Title
Specific volume and viscosity of ethanol-water mixtures under
high pressure
Author(s)
Tanaka, Yoshiyuki; Yamamoto, Takeshi; Satomi, Yoshimasa;
Kubota, Hironobu; Makita, Tadashi
Citation
The Review of Physical Chemistry of Japan (1977), 47(1): 1224
Issue Date
URL
1977-07-20
http://hdl.handle.net/2433/47042
Right
Type
Textversion
Departmental Bulletin Paper
publisher
Kyoto University
The
Review
of Physical
Chemistry
of Japan
TLC I2E\9EN' OF PHYSICALCHEII1$TRTOFJAPAN,V01.. 47, ~O. I,
12
VOLUME AND VISCOSITY
SPECIFIC
1 (1977)
Vol. 47 No.
1977
OF ETHANOL-WATER
MIXTURES UNDER HIGH PRESSURE
13v YOSHIVL'RI
T,a\ARa,
HlaoNOau
TA6 ESHI ~:fyLt at0T0. S USHIa[.tSA $ATOa[I,
I:ceora
Ann Taoasxr
IVfasaTA
The specific volume and the viscosity of enthanol-water mixtures at 23'
(29S15K) and 30'C (323.1 SIi) have been measured under pressures up [0 3200
and 800 bar (IOsPa), respectively. The measurements were performed by a
modified Adams piezometer and a fallingtylinder
viscometer. The maximum
uncertainties are estimated to be 0.05°6 for the specific volume and 2q; for the
viscosity.
The specific volume of the pure components and their mixtures is found
to decrease monotonously with increasing pressure. The results obtained are
compared with several sets of literature values. The numerical data at each
temperature and composition are correlated satisfactorily as a function of pressure by both polynomial and the Tait equations- I[ is also found that a definite
minimum appears on /he isothermal compressibility versos composition isobars,
arising from the complex interactions between hydrogen-bonded water and
alcohol molecules.
The viscosity ai pure ethanol and mixturesis found to increase almost
linearly with increasing pressure, whereas that of water is nearly independent
of pressure in these experimental conditions. The viscosity isotherms can he for•
mulcted by a quadratic equation of pressure within the experimental error, As
for the composition dependence of the \•iscosity, a distinct maximum appears
near 0.3 mole fraction of ethanol on all isobars a[ both experimental temperatures.
Introduction
The physico-chemical
properties
of science. The solutions
molar volume, compressibility,
been yet inadequately
pressure
excess
velocity
understood.
are important
thermodynamic
of aqueous solutions
often show some anomalies
both
engineering
However
properties, especially under high pressure.
The present investigation was undertaken
ty data under high pressure
and 30'C under pressures
modified
properties
viscosity
in many fields
such as partial
and so on. which have
in a wide region of temperature
designs and in theoretical
extensive
mi-elutes. Numerical
data have been determined
Empirical
results.
of
on these
P-I'-T and viscosi-
and 800 bar for viscosity,
viscometer.
from the experimental
and accurate
and
investigations
have been only a few measurements
to provide
and afalling-cylinder
for both properties
(Received /t/ay ?i, 1977)
there
up to 3200 bar for specific volume
Adams piezometer
also been presented
for ethanol-water
of mixtures
are of interest
physical
of sound, sound absorption,
Such properties
in chemical
properties.
of alcohols
in various
correlation
at 25'
employing
a
formulas have
The
Specific
Volume
and
Viscosity
Review
of Ethanol-R'aler
of Physical
Mixtures
Chemistry
u;gh
under
of Japan
Vol. 47 No.
Pressure
l3
Experimentals
P-V-T measurements
The specific
volume of the ethanol-water
mixtures
has been measured
by a modified
Adams
piezometer~l similar to that used by \ewitt et al.zt The piezometer is made of Pyrex glass. The schematic diagram is given in Fig. 1 and the typical dimensions are summarized in Table 1. The volumes
of the piezometer
or mercury.
and the capillary
The piezometer
stem were determined
was set in a high pressure
dows which enable us to observe and control
high pressure
vessel u•as immersed
was measured
by Heise Bourdon
pressure measuremenu
The mercury
is estimated
trapped
by weighing them filled with distilled
precisely
i¢ a thermostat
vessel equipped
the mercury
with a pair of optical
le\•el in the capillary
bath controlled
gauges calibrated
within
--X0.01°C. The pressure
against a pressure balance.
