IndianJournalof Chemical
Technology
Vol. 1,March1994,pp.93-97
.
'"-"
It-
Densities and viscosities of the binary aqueous mixtures of tetrahydrofuran
and 1,2-dimethoxyethane at 298, 308 and 318 K
BijanDas.Mahendra
NathRoy& Dilip K Hazra*
Department
of Chemistry,
NorthBengal
University.Darjeeling
734430.India
Received
10June1993:accepted13October1993
The densitiesand viscositieshave beendetermined for the binary systemsof water with tetrahydrofuran and 1,2-dimethoxyethaneat 298, 308 and 31~ K. From the experimentalresults,the exces~
-,
'"
molar volumes (VE) and the deviation of viscosity from the mole fraction average(11,,)have been
derived. These are explained on the basi~ of molecular interactions betweenthe componentsof the
mixtures.
I.:
)
There has been a recent upsurge of interest I -I in
the thermodynamic properties of binary liquid
mixtures. These have been extensively used to ohtain information on the intermolecular interactions and geometrical effects in these systems-l.
We have presented here the densities and viscosities for tetrahydrofuran-water and 1,2-dimethoxy-
The kinematic viscosities were measured hy
means of a suspended Uhhelohde-type viscometer
with a flow time of water of about 539 s at 298
K. Temperatur~ control during viscosity measurements was ::I:0.01 K. The precision of the viscosity measurements was ::I:0.05%. The kinematic
viscosities (v) were converted into the absolute
ethane-water
viscosities
..
mixtures
at 298, 308 and 318 K.
(1])
by
multiplying
the
former
with
density (p).
J
J.,
Experimental Procedure
The purification of 1,2-dimethoxyethane (Fluka,
purum) has been described earlier~. The solvent
was shaken well with FeSO~ (A.R., BDH) for 1-2
h, decanted and distilled. The distillate was refluxed for 12 h and redistilled over metallic sodiurn. The purified solvent had a density of 861.32
kgm 1 and a coefficient of viscosity of 0.4236
mPa s at 298 K which agree well with the reported values".
Tetrahydrofuran (Merck, India) kept several
d~y~ over KOH, ~as refluxed for 24. h and then
dlstll~~d ove~ LI.AIH~. The de~slty (880.72
kgm .) and vIscosity (0.4630.mPa s) at 298 K of
the ;olvent co~pared well with the rep<?rted ~alu~s ..All s<;>l~tlonswere prepared hy weight with
deionized dl.s~llledwater..
The densIties were measure~ with an OstwaldSprengel type pycn.ometer h~vmg a bulb volu~e
of 25 cn1' and an Internal diameter of the capl~lary of at
about
mm.and
The318pycnometer
was callbrated
298, 1308
K with doubly
dis-
.
11d
t
Th t
t
t I h d
tI e wa er.
e empera ure con ro a an acf + 0 01 K h
d .bit.
f h
curacy 0 -.;
t e repro UCI Ity 0 t e
dellsitymeasurementwas ::1:3x 10--'kgm-J.
.Autht' to whomcorrespondence
shouldbeaddressed
Results
The experimenal results of densities and viscosities at various mole fractions of organic solvents
and at three different temperatures are reported
in Table 1.
Binary liquid mixture viscosities have heen represented by a number of correlations in terms of
their pure component properties and interaction
parameters. Grunberg and Nissanx proposed the
following equation:
In" = x I In "1 + x ~In ,,~+ x I x ~d
...(I)
where xland X2are the mole fractions of tetrahydrofuran (or 1,2-dirnethoxyethane) and water respectively, "I, "II and "I~ are the respective coefficients of viscosity of the mixture, tetrahydrofuran
(or 1,2-dimethoxyethane) and water, and d is a
constant proportional to the interaction energy
and is regarded as a measure of interaction between the components. The values of d are given
.T able I .
In
h
The excess molar volumes have been calculated
h 4' II ..
Y t e.o owIng equation:
VF= V-(x1 V1+x~ V~)
...(2)
where JI; VI and V 2 are the molar volumes of the
mixture, tetrahydrofuran (or 1,2-dimethoxyethane)
I
I
I
94
INDIAN J. CHEM. TECHNOL., MARCH 1994
I
I
Table I-Values
.\"(
p
of densities (p), viscosities (,,) and Grunberg- Nissan par~meters (It JI
"
kgm-J
mPas
d
Xl
Tetrahydrofuran( 1 )-water(2)
P
'1
kgm-3
mPas
4
C
;).
