0.9259
0.9227
0.9194
0.9154

0.00
34.62
60.93
79.20
89.65
92.52
88.02
76.33
57.66
45.75
32.17
24.74
16.90
6.27
0.00

NMP (1) + 2-BE (2)

0.000
442.49
446.53
0.132
450.85
0.255
455.01
0.369
458.83
0.477
462.26
0.577
465.29
0.672
467.95
0.761
470.26
0.845
472.27
0.925
472.82
0.948
473.18
0.963
473.52
0.978
473.85
0.993
474.01
1.000

442.48
446.63
450.85
455.15
458.94
462.19
465.19
467.91
470.36
472.21
472.83
473.14
473.45
473.77
474.08

0.01
0.10
0.00
0.14
0.11
0.07
0.10
0.04
0.10
0.06
0.01
0.04
0.07
0.08
0.07

0.000
0.061
0.127
0.198
0.277
0.363
0.459
0.568
0.691
0.833
0.880
0.913
0.947
0.982
1.000

0.000
0.053
0.116
0.189
0.272
0.366
0.471
0.588
0.716
0.853
0.897
0.926
0.955
0.985
1.000

0.000
0.008
0.011
0.010
0.005
0.003
0.012
0.020
0.025
0.020
0.016
0.013
0.008
0.003
0.000

0.8694
0.9008
0.9271
0.9485
0.9657
0.9789
0.9886
0.9951
0.9988
0.9994
0.9997
0.9999
1.0000
1.0000

1.0000
0.9970
0.9889
0.9766
0.9609
0.9425
0.9220
0.8998
0.8764
0.8522
0.8448
0.8398
0.8348
0.8298

0.00
78.03
130.83
162.33
175.73
173.71
158.51
132.06
95.92
51.49
36.73
26.57
16.10
5.41
0.00

x1

Texp

Standard uncertainties u are: u(T) = 0.05 K, u(P) = 0.05 kPa, and the combined standard uncertainty uc is uc (x1 ) = 0.001.

1

2

GE

56

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

Table 7
Densities (/kg m3 ) and excess molar volumes (VE /106 m3 mol1 ) of NMP + ME, NMP + EE, and NMP + BE at T = 303.15, 308.15, 313.15 and 318.15 K.
x1

303.15 K

308.15 K

313.15 K

318.15 K

VE

VE

VE

VE

NMP (1) + ME (2)

0.000
0.084
0.171
0.261
0.354
0.451
0.552
0.657
0.767
0.881
0.916
0.940
0.970
0.988
1.000

955.74
965.64
975.06
983.98
992.29
999.91
1006.73
1012.64
1017.50
1021.17
1022.00
1022.50
1023.01
1023.30
1023.45

0.00
0.26
0.49
0.68
0.82
0.90
0.92
0.85
0.69
0.42
0.31
0.23
0.12
0.05
0.00

951.14
961.46
971.25
980.47
989.00
996.77
1003.64
1009.49
1014.17
1017.52
1018.23
1018.64
1019.04
1019.24
1019.34

0.00
0.30
0.55
0.77
0.92
1.02
1.03
0.96
0.78
0.47
0.35
0.26
0.13
0.05
0.00

946.25
957.05
967.28
976.83
985.62
993.52
1000.44
1006.19
1010.64
1013.58
1014.14
1014.43
1014.68
1014.78
1014.82

0.00
0.34
0.63
0.87
1.05
1.16
1.17
1.09
0.88
0.53
0.39
0.29
0.15
0.06
0.00

941.59
952.92
963.59
973.49
982.52
990.55
997.46
1003.04
1007.15
1009.56
1009.93
1010.07
1010.13
1010.10
1010.06

0.00
0.39
0.72
1.00
1.20
1.32
1.34
1.24
1.01
0.61
0.45
0.33
0.17
0.07
0.00

NMP (1) + EE (2)

0.000
0.101
0.202
0.302
0.402
0.503
0.602
0.702
0.802
0.851
0.901
0.926
0.951
0.982
1.000

921.21
936.06
949.87
962.64
974.38
985.10
994.78
1003.45
1011.12
1014.58
1017.78
1019.29
1020.74
1022.50
1023.45