The uncertainty
in
to be less than QI o.
in the piezometer
was gashed
with ethanol
and weighed alter drying.
i~
z
G
~~
E
z
~r
a
a
~~
i
s
.I°I
fO~°
Schematic diagram of
modified Adams piezo•
meter
win-
stem. The
A
Fib. 1
water
Fig. 1
~,
9
Schematic diagram of falling-cylinder viscometer
1. Pyrex glass tuhe
6. Thermister
2. Falling rylinder
7. Pivot
3. Laser beam
8. O-ring
a. Optical window
9. Sample inlet
5. High pressure vessel
Q L, H. Adams, 1.:Luer. C/rem. Sar., 53, 3769 (1931)
21 D. T1. :~ewitt and K. E. ~i'eale, !. Chem. Soc., 3092 (1951)
1
(1977)
The
Y. Tanakn,
14
T. 1'omamoto,
Table
1
Review
1'. Satomi,
Dimensions
of Physical
H, Kuhota
of Instruments
Chemistry
of Japan
Vol. 47 No.
1
and T. 14akita
used
Piezometer
a[ 25'C
Length
Outer
diameter
Inner diameter
Total volume
Volume of capill sn•
16.7 cm
1.G cm
].4 cm
t 8.2215 cms
0.03616
at 29'C
V iscome[er
Glass tube
Length
Outer
diameter
Inner diameter
Plummet
Length
Diameter
11'eight
Volume
Density
cmr
15.5 cm
1.0869 cm
0.80}2 cm
3.570 cm
0.7607 cm
3.5278 g
1.5199 cms
2.321 g•cm-~
The specificvolume of the sample liquid aas calculatedby the followingequation
= I'„(l-ke)-I'c(1-ke)-Qf•ea~pxq)
(1)
1'~p,.
e•here
v
:specific
volume of the liquid at P bar in cm'•g''.
P„
:inner
volume of the piezometer
Pc
:inner
volume of the capillary
trapped
at Ibar in cm',
at Ibar in cma.
lime :weight
of mercury
in g,
pa
:density
of [he liquid at 16ar in g•cm-",
pue
ke
:density of mercury at P bar in g•cm''.
:compression of Pyres g]ass at P bar.
The values of kx and pFte mere cfted from the results of ~damsll
The densities
pycnome[er
Viscosity
of mixtures
and partly
mined principally
and Grindley
were determined
et a!_a) respectively.
experimentally
by a
cited from the handhookS%
has been measured
by a talking-cylinder
viscometer.
based on the Stokes ]aw on a rigid sphere
The details of the theoretical
The schematic
of a precisely
pressure
measurements
The viscosity
fluid.
under the atmospheric
diagram
falling
The viscosity
n•as deter
in an infinite homogeneous
basis are described by Swift et af.5 %>
of the viscometer
bored Pyrex glass tube equipped
employed
coasially
is given in Fig. 2. The apparatus
in a high pressure
consists
vessel and a glass cylind-
3) T. Grindley and J. E. Lind, Jc, J. CSem. Pkys., W, 3983 (1971)
4) R, H. Perry and C. H. Chilton, "Chemical Engineers' Handbook" (5th edJ \IcGrae~-Hill Kogaku•
sha, Ltd. (1973)
5) C, lV. Swift, J. A. Chrish• and F. Kurata, :1. L Ch. E. Jmnrml, 5, 98 (1919)
G) J. Lohrenz, G. \V. Swift and F. Kurata, ibid., 6, 547 (1960)
i) ]. Lohrenz and F. Kurata, iMd.,8, 190 (1962)
(1977)
The
Review
of Physical
Chemistry
of Japan
Vol. 47 No.