1,2-Dimethoxyethane( 1 )-water(2)
2~
298 K
0.0000
0.0271
0.0587
0.0967
0.1427
0.1998
0.2726
0.3682
0.4500
997.07
992.81
986.88
978.33
969.97
958.98
946.28
932.19
921.69
0.890
1.201
1.490
1.680
1.732
1.618
1.490
1.224
1.024
12.04
10.01
7.99
6.20
4.78
3.50
2.40
1.76
0.0000
0.0399
0.1251
0.1800
0.2525
0.3124
0.3552
0.4198
0.4648
997.07
996.72
974.98
963.22
947.75
935.11
926.50
915.65
909.09
0.890
1.502
2.070
2.020
1.699
1.413
1.2,!-0
1.016
0.895
14.43
8.56
6.11
4.42
3.23
2.60
1.95
1.41
0.4998
0.6000
915.92
905.52
0.924
0.758
1.45
0.96
0.5088
0.5499
903.10
898.17
0.800
0.729
1.08
0.85
0.6921
0.7500
0.8000
891.12
883.99
880.69
0.656
0,608
0.579
0.69
0.5R
0.58
0.5955
0.6622
0.7199
892.89
885.83
880.31
0.670
0.600
0.558
0.66
0.44
0.33
0.9000
1.0000
875.35
880.72
0.516
0.463
0.48
0.0000
0.0587
994.06
983.09
0.722
1.133
8.70
0.7550
0.8051
0.8584
0.8999
0.9511
877.25
872.50
869.36
866.80
863.97
0.540
0.502
0.474
0.460
0.441
0.33
0.16
0.06
0.09
0.08
0.0967
974.34
1.267
7.01
1.0000
861.32
0.424
0.1427
0.1998
963.34
951.24
1.323
~.293
5.56
~.~O
0.0000
994.06
0.722
0.2726
938.10
.189
2. 3
0.0399
986.81
1.200
13.90
0.3682
0.4500
0.4998
923.15
913.08
907.68
0.989
0.852
0.784
:~
1.6
.31
0.1251
0.1800
0.2525
969.48
957.34
941.00
1.484
1.488
.1.352
7.30
5.66
4.16
0.6000
0.6921
0.7500
0.8000
0.9000
89624
888.49
.883.80
880.69
875.35
0.653'
0.572
0.539
0.512
0.472
0.89
0.61
0.53
0.47
0.52
.0:3124
0.3552
0.4198'
0.5088
0:5499 ,
927.26
918.32
901.63
893.15
888.12'
1.185
1.076
0.933
0.788
0.732
3.22
2.72
2.}4
1.63
1.45
1.0000
870.33
,,~
1I
'"
I
I
1
308 K
308 K
0.428
318 K
0.0000
0.0271
990.17
0.598
-J
(
0.5955
882.90
0.678
1.29
0.6622
8:76.66
0.601
1.04
0.7199
870.84
0.544
0.84
985.79
0.752
9.11
0.7550
867.87
0.~13
0.72
0.0587
0.0967
' 977:30
968.78
0.897
0.997
7.77
6.31
0.805l
0.!!584
863.98
860.25
0.470
0.4~4
0.49
0.27
0.1427
958.52
1.045
5.06
0.8999
857.7~,
0.413
0.09
0.1998
944.96
1.036
3.96
1.0000
851.29
0.385
0.2726
0.3682.
929.13
915.20'
0.959
0.830
2.97
,
2.08
0.4500
0.4998
904,06 ..0.7-14
897.32
0.661 i
1.49!
1.25
0.0000
0.0399
990.17
982.54
0.598
0.960
12.90
0.6000
0.6921
0.7500
0.8000
0.9000
886.30
877.59
873.84
870.51
865.47
0.564
'0.506
0.47-3
0.452
0.422
0.S2
0.60
0;45
0.39
0,40
0.1251 ,
0.1800
0.2525;
0.3124
0.3552
965;76
948.61
929.02
915.25
908.10
1.142
1.152
1.100
1.016
0.940
6.52
5.09
3.20
3.25
2.81
1.0000
861.40
0.390
895.56
0.834
2.29,
(Contd)
-
~
,
,
~
318 K
"O.419R
-~
DAS etal.: BINARY UQUID MIXTURES
95
Tab!.: 1-- V3Iu.:~of densilie~(,oj, vi~cositie~(1])anu Grullbcrg- Ni~sanparaml..tcr~
(.1)j- Contd.
