1. No category

IJPRD, 2014; Vol 6(12):January-2015(12 - 18)
International Standard Serial Number 0974 – 9446
-------------------------------------------------------------------------------------------------------------------------------------------------DENSITIES AND VISCOSITIES FOR BINARY MIXTURES OF ETHYLENEDIAMINE WITH WATER AT HIGHER
TEMPERATURE
G.P. Borse *1 and U.G. Deshpande2
1*
2
Department of Chemistry, R.L. College, Parola – 425 111.
Department of Chemistry, Pratap College, Amalner – 425 401.
ABSTRACT
The densities and viscosities of Binary mixtures of
ethylenediamine with water have been measured at six
temperatures over the entire range of mole fraction of the
compounds at atmospheric pressure. From these measurements,
excess molar volume (vE), viscosity deviations (), excess Gibbs
free energy of activation GE* of viscous flow, Grunberg Nissan
(d), Tamura and Kurata (T12), Hind et al (H12), Katti Chaudhari
(Wvis) interaction parameters were derived. The negative values
of excess molar volumes were exhibited by the systems. These
results suggest strong hydrogen bonding interactions in the
composition of the entire mole fraction.
Keywords: ethylenediamine,
deviations, densities etc.
Binary
mixtures,
INTRODUCTION
The physical properties of a binary mixture
such as viscosity and density are important from
practical and theoretical points of view to
understand the theory of liquids. Their properties
are extremely useful for the design of types of
transport and process equipment in chemical
industries.
The present paper is an attempt to study
the excess properties of the binary mixtures in a
Correspondence Author
G.P. Borse
Department of Chemistry,
R.L. College, Parola – 425 111
MH, India
viscosity
systematic way. The paper describes the binary
mixtures of di-amine which are industrially
important organic compounds.
Properties such as viscosities and excess
molar volumes of binary mixtures of ethylene
diamine and water are studied here.
EXPERIMENTS –
METHODS
Ethylenediamine (A.R. Grade from S.D. Fine
Chemicals) was kept over potassium hydroxide and
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International Journal of Pharmaceutical Research & Development
calcium oxide for 48 hours and then distilled. The
first and last fractions were discarded only the
middle fraction was collected and stored and
protected against moisture and carbon dioxide.
Triple distilled water (specific conductance less
than 10 S cm-1) was employed in making of the
compositions.
Densities of the pure components and their
compositions were measured on a vibrating tube
density-meter, reproducible to 1 x 10-5 gm cm-3
(Anton paar model DMA 5000) measuring with high
temperature accuracy (± 0.001 K) in a wide
temperature range.
The density-meter was
calibrated with triple distilled water, the observed
density was 0.998212 gm cm-3 at 20 °C which is
closer to literature value.1 The mixtures were
prepared by mixing known masses of pure liquid in
air tight, narrow-mouth ground stoppered bottles
taking precautions to minimise the evaporation
losses. All measurements of mass were performed
on an electronic balance with accuracy of 0.1 mg.
Measurement of the dynamic viscosity 
viscosities and various compositions was carried
out by using a suspended level Cannon-Ubbelohde
viscometer.
The viscometer was suspended
vertically in a constant temperature bath (± 0.05
°C). The time given to attain thermal equilibrium
for content of viscometer was 15 min. The flow
time was measured to an accuracy of 0.1 S till a
constant flow time was observed. The viscometer
was separately calibrated with benzene and
toluene (HPLC grade).
At 303.15 K, the
reproducibility in the viscosity measurement was ±
0.01 mPaS. Viscosities of the pure component of
water were taken from the literature.
RESULTS –
Excess molar volumes VE were calculated
from the measured densities2,3 () by using the
relation.
VE
=
(x 1 M 1 + x 2 M 2 )
− (x 1 V1 + x 2V2 )
ρ
ISSN: 0974 – 9446
——— (1)
Where, x1 and x2 are mole fractions, M1 and M2 the
molecular weights and V1 and V2 are the molecular
volumes of ethylenediamine (1) and water (2)
respectively. The experimental densities, excess
molar volumes, viscosities and deviation in
viscosities of binary mixtures of ethylenediamine
(1) + water (2) at six different temperatures are
reported in Table 1.