Specific Volumeand Viscosity of Ethanol-R'ater \lixtures under I3ig6 Pressure
15
rical plummet with hemispherical ends. The ins[m ment dimensions are listed in Table I. A sample
liquid was introduced into both sides of [he glass tube though a fine flexible pipe made of stainless
steel. The plummet is provided with four small projecting lugs at each end of the cylindrical part, which
act as a guide to keep the plummet concentric when it falls. The falling time of the plummet was
determined within X0.1 ms by an electronic time-interval counter with the aids of a He \e
laser beam passed through a pair of optical windows and a phototransister.
gas
The viscometer could
be rotated on a horizontal axis in order to return the. plummet to its starting position. The temperature
of the sample e•as maintained constant within x0.05°C by circulating a thermostatic duid through
the jacket around the pressure vessel and measured by a thermister device.
The pressure was meas-
ured by a 6ourdon gauge n•ith the same accuracy asthe case of P-V-T measurements. The falling time
ranged from 5 to 20 seconds according to the change of the viscosity of samples and was measured
about 20 times at each experimental
condition. 'The mean reproducibility of the falling time is
within 0:5%. The arithmetic mean values nere taken as the final values.
Due to the geometric effect of the plummet and the wall effect of the glass tube, the stokes law
is not valid strictly for afalling-body otber than a rigid sphere in an infinite homogeneous fluid.
'therefo
re. the calibmtion of the present viscometer is required with fluids of known viscosity. The
basic equation at the falling-body viscometer is as follows
where
r
:viscosity of a liquid at P bar irr l0'sPa•s,
p :density of a liquid at P bar in g~cm ',
pe :density of the plummet a[ P bar in g•cm'a,
7 :falling time in s.
The instrument constant ti and its change with both temperature and pressure were determined
based on the experimental viscosity values under the atmospheric pressure obtained by an O;twald
viscometer and the standard viscosity values of water correlated be the International Association
for the Properties of Steam sl The densities of mixttres were calculated from Eq. (3) obtained in the
present work. R'hen the resistance iactorsl is plotted against the Reynolds number in logarithmic
coordinates. the calibration curve is found to be a straight line with a slope of about - 1. This me.•tns
that each measurement was carried out in a laminar flow region with lower Reynolds number than
0.5 throughout the experimental Condition.
Materials
Extra pure ethanol was obtained from N'ako Pure Chemical Industries, Ltd. The reported
purity is more than 99.5% in vrolume. Ethanol and water tsere purified several times by the frac•
floral distillation. The mixtures of ethanol and water were prepared by weighing. using an analytical
balance wfth a sensitivity of t0.tmg. Therefore their composition, mole fraction of ethanol, should
8) .International Association for the Properties of Steam, "Dynamic Viscosity of water Substance"
'the Eighth International Conference nn the Properties of Steam
, Glens, France (t9i;)
1
(1977)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
l6
T. Tanaka,
be substantially
accurate
T. Yamamoto,
within
0.01 %.
Uncertainty of experimental
results
Y. Satomi,
H. Kubota
and T. Makfta
The numerical data of the specific volume and the viscosity obtained contain a definite uncertainty resulting from several sources of experimental errors. The main sources and their portions in
the final values are estimated as follows
(Specific e•olume measurement)
Error source
Uncertainty emttribnting to
Temperature
=0.001 %
Pressure
y--0.01%
Composition of mixture
=0.01 %
Piezometer volume
=0.01%
(Viscosity iwfeasurement)
Error source
LSxerfainfy cortlribalirag fo r
Temperature
Pressure
Composition of mixture
Falling time
Density
Instrument constant, li
.0.1 %
=0.01 %
±0.02%
x-0.5%
x-0.01
-r1.0%
Taking into account the above estimations, the uncertainties probable in the present measurements
may be less than 0.05% for the specific volume data and 2.0% for the viscosity data. This fact has
been verified satisfactorily by the comparison with the reliable data of pure components by other
authors, as partly described below.
Results
P-V-T
and
Discussions
data
Table
pressures
2 lists the measured
up to 3200 bar.
P-C-T relations
X is the mole
fraction
for ethanol-water
of ethanol
mixtures
in the mixtures.
at 25' and 50'C under
The results are also
plotted in Figs. 3 and 4 together
with the previously
published
data for
mixtures
for comparison.