0.00
0.48
0.84
1.09
1.23
1.26
1.20
1.03
0.78
0.62
0.43
0.33
0.23
0.08
0.00

916.48
931.85
946.07
959.15
971.10
981.93
991.62
1000.20
1007.68
1011.01
1014.06
1015.48
1016.84
1018.47
1019.34

0.00
0.54
0.94
1.21
1.36
1.40
1.33
1.15
0.86
0.68
0.48
0.37
0.25
0.09
0.00

911.88
927.80
942.45
955.84
967.97
978.86
988.50
996.91
1004.10
1007.23
1010.06
1011.37
1012.59
1014.05
1014.82

0.00
0.60
1.05
1.35
1.52
1.56
1.48
1.28
0.96
0.77
0.54
0.41
0.28
0.10
0.00

907.79
924.28
939.35
953.02
965.30
976.19
985.68
993.82
1000.58
1003.46
1006.00
1007.14
1008.20
1009.43
1010.06

0.00
0.67
1.17
1.51
1.70
1.75
1.66
1.43
1.08
0.86
0.60
0.46
0.32
0.12
0.00

NMP (1) + BE (2)

0.000
0.132
0.255
0.369
0.477
0.577
0.672
0.761
0.845
0.925
0.948
0.963
0.978
0.993
1.000

892.28
914.72
934.22
951.20
966.04
979.00
990.36
1000.30
1009.04
1016.72
1018.83
1020.19
1021.52
1022.82
1023.45

0.00
1.30
2.08
2.46
2.55
2.42
2.12
1.71
1.20
0.63
0.44
0.32
0.19
0.06
0.00

888.19
911.20
931.07
948.27
963.19
976.12
987.35
997.10
1005.59
1012.95
1014.97
1016.26
1017.52
1018.74
1019.34

0.00
1.40
2.22
2.62
2.72
2.58
2.26
1.82
1.28
0.67
0.47
0.34
0.20
0.07
0.00

884.17
907.80
928.06
945.46
960.43
973.27
984.32
993.80
1001.93
1008.89
1010.77
1011.97
1013.14
1014.27
1014.82

0.00
1.50
2.39
2.82
2.92
2.76
2.42
1.95
1.37
0.71
0.50
0.36
0.22
0.07
0.00

880.02
904.37
925.08
942.72
957.74
970.48
981.30
990.46
998.18
1004.66
1006.39
1007.49
1008.55
1009.57
1010.06

0.00
1.63
2.58
3.04
3.14
2.98
2.61
2.10
1.47
0.77
0.54
0.39
0.23
0.08
0.00

Standard uncertainty uc (x1 ) = 0.001, uc () = 0.00001 g cm3 .

with the standard deviations are presented in Table 8. The variation

of the smoothened excess molar volumes of all the three binary
mixtures (NMP + 2-ME, NMP + 2-EE and NMP + 2-BE) with the mole
fraction of NMP at different temperatures are presented in Fig. 3.
From Figs. 2 and 3, it is observed that for all the systems under
study excess Gibbs energy and excess molar volume values are negative and non-linear with minima at near equimolar composition,
showing the presence of complex formation between the unlike
molecules of the binary mixture components; and the interactions
between the binary liquid mixtures follow the order:
NMP + BE > NMP + EE > NMP + ME
In NMP, the molecules are self-associated through the dipolar
interactions whereas in 2-alkoxyethanols molecular associations
are through both intermolecular hydrogen bonding and dipolar
interactions. Mixing of NMP with 2-alkoxyethanol results in the
mutual dissociation of the structures present in pure liquids
with subsequent formation of new hydrogen bonds (C O H O)

between proton acceptor oxygen atom of C O group of NMP

molecules and hydrogen atom of OH groups of 2-alkoxyethanol
molecules [47] as the hydrogen bond between hydroxyl groups and
carbonyl oxygen atoms are stronger than those formed between
homo-cooperative hydroxyl molecules [25]. It is well known that
the dispersion forces cause positive contributions to excess values, while dipoledipole, dipole-induced dipole, charge-transfer
interaction and hydrogen bonding between the components of dissimilar molecules of binary mixture makes negative contributions
[4850]. Figs. 2 and 3 also suggest the dependence of the strength
of interactions on the chain length of alkyl group of alkoxyethanols
perhaps due to the increase in the +I effect in the order of methyl
group of 2-ME, ethyl group of 2-EE and butyl group of 2-BE. Thus,
the strength of interactions between NMP and alkoxyethanols follows the order: NMP + BE > NMP + EE > NMP + ME.
From Fig. 3, it can be seen that the value of negative excess
molar volumes increases with the rise of temperature, in all the
three binary systems under investigation. It is well known that,