Dynamic viscosities () of ethylenediamine
(1) and water (2) mixtures of different
temperatures were calculated by measuring
density and flow time of the mixture (Table 1). The
viscosity deviation was calculated6,7 by the
equation (2)
——— (2)

=  – {x1 1 + x2 2}
The experimental values of  are also
reported in (Table 1).
On the basis of theory of absolute reaction
rates, the excess Gibb’s energies (G*E) of
activation was calculated 8,9 from equation (3)
  η V 
 η V 
∆G * E
 − x 1 ln  1 1   ——— (3)
= ln 
 η V 
RT
  η 2 V2 
 2 2 
where v, v1 and v2 are the molar volumes of
the binary mixture and pure components and
calculated values of GE* are shown in Table 1.
The activation parameters G*, H*
and S* were calculated using Eyring and John’s
equation10,11.
hN
 ∆H * ∆S * 


=
exp 
−
——— (4)
V
R 
 RT
where  is viscosity of binary mixture in Pa.S
and h, N and V are Planck’s constant, Avogadro’s
number and molar volume respectively.
When ln (V / hN) is plotted against
1/T, the slope is equal to H*/R and intercept is
equal to – S*/R. Using graphical method, the
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13
International Journal of Pharmaceutical Research & Development
They suggested a regular solution model of
approximation.
Hind et el13 calculated second viral
coefficient H12 by the equation —
m
= x1² 1 + x2² 2 + 2 x1 x2 H12 ——— (6)
It could give a useful description of the
behaviour of the mixtures. Where H12 is the Hind
et al interaction parameter.
Tamura and Kurata14 gave the definition
mutual viscosity and derived a new Semi—
empirical equation —
h
= x1 1 1 + x2 2 2 + 2(x1 x2 1 2)½ T12
——— (7)
where 1 and 2 are the volume fractions of
components 1 and 2 respectively, T12 is Tamura and
Kurata constant.
Gruenberg and Nissan15 derived an
equation correlating the viscosity of liquid mixtures
with viscosity and constituents, composition of the
mixture and interaction parameter between the
molecules
ln 
= x1 ln 1 + x2 ln 2 + x1 x2 d ——— (8)
where, , 1 and 2 — are the viscosity of binary
mixture, ethylenediamine (1) and water (2)
respectively, d is Gruenberg and Nissan constant.
Wvis, H12, T12 and d values were calculated
by eqn. 5, 6, 7 and 8 are presented in Table 4.
DISCUSSION
The graphical presentation of the excess
molar volumes of ethylenediamine + water as
shown in Fig. 1. In this system also the values of
excess molar volume are found to the indeed
negative, indicating strong hydrogen bonding
interactions in the composition; of the entire mole
fraction range. Maximum deviation in the excess
molar volumes occurred at 0.42 mole fraction. The
largest value in this system of excess molar volume
is — 1.990330. It is observed that changes in the
excess molar volume values are almost same in the
temperature region 318.15 K to 328.15 K.
0.00
0.00
0.20
0.40
0.60
0.80
318.1
5K
320.1
5K
322.1
5K
324.1
5K
1.00
-0.50
VE (cm3 mol-1)
activation parameters H* and S* were obtained
and G* was obtained using the equation G* =
H*– TS* values obtained are presented in Table 3.
The interaction energy for the activation
flow were determined using Katti and Chaudhari12
equation —

Wvis =
RT
[ln η V − x 1 ln η 1V1 − x 2 ln η 2 V2 ] ——— (5)
x1 x2
ISSN: 0974 – 9446
-1.00
-1.50
-2.00
-2.50
X1
Fig. 1 : Excess molar volume (VE) for the system
ethylenediamine (1) + water (2) from 318.5 K to 328.15
K.
In this binary system molecular association
of ethylenediamine (1) and water (2) is found to
take place. The hydrogen bond in association of
ethylenediamine and water is N—H ———O type.
The strength of which is determined by the
geometry of the molecules and nature of the
substituent ethane moiety. In non—electrolyte
systems, positive deviations from ideal behaviour
are attributed to dispersion forces and negative
deviations to the geometric considerations.
Graphical presentation of the experimental
 values plotted against the fitted equations are
as shown in Fig. 2.