The specific
volume
decreases
monotonously
pressure
throughout
present
results
[he experimental
agree quite
conditions
at each compwitiop
well with the values given
of mixtures.
pure
with
water and
increasing
.4t 25'C, the
by Kell ed alsl and Grindley
eE als)
for
pure water up to 3000 bar and those of \foesveldto] for mixtures up to 1500 bar. However, some
discrepancies between the present work and the recent report of Y"usa e! al.tt~* are found to be up
9)
10)
If)
a
G. S. Kell and E. 1Vhalley, Phit. Trans. Roy. Soc. London, A258, 565 (1965)
A. L. bfoesveld, Z. Pbys. Cke,n., t0.5, 450 (1923)
M. Yusa, G. P. Wathur and R. A. Stager, J. Cbem. Eng..Dala, 22, 32 (1971)
This report was published recently after the completion of experimental part of this study.
The
Specific
~bfume
Table
2i°C
P(bar)
2
and Viscosit} • of Ethano]-1Vater
The Specific Volume
i0°C
of Physical
Mixtures
oT Ethanol-Water
2~ C
50'C
P(bar) v(cm3/B) P(bar) v(cm3/g)
n(cm3/g)
Review
P(har) nr(cm3/g)
under
Chemistry
High
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Pressure
25'C
50`C
P(har) v(cm3/gJ P(bar) (cm3/g)
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Vol. 47 No.
Mixtures
]181.9
.Y=0.20
X-0.00
of Japan
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2247.9
2414.3
2588.8
2759.0
2931.9
3103.6
1.31207
1.29134
1.28152
1.21198
1.26767
1.25453
1.24948
1.24297
1.2365fi
].22947
1.22392
L 20357
1.]9502
1.18682
1.17106
1.15339
i. 14330
1.137]5
1.13239
1.12246
1.11828
1.10914
L 10530
1
(1977)
The
18
1'. Tanaka,
T. I'amamato,
Review
S, 5atomi,
of Physical
H. Iiubota
Chemistry
and
T. btak
of Japan
47 No. 1 (1977)
Vol.
ita
1.30
°
o, d'Q'
0° ~
O
°b
c e0
P°
°~
~.
oQ
a
~,
°
0
o °
Q a ,~
1.10
oa
°o
° °
o 4~
p~b
b°
°E
° ° oOo 4
° ° o
1.00 •o~
i.2
-
0
Ev
E
0
a
°°
^° ~~6
a~
°°
o~
° ~e
O~
o° ° o,
°^
°°
oPo
° o° °°
° o°
°~ °
~
m t.1a
x
EIOll
o~
,
o °
.
°
P
°
o
0
4
•
o°
0.8
o
40
.o~
~
0.2
°
0.1
o
•
2000
°
O.fi 0
0
0.4
°
o
a
1000
°°
°
0
Eu
E
0
~e
.V
.0
°•
0
0
l
1.I0
an
1.00
°p
to 0.4%
°
.0
°
°°
° °
O°
°
06°O.g°
°
0.4°
o
° o
0
°
° 0 .2
~ °°
0,1
=
°
a°
o
0°°+Oa
0.90
3000
0
IOOD
•a°
1000
3000
Pressure/bar
Fig.
Pressure dependence of the specific
.•olume of ethauof-water mixtures
at i0'C
C1; This work. *: 3), ~: 9)
4
Coefficients of the Specific
5~
Volume Isotherms (Pin harj
r'=A~ tA2Pt.faP~+A~P3
i'=At
t.
so
°
1
°
° °
volume of ethanol-water mixtures
at 2i C
C: This work, *: 3), ~: 9),
x:10), /:I1)
25
£tnx
°
o
Wdt
ef °<,e~
' °
Pig. 33 Pressure dependence of the specific
Temp.
(°C)
x
°D
°OpOp
o
o°a
°°
~°
°
Pressure/har
Table 3
50'C
o
50
•op
[Va~
O
er
~ .