:.
."1
().4648
0.5088
0.5499
0.5955
0.6622
0.7199
P
kgm""
888.52
882.84
877.76
872.43
865.98
H60.49
'1
mPas
.1
XI
0.770
0.704
0.654
0.600
0.530
0.462
2.02
1.74
1.56
1.34
I.OS
0.64
O.755{)
0.8051
O.R584
0.8999
0.9511
1.0000
P
k~-3
1]
mPas
d
857.66
853;73
850.05
846.32
844.01
840.76
0.456
0.422
0.400
0.392
0.378
0.350
0.73
0.54
0.48
0.67
1.09
0
0,8
-02
0-7
,
0-6
,
-;
-04
~ 05
-0
A.
E
E.
E
oQ
n
~'
1:"'0-1.
U
101-
>
03
..-0
M
0-1~
r
-08
0
XI
.0
f
°Zc.
0.,4
0'6.
0~8
1
'XI
~
r ;
.and
.~
.V=
~
):..,.
Fig. 2 -Variation of ~ 1] for the systemtetrahydrofuran(I )-water(2) at 298 K (0), 308 K «t) and 318 K (8).
Fig. I-Variation of VE for the systemtetrahydrofuran(l)-wa- where Y is VE (cm3 mol-I) or 6.1] (mPa s) and
ter(2) at 298 K (0), 308 K «t) and 318 K (8).
~; ,AI ,A2, ..., etc. are' adjustable parameters.
water, respectively.
defined by
(M
M
)1
IXI+
2X21P
The
molar volume
V is
...3
( )
These parameters were evaluated by the method
of least-squares. The values of these parameters!
along with the standard deviations a( Y) of Y asl'
defined by
here M, and M2 are the.molecular .weights of t~e
pure components and p IS the densIty of the mIXlUre.
'are
The deviation of the viscosity from the mole
a( Y)=[1: (~bsd -~alcd)2/(NM)]o.s
...(6}
"
gIven In Table 2. In Eq. (6), N is the number
of parameters.
fraction average is calculated from:
~1]= 1]-(x,1]1 +X21]2)
...(4)
Graphical r~presentations of VE and 6.1] as a
function of x, are given in Figs 1-4. The properties VE and 6.1] were fitted to the Redlich-Kister
equation9:
Discussion
It ~ ~ell-knownl()
t~at the sign and magnitude
~f V. gIve a. goo~ estImate. of the s!rength of unlIke. !ntera;tIons
In the bInary. ~Ix~res.
Large
pOSItIVe. V values are taken as ~dICatIVe of weak
InteractIons whereas large negatI~e valu~s of VE
are usually found when these InteractIons are
strong and intermolecular association "complexes"
are believed to be present..
y= XI X2I ~ (X2 -XIY
j
...(5)
-
9~
INDIAN J. CHEM. TECHNOL., MARCH 1994
The systems tetrahydrofuran-water and 1,2dimethoxyethane-water show negative VE values
over the entire mole fraction range and over the
entire range of temperatures stUdied (Figs 1 and
3). Several effects may contribute to the VE values. One of the effects which may contribute to
VE is the disruption of (i) the hydrogen bonds
0
-02.
present in the self-associated water molecules and
(ii) the intermolecular dipolar interactions in tetrahydrofuran and 1,2-dimethoxyethane. Secondly,
the effect which gives a negative contribution to
VE is the difference in molecular sizes between
the two components in the mixtures. The molar
volumes of water, tetrahydrofuran and 1,2-dimethoxyethane at 298 K are 18.05, 81.75 and
104.65 cm3, respectively, which might allow the
components to fit into each others' structures
both in tetrahydrofuran-water and 1,2-dimethoxyethane-water systems, so that a reduction in volume occurs in each case.. A third effect whose
1.3
1-2
-0.4
1.1
-10
'0
09
e
n
"
fj
n.
>
..08
0.6
07
E~ o~
co<!
05
0"
03
-08
01
0.1
00
-0.1
0
0.2
.0.0
0
.I
0.1
0-2
-..