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14
International Journal of Pharmaceutical Research & Development
ISSN: 0974 – 9446
X1
0.00
0.20
0.40
0.60
0.80
1.00
0
0.5
1
P
a
s
)
∆
η(m
318.15 K
1.5
320.15 K
322.15 K
2
324.15 K
326.15 K
2.5
328.15 K
3
3.5
4
Fig. 2 : Viscosity deviation for ethylenediamine (1) water (2) from 318.15 K to 328.15 K
The value of  are positive over the entire
range of mole fraction and maximum positive value
at mole fraction  at six temperatures due to
association between ethylenediamine (1) and
water (2) molecules through hydrogen bonding (to
form adducts between them) over the dissociation
effects in the system16.
2.10
*Ex10-4 (Jm
ol-1)
∆G
2.05
318.15 K
2.00
320.15 K
1.95
322.15 K
1.90
324.15 K
326.15 K
1.85
328.15 K
1.80
1.75
0.00
0.20
0.40
0.60
0.80
1.00
X1
Fig. 3 : Excess energy of activation for viscous flow
Excess energy of activation for viscous flow is shown in Fig. 3. The observed GE* values are positive17,18 for
entire mole fraction of ethylenediamine (1) + water (2). Large positive values indicates the specific interaction
due to complex formation through intermolecular hydrogen bonding interaction between ethylenediamine (1)
and water (2) molecules (unlike molecules) compared to like molecules.
The observed values of H* and G* for the binary mixture are positive as shown in Table 3. The G*
and H* values steadily increases with conc. extraction upto 0.34 mole fraction and then decreases.
The viscosity values of Binary mixtures of the system are fitted in eqn. 5, 6, 7 and 8 to evaluate
Chaudhari—Katti (Wvis), Hind et al (H12), Tamura—Kurata (T12) and Gruenberg Nissan (d) interaction
parameters from the analysis of these table (4), the values of these parameters indicate strong specific
interaction between the component of ethylenediamine (1) + water (2) molecules.
The positive values of d and Wvis indicate the presence of strong specific interaction between unlike
molecules.19,20
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International Journal of Pharmaceutical Research & Development
ISSN: 0974 – 9446
Table — 1 : Densities, Viscosities, excess molar volume, excess viscosities and Gibb’s Energy of activation of
Viscous flow for ethylenediamine (1) + water (2) at 318.15, 320.15, 322.15, 324.15, 326.15, 328.15 K
 (gcm—3)
 (mPa-S)
VE (cm3, mol—1)
0.00
0.10
0.990188
0.982588
0.598680
2.129875
—
—0.603484
—
1.494083
—
1.879991
0.23
0.979226
4.400016
—1.491199
3.315981
2.043570
0.34
0.967176
4.477770
—1.896767
3.752913
2.064908
0.38
0.42
0.961322
0.955328
4.327451
4.144480
—1.958261
—1.990330
3.587759
3.389934
2.051759
2.035615
0.45
0.950436
3.915129
—1.971753
3.149449
2.016747
0.50
0.942282
3.532876
—1.932342
2.748641
1.982562
0.60
0.80
0.926548
0.899183
2.853656
2.010784
—1.726711
—1.025662
2.032310
1.115217
1.909731
1.776331
1.00
0.876295
—
—
X1
 (mPaS)
GE* (J mol—1)
318.15 K
X1
320.15 K
0.00
0.10
0.23
0.34
0.38
0.42
0.45
0.50
0.60
0.80
1.00
322.15 K
0.00
0.10
0.23
0.34
0.38
0.42
0.45
0.50
0.60
0.969791
—
—3
 (gcm )
 (mPa-S)
E
V (cm , mol )
 (mPaS)
GE* (J mol—1)
0.989419
0.981686
0.977629
0.965393
0.959508
0.953488
0.948593
0.940432
0.924692
0.897331
0.874398
0.576280
2.013648
3.685177
4.091936