0.90
°
o
oo
~
1.30
zs•c
00
t asP+
~'IFX IQI6
Afas. llev,
~~o~
:12k 10~
:12 % 10a
0
1002799
-
0 .87462
0.8722b
0.023
0.084
1.03802fi
0.89155
-
2 .45fi6i
3.2101
0.022
0.079
o.zo
1.071118
-0 .443342
-0 .436395
-0 .497623
0.62fi552
o.~o
0.856201
-
0 .95734
0.024
0.071
o.ao
1.136153
2.320940
-
6 .04088
6.701070
0.025
0.07A
0.60
1.13933(
-0 .144170
-0.943990
3.22?030
-
7.910364
7.73$71
0.031
0.114
0.80
1.232849
-1.103108
3.181940
-
9 .09383
9.1 / 881
0.043
0.124
1.00
1.273663
-1 .303024
4.16.938
0.028
O.OHi
0
0.10
0.20
0.40
0.60
0.60
L00
1.012369
0.54"835
-
0.031
O.Oi 1
0.836348
-
O.SSi i2
1 .20089
1.26276
1.057173
-0 .4252248
-0 .460342
O.OiI
0.143
1096419
-0 .558459
1.121898
-
1.10525
1.91894
0.038
0.099
1.167762
?.400286
-
3 .64916
0.092
0.279
1.213160
0.553410
-0.903382
1.101615
2,52140
0.052
0.203
1.271486
-1.343178
5.624636
20.78308
0.039
O.1I0
1.311651
-1571652
6.942738
-16 .81337
-20 .77829
25.21906
0.069
0.224
at high ethanol
water
are
exists
no data on mixtures
in good
mole
agreement
fractions
leith
available
and high
the
values
in literature
:Il X (012
Ave. Dev,
~~~
~~
11.0980
pressures.
of Kell
As for 60`C,
et aJS> and
for direct
-7.12415
the present
Grindley
comparison
results
et al.31 However
with the present
worl.
for pure
[here
The
Specific Volume
and Viscosity
Table
4
i0
For each
pressure
temperature
of Elhanol•Nater
Coefficients
Mixtures
under
Chemistry
High
0.00
2751
0.2911
o.w
0.07
0.10
3121
0.2989
o.oa
o.lo
0.20
2283
0.2511
o.os
o.lo
0.40
1552
0.2308
O.Oa
0.18
0.60
I l3i
0.2f79
0.07
0.19
0.80
nR9
0.21 i9
0.03
O.OR
1.00
7iR
01061
0.06
0.13
0.00
3311
0.3241
O.Oa
0.08
0.10
1952
0.2881
0.03
0.11
0.20
2401
0.2792
O.Oa
O.li
0.40
1331
0.2504
0.09
0.11
0.60
I ilO
0.2686
0.07
0.19
0.80
92l
0.2282
0.05
O.li
1.00
i90
0.2279
0.03
0.1 i
quartic
Vol. 47 No.
t9
of the Tait Equation
Ave. Dec.
(4i)
the
of Japan
Pressure
C(-J
and composition
by the following
of Physical
R (bar)
Temp.
(•C)
25
Review
specific
\fax. Dec.
(,.°o)
daL3
data are correlated
n
volume
as a function of
equation
(3)
and the Tait
equation
Clogl8}t ~
where
~o is the specific
volume
coefficients
were
the average
and the maximum
determined
polynomial
equation
gives
at the atmospheric is pressure
6y the
least
deviations
a better
squareses method
of the
fit to the
and P the
as given
experimental
data ~ in
in general,
general,
(4)
data
the
the
press
pressure
in Tables
Tab
in bar.
3 and
The
4 together
from the
th formulas.
isothermal
isothermal
liT=-vv ~
~0o ~T
~T
empirical
although
with
the
compressibility
(~)
is calculated by the Tait equation because the polynomial
polynomial equation
equation som
sometimes gives unexpected
behaviors by the diiieren[iation. The functional1 dependences of the isothermal
isoth
compressibility nn
composition are shown in Figs. 5 and 6 at 25° and i0`C,
50`C, respectively.