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

57

Fig. 2. Variation of excess Gibbs energy (GE /J mol1 ) with the mole fraction of NMP
for  NMP + ME, NMP + EE, and NMP + BE binary systems.
Table 8
Coefcients Aj1 of RedlichKister equation, Eq. (11) and the corresponding standard
deviations (
) of excess molar volumes (VE /106 m3 mol1 ) for the three binary
mixtures of NMP at different temperatures.

Fig. 1. Experimental boiling point temperatures (T/K) at 95.3 kPa against the mole
fraction of NMP in liquid phase (x1 ) and vapor phase (y1 ) for the mixtures of (a)
NMP + ME, (b) NMP + EE, (c) NMP + BE.

T/K

A0

NMP (1)+ ME (2)

303.15
308.15
313.15
318.15

3.6768
4.1433
4.7064
5.3773

0.3497
0.3764
0.4096
0.4504

NMP (1) + EE (2)

303.15
308.15
313.15
318.15

5.0474
5.5966
6.2458
7.0010

NMP (1) + BE (2)

303.15
308.15
313.15
318.15

10.1402
10.8183
11.5998
12.5109

A1

A2
0.0400
0.0505
0.0670
0.0775

A3

A4

0.0019 0.0140
0.0036 0.0149
0.0040
0.0033
0.0079 0.0093

0.0007
0.0006
0.0004
0.0003

0.2901
0.3275
0.3666
0.4096

0.0428
0.0051 0.0553
0.0680 0.0038 0.0339
0.1180 0.0116
0.0061
0.1099 0.0088 0.0435

0.0006
0.0003
0.0002
0.0004

1.5155
1.6630
1.8329
2.0300

0.1882
0.2205
0.2970
0.3590

0.0004
0.0004
0.0002
0.0005

0.0323 0.0506
0.0397 0.0534
0.0451 0.0014
0.0577
0.0152

Fig. 3. Plot of excess molar volume (VE /106 m3 mol1 ) with mole fraction of NMP for the systems: (a) NMP (1) + ME (2) (b) NMP (1) + EE (2) (c) NMP (1) + BE (2) at  303.15 K,
 308.15 K,  313.15 K, and 318.15 K.

58

K.R. Reddy et al. / Fluid Phase Equilibria 336 (2012) 5258

as the temperature is increased, thermal energy facilitates

breaking the associated molecules of the pure components of
NMP and 2-alkoxyalkanols in to their monomers and hence they
form hetero associates by hydrogen bonding between NMP and
2-alkoxyethanol molecules [25].
4. Conclusions
VLE data for the binary mixtures of NMP with 2-alkoxyethanols
are measured at 95.3 kPa using a Swietoslawski type ebulliometer. From the observed VLE data of NMP +ME, +EE, and +BE no
minimum or maximum boiling point azeotropes at the pressure
of 95.3 in any of the three investigated binary mixtures over the
entire composition range. The experimental VLE data for the three
binary mixtures are correlated by the Wilson model. Also, densities of all the three binary systems over the entire mole fraction
range are experimentally determined and excess molar volumes
are computed at a temperature range 303.15318.15 K. Our VLE
results indicate that all three binary systems are nonideal liquid
mixtures deviating from Raoults law due to strong intermolecular interactions which are in good agreement with the results
obtained by the excess molar volumes. From GE and VE data it is
concluded that molecular interactions between unlike molecules
take place through hydrogen bonding between oxygen atom of
C O group of NMP molecules and hydrogen atom of OH groups
of 2-alkoxyethanol molecules.
Acknowledgements
One of the authors, K. Rayapa Reddy wishes to thank University
Grants Commission of India for awarding teacher fellowship under
FDP scheme and Director IICT, Hyderabad for providing laboratory
facilities. He also expresses his gratefulness to Rev. Fr. Dr. Francis
Xavier SJ, Principal, Andhra Loyola College, Vijayawada for granting
study leave.
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