3.960494
3.800613
3.600639
3.267645
2.674276
1.913185
0.932590
—
—0.622074
—1.500175
—1.903590
—1.964794
—1.996210
—1.988136
—1.938805
—1.733145
—1.031536
—
—
1.401737
3.0269456
3.394511
3.248816
3.074683
2.864019
2.512911
1.884204
1.051857
—
—
1.887672
2.045595
2.064970
2.052151
2.036453
2.018237
1.985339
1.915585
1.785416
—
0.988647
0.980794
0.976033
0.963611
0.957694
0.951649
0.946750
0.938583
0.922836
0.553880
1.897421
3.370339
3.706223
3.543537
3.456747
3.226149
3.001817
2.494885
—
—0.628994
—1.499169
—1.901862
—1.963261
—1.995185
—1.987368
—1.938815
—1.732439
—
1.309390
2.737412
3.036230
2.909883
2.759433
2.518589
2.277182
1.736099
—
1.894608
2.045702
2.092648
2.050232
2.035082
2.012740
1.986351
1.920769
3
—1
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16
International Journal of Pharmaceutical Research & Development
ISSN: 0974 – 9446
0.80
1.00
324.15 K
0.00
0.10
0.23
0.34
0.38
0.42
0.45
0.50
0.60
0.80
1.00
326.15 K
0.00
0.10
0.23
0.34
0.38
0.42
0.45
0.50
0.60
0.80
1.00
328.15 K
0.00
0.895445
0.872501
1.815586
0.895390
—1.032595
—
1.988497
—
1.793866
—
0.987876
0.979883
0.974437
0.961828
0.955880
0.949809
0.944907
0.936733
0.920980
0.893576
0.870604
0.531480
1.781193
3.055500
3.320450
3.226581
3.112882
2.971659
2.736288
2.315497
1.717980
0.858182
—
—0.635981
—1.498165
—1.900093
—1.961723
—1.993816
—1.986594
—1.938783
—1.735651
—1.034789
—
—
1.217042
2.448876
2.677889
2.570951
2.444183
2.293159
2.041453
1.587993
0.925137
—
—
1.900912
2.043735
2.057644
2.045754
2.032704
2.017265
1.990128
1.932061
1.772214
—
0.987107
0.978981
0.972839
0.960046
0.954062
0.947965
0.943063
0.934883
0.919122
0.891075
0.868706
0.509081
1.664965
2.740662
2.934678
2.858624
2.769014
2.657169
2.470759
2.136114
1.620385
0.820989
—
—0.642939
—1.497107
—1.898369
—1.960056
—1.992305
—1.985814
—1.938760
—1.736861
—0.995953
—
—
1.124695
2.159843
2.319548
2.232018
2.128932
2.007729
1.805724
1.439838
0.861777
—
—
1.906476
2.039180
2.049227
2.038026
2.024498
2.009422
1.982532
1.926336
1.809831
—
0.986334
0.486680
—
—
—
0.10
0.23
0.34
0.38
0.978080
0.971244
0.958264
0.952252
1.548739
2.425824
2.548904
2.492667
—0.650049
—1.496210
—1.896701
—1.958729
1.032348
1.870809
1.961206
1.893085
1.911650
2.031329
2.036337
2.026060
0.42
0.45
0.50
0.60
0.946130
0.941120
0.933034
0.917265
2.425148
2.342679
2.205230
1.956728
—1.991203
—1.980949
—1.939892
—1.738174
1.813682
1.722299
1.569995
1.291782
2.013752
2.000427
1.976698
1.927255
0.80
1.00
0.889836
0.866808
1.522785
0.78379
—1.039243
—
0.798417
—
1.816843
—
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International Journal of Pharmaceutical Research & Development
ISSN: 0974 – 9446
Table 2 The activation parameters G*, H* and S* of ethylenediamine (1) + Water (2) mixtures are various
temperature
X1
G* x 10-4
* x 10-4
S*
-1
-1
(J mol )
(J mol )
(Jkmol-1)
1)
0.00
0.6070
0.4081
6.2525
2)
0.10
0.9457
0.6245
10.0962
3)
0.23
1.5533
0.9554
18.7906
4)
0.34
1.7584
1.0669
21.7352
5)
0.38
1.7139
1.0454
21.0143
6)
0.42
1.6454
1.0114
19.9265
7)
0.45
1.5593
0.9678
18.5945
8)
0.50
1.3898
0.8818
15.9665
9)
0.60
1.0189
0.6933
10.2336
10)
0.80
0.9361
0.6473
9.0763
11)
1.00
0.4897
0.4066
2.6112
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