It is found [hat a detinite
minimum exists near x=O.l on the lower pressure
re isobars than 2000 har.
tzar. As
~1 well known in the case
of pure water. the isothermal compressibility has
as a minimum near 50'C on
/ the isobars lower than
age
o;
low
ethanol
composition,
and disappears a~i[h
2000 bar. This anomaly could be seen in the range
composi
increasing composition near x=0.1, where the isothermal
othermal compressihility
compressibility is independent of temperatore under each pressure. Furthermore, it seemss that another inflection might
mi
occur at higher mole
fraction of ethanol near x=0.7 on the low pressure
sre isobars. (Concerning this
th. second inflection, more
detailed experimental results will be reported in the near future.) Yusa e!
et a/!»
al, have found the similar
1
(1977)
J
The
?a
1'. Tanaka,
T. Famamoto.
Review
Y. Satomi,
of Physical
H, Kubota
Chemistry
and
T. Makita
i
Composition
of Japan
Vol. 47 No.
1
,
~r
bac
25°C
I0.0
0T
a
d
n 5.0
Ea
n
E
s
0
bOpbar
~ 1000
atbatb
~I
f•~
Fig,
or
201N1 bar
o3000
b
dependence
of [he
isothermal
rompressibilit}•
of
ethanol•n~atermistures
a[ 2i`C
under
high pressure
ar
0
0
0.7
o.a
Mole
0.6
fraction
0.8
t.a
of ethanol
bar
a
0
T
50'C
10.0
L
v6
s
0
Ae
600 bar
o'
5.0
11
.~~
°J~~o
1000
2000
o-~c
0
3000
Fi¢.
Composition dependence of the
isothermal
compressibility
of
ethanol-water
mis[ures at 50°C
fi
ab l
bar
under
high pressure
har
v
0
A
O
"
0
phenomenon
attributed
0.2
0.4
0.6
0.8
Bole fraction of ethanol
in his isothermal
compression
to complex interactions
1.0
versus composition
between the hydrogen-bonded
isobars.
n•ater
anomaly
would
be
and the bifunctiohal
These
nature
of
alcohol molecules.12~131
Viscosity
The viscosity of ethanol-water
mixtures
raw data are tabulated
in Table
compared
of composition
l2)
l3)
l4)
15)
16)
l7)
IS)
l9)
20)
21)
22)
as a function
has been measured
5. Values of the tdscosity
at 25` and 50`C up to 800 bar. The
obtained
to other data available
at the atmospheric
in literaturel+`~7
pressure
are
in Pig. 7. The cis-
F. Franks and D. J. G. Ives, Oxarl. Rev., 3Q I (19fi6)
G. Ne'methy and H. R. Scheraga, 7. Chern. Phys., 36, 3382 (1962); ihui., 36, 3401 (1962)
J. Tranbe, sar., i9, sn (lass)
.a. E. Dunstan. Z. Plrys. Cheru., 49, 590 (1904)
E. C. Bingham. G. F. White. A. Thomas and J. L. Cadwell, Z. Plrys. Chem., 83, 641 (1913)
V4'.Herz and E. illartin, Z. anorg, allgem. Chem., 132, 41 (1924)
5. W. Sabnis, W. V. Bbagwat and R B. tanugo, J. Indian Chere. Soc., 25, SiS (1948)
31. Kikuchi and E. Oikawa, Nippon ICagahaZarshi, 88, 7259 (1961)
R. L. ICay, J. Solafim+Chenr., 5, Si (1976)
E. L, Lederer, (Coll. Reih., 34, 270 (1932)
:1. 9basaade, V. A. Agaev and A. DI. Cierimov, Rxtt. J. Plryt. Gram., 45, 1517 (19i 1)
(1977)
7
The
Specific
Table
1`
Temp. ('CJ
F (bar)
and Viscosity of E[hanol-Naler
\`nlume
Review
of Physical
Chemistry
Vol. 47 No.
of Japan
Dfixlures under High Pressure
21
The Viscosity of Ethanol-1Va[er '.Mixtures (10-sPa~s=cP)
i
0.00
0.20
0.30
0.40
_>i
50
25
50
15
50
25
50
1
0.8911
O.i468
2.331
1.060
2.314
1.108
1.148
1,072
98
0.8891
0.3456
1.400
1.134
2.407
1.155
2.249
1.146
196
0.8882
0.5104
2.461
1.136
2.481
1.1 h8
2:352
1.166
29a
0.3872
O.ii22
2.SOG
1.17 i
2,159
1.211
z.as9
1x14
392
0.8866
O.iial
IS6i
LIST
2.638
1.249
2.527
L26a
490
0.8864
OSi6l
1.601
L200
2.703
1.275
2.611
L 293
589
0.8866
O.ii83
2.666
1.131
2.171
1.341
2.102
1.333
686
0.3322
2.701
2.845
2.779
iS5
0.8881
2.771
2.939
2.88a
.Y
Temp, (°C)
P (bar)
25
O.GO
i0
0.78
25
osa
so
,.~
25
i!)