03
0",
XI
Y
0.6
X
0.7
O~
09
10
I
Fig. 3-Variation
of yE for 1,2-dimethoxyethane(I)-water(2)
at 298 K (0), 308 K «I) and 31H K (8).
Table 2-Coefficients
05
Fig. 4-Variation of ~1J for 1,2-dimethoxyethane(I)-water(2)
at 298 K (0), 308 K «I) and 318 K (8).
of Eq. 5 for yE and ~1J and the standard deviation~ 0( Y)at 298. 308 and 318 K
Temp.
K
~)
yE
298
308
318
-3.099
-3.354
-2.985
~1J
298
308
318
yE
298
308
318
0.900
0.798
0.628
AI
Az
A,
Tetrahydrofuran-water
-2.467
0.457
-0.510
-1.1)08
1.167
-1.675
-2.410
1.882
-1.O6R
3.018
2.208
1.841
5.355
3.030
2.675
4.109
2.655
1.573
A.j
0( Y)
-1.389
-2.247
-4.103
0.007
0.007
0.015
-.(
0.673
1.37 I
0.106
0.018
0.005
0.007
-4.324
2.105
1.371
0.004
0.003.
0.004
...
1.2-Dimethoxyethane-water
-6.378
-6.239
-6.024
-3.749
-4.765
-4.288
0.505
-4.040
-4.611
-2.439
0.872
-0.025
-j
~1J
298
308
318
0.552
1.147
1.072
3.497
2.495
1.648
7.945
2.248
0.032
6.751
4.861
3.923
1.]04
4.783
5.264
0.00]
0.007
0.004
DAS et al.: BINARY
.)
contribution
is
the
molecules.
value
between
contributions
.positive
these
)
and
~
two
values
two
would
interactions
depend
opposing
indicate
studied
d
of specIfic
between
the
the
the
the
effects.
.study
it is clear
hydrogen-bonding
unlike
molecules
predominate
found
range
m
to(Figs
be
d.
I~ate~
bondIng
molec,ules
.(t~
h
t e
mter-
form
ad-
1 Aminabhavi
T M & Raikar
S K, J Chern
expected
on
the
port);
the
is
rather
basIs
of
difficult
the
than
VIscosIties
of
105.
4 Douheret
5 Nandi
G & Pal A, J Chern Eng Dala, 33 (1988) 40.
D, Das S & Hazra
formation
of
intermolecular
com-
D K, Indian
between
orogen
bonding.
!
A
K
&
~~anlc
Solvent
DIckinson
T
J Chern,
27A
Systems, edIted by
(Plenum,
New
York),
X Grunberg L & Nissan A P-!, Nature (London), 164 (1949):
799.
9 R~dlic.h 0 & Kister A T, Ind Eng .chern, 40 (1948) 345.
10
Prigogtne
I,
The
Theory
of
Solutions
(North-Holland,
Am-
sterdam),(1971).
plcxcs
t
CnemlStryof
Covington
1973.5.
the
Nissan
parameter
d is found
1) for both the systems.
This
Eng Data, 38
En!!. Data. 36 (1991-) 360.
.1 RitzouiisG,(anJChern,67(19!!9)
7 PhY~lcal
flow
over
M & TassI L, J Chsrn
would
the
for
2 MarchettI
1]1J1J.1).1]O.
A, Pretl C, Tagllazucchl
ture
where
that
interactions
References
different
p.
.L
between
the
other
present
(1988) 574.
6 Rena~dE&Jus~iceJ-C,J!J'olurio~Chenl,.3(1974)6~3.
su
\
the
binaries
effects
struc-
pure components.
The
Grunberg
and
to be positive
(Table
,>
from
these
ducts
between
them)
over
the dIssocIation
in both
systemsll.12,
This
results
in a liquid
be
..
97
negative
at three
hydrogen
unlike
Thus
both
binaries.
...
evlatlon
poslt.lve
upon
MIXTURES
contributions.
that
in these
systems
...
ThIs
~.
to be negative
the
the entire
values compositional
of 1\1/ are
predommC)nce
..action
VF
predominate
temperatures,over
2
the
expected
hydrogen-bond
of
experimental
For
is also
unlike
actual
balance
The
VI'
of
between
The
to
existence
UQUID
the
unlike
molecules
through
hy-
11 FortRJ,MooreWR,
Trans FaradaySoc, 62 (1966) 1112.
12 Nigam R K & Singh P P, IndianJ
Chern, 9 (1971)691.