1
1.740
0.9405
1.423
O.SIOI
1.081
0.6881
93
1,843
1.029
1.513
O.Siii
1.110
O.i 473
196
].9+t
1-039
1.614
0.8339
1?46
0.7758
291
2.031
L113
1.703
0.9397
1.326
0.3379
392
2.131
1.166
1.300
0.9969
1.397
O.R800
190
2.220
LIS2
l.ais
L.D13
L4ii
0.9261
189
2.330
1.231
1966
1.051
L517
0.9682
686
2.389
2.052
1.6t3
755
2.131
2.IOi
1.691
3.0
e
9 ~
r
:.a
a
e
T
.e
50'C
~o g
~.~
2SC
~o
~w
Fig-
Q ,~
~~
7
Composition dependence of the viscosity o[ ethanol-water mixtures at
2i' aad 50'C at the atmospheric
pressure
~: This work, ~: ll), ~: Id),
~
a~
~ : 19). O : 20).0:
20. O:
22)
a
0
cosity
data
temperature.
display
0.2
dole
0.4
fraction
a maximum
Agreement
0.6
0.8
of ethanol
at a composition
of the. data
among
L0
from
researchers
0.2
to 0.3
mole
is comparati.~ely
fraction
of ethanol
at each
good at 25°C, except
the
1
(1977)
r
The
22
l'. Tanaka,
2SC
T. S'amamota,
x
1' . Satomi,
X0.3
--_ -__ ~
N
W
of Physical
H. Kubota
Chemistry
0.4
0.
1
(1977)
and T. \fakita
S ~ .
,r
p.8 __~_"
FiR, b
"-__
z.a
,r'__
Vol. 47 No.
~~
U1
- _-
_
TO
of Japan
--"`~`
__-'
3.0
O
Review
_~_.~I.U
Pressure dependence o1 Che
xiscosit.• of ethanol-water
mixtures at 25°C
Ethanol
~:
7
11), ~:
23)
i.o
a
soa
isoa
iooa
Pressure/bar
so•c
1.5
"o•y-'~
0.2~6.~
;e~
0.2
_-~a
A
0.
Fig. 9
0
T
O
~-
1.0
_-
Pressure dependence of the
viscosity of ethanol-water
mixtures at i0°C
;~: This work, ~: S),
• : 22). ~ : 23)
~~
7
0
Water
0.5
0
results
500
Pressure/bar
reported
Inconsistency
1000
be Yusa et al.,~~~ whose data are about -4~ higher than others near the maximum.
of the data is found to increase
at 50'C,
where the largest
deviation
between
the
data of Sabnists~ and those of Traubet+> is about 13% near x=0.z.
The viscosity
data obtained
at high pressures
are also compared
with those in literatures.
The
pressure effects on the viscosity are shown in Figs. 3 and 9 together with the results of ~baszade et
alsz7 and Yusa et al.tty for mixtures and those of Golubev e! aL~~ for pure ethanol. Figs. S and 9 include
partly interpolated data to the same compositions by a graphical method, because the previous data
under pressures available for a direct comparison are limitted. It is found that agreement among the
four sets of data is rather good at low pressure;.
pressure.:
serious
inconsistency
but that the discrepancy
is found in the results
for pure ethanol
23) I. F. Golubev and V. A. Petrov, Trudy GL1P, \o. ?, 5 p9i3)
increases
withincreasing
In the results of Yusa eE
The
Specific
Volume and Viscosity
Review
of Ethanol-Water
of Physical
Mixtures
under
Chemistry
High
of Japan
Vol. 47 No.
Pressure
?3
af.,tt}
thepressure
coefficient
ofviscosity,
~P ~.,forethanol
israther
small
at25°C,
while
the
data of Golubev et af.'af and the present work give an obvious positive pressure dependeaces. The
viscosity of the mixtures increases abnost linearly with pressure; whereas that of water is almost
independent of pressure in this pressure range.
The viscosity isotherms in this arork cna be represented by a quadratic equation of pressure.
B=Br + BeP} BaPr
where ~ is the viscosity in 10-'Ya•s (=cP)
(G)
and P the pressure in bar. The coefffcien[s for each
mixture are determined by the least squares method and listed in Table G with theaverage
and the
maximum deviations.
The composition dependence of [he viscosity under high pressures is shown in Fig. 10. Each
isobar also exhibits a maximum near the composition z=0.3. The maximum shii[sslightly
ethanol fraction with increasing pressure or temperature.
to higher
Conclusion
This paper represents the raw experimental data on the specific volume and the eiscosicy of
ethanol-water miz[ures as functions of temperature. pressure and composition. This basic
information would be necessary to solve the complicated behavior of ageous solutions of hydroxycompounds, which are yeCinadequately wtderstood.However, the temperature range is narron- in
the present measurements,.and more detailed measurements is thought to be needed fully near the
composition where the anomaly appears. Furthermore; the relationship between the equilibrium
(thermodynamic)properties aad the non-equilibrium(transport) properties should be derived, especially as for the appearance of anomalies, as well as in the case of aqueous solutions of other alcohols.
Table6 Coefficients
of the ViscosityIsotherms:n=B,+BzP+N3PrtP in bar)
Temp.
('C)
l"
0.20
25
50
B,
2.34083
Liz x 10+
BB x 108
Ave. Dev,
(,.°o)
Alac. Dev.
(.°o)
5.83501
-
6 .0312
0.25
o.4i
1 .31 i
0.25
o_4i
0.3i
0.30
2.32078
8.15612
-
0.40
2.li289
9.86471
-
3 .620
0,24
0.60
1.74644
10.0016
-
3.1239
0.41
1.ZI
0.78
1.41928
10.3408
0.24
0.>3
1.00
1.08861
8.16148
-18 ,7226
- 6 .331
0.16
0.3fi
0.20
1.08858
3.1009
-13.262
0.74
1.49
0.30
1.11481
1:644G8
0.60
1.13
0.40
1.Oi 846
1.2 t 148
18.153
-15 .191
0.53
].Si
0.60
0.94929
6.1578
-31 .312
O.Si
1.i9
0.80
0.80963
4.11241
0.6G
1.3fi
1.00
0.690264
5.07855
6.664
5 .883
0.44
1.12
-
1
(1977)
3
The
2-0
T. 1'amamMO,
1'. Tanaka
Review
Y. Satomi,
of Physical
H, Rubola
Chemistry
of Japan
Vol. 47 No.
and T. ~lakila
3.0
`
9
~~ R
\
8
~\
8J.~a
~
6
?>'C
z\o \
'6~~\~
2.0
A
0
.e
Fig.
Composition
dependence of the viscosiq~
of ethanol-eater
mixtures
at 25' and
>0'C under high pressure
I:
1 bar, 2: 98 bar, 3: 196 bar,
~: 294 bar, 5: 392 bar, 6: i90 bar,
i0'C
is 389 bar,
>` i
8: 686 bar, 9: 785 bar
Pa _
8 ~ b~9
ar
5~
3 a
0.2
1.0
10
1
Pb~a
0
0.2
\lole
O.i
fraction
0.6
0.8
1.0
of ethanol
Acknowledgment
The authors wish to thank D4r. Akihikb Ogiho (Bridgestone Tire Co., Ltd.) and Dlr. Sadao
Yabu (Dlatsushita Electric 1Corks, Ltd.) for their careful experimental nrorks, and are also indebted
[o Miss I:aori Pujishi[a w•ho performed helpful work in the preparation of [his paper.
Depurh+rentof C4emical Engirreerireg
Fatally of Engineering
Psabei'uiaersity
%be 657, Japan
1 (1977)