Title
Specific volume and viscosity of methanol-water mixtures
under high pressure
Author(s)
Kubota, Hironobu; Tsuda, Sadahiro; Murata, Masahiro;
Yamamoto, Takeshi; Tanaka, Yoshiyuki; Makita, Tadashi
Citation
Issue Date
URL
The Review of Physical Chemistry of Japan (1980), 49(2): 5969
1980-02-20
http://hdl.handle.net/2433/47079
Right
Type
Textversion
Departmental Bulletin Paper
publisher
Kyoto University
The
Review
of Physical
Chemistry
of Japan
Vol. 49 No.
59
THE REVIE\V OP PHYSICAL CHEDSISTRYOF JAPAS, VOL. 49, No. 2, 1979
SPECIFIC VOLUME
AND VISCOSITY
MIXTURES
UNDER
OF METHANOL-WATER
HIGH
PRESSURE
BY HIRONOBU KUBOTA, SADAHIRO TSUDA, IIASAHIRO
TAI:ESHI
YAa[A]SOTO, YOSHIYUKI
New experimental
data on the specific
h'lURATA
TANASA A\D TADASHI itSAIiITA
volume and the viscosity
of methanol-water
mixtures are presented
as functions of temperature,
pressure and composition.
The specific volume has been measured by means of an improved
"high pressure
burette"
apparatus
within an error of D.0> percent, covering temperatures
from 10 [o
75'C and pressures up 101000 bar. The viscosity has been obtained by afalling-cylinder
viscometer
with the uncertainty
of less thao two percent,
covering
the same temperature range and pressures up to 700 bar.
The specific volume of this system is found to decrease monotonously
with increasing pressure.
The experimental
results
agree well with several literature
values.
The numerical
data at each temperature
and composition
are correlated
satisfactorily
as a (unction
of pressure
by the Tait equation.
The isothermal
the excess volumes are also determined
from the experimental
n definite minimum appears on the isothermal
compressibility
bars at temperatures
lower than 1i°C.
The excess volumes
increase with increasing pressure ar lowering temperature.
compressibilities
and
data.
It is found
versus composition
are always negative
that
isoand
The viscosity of pure methanol
and its water mixtures is found to increase
linearly wi[b increasing pressure, whereas that of water decreases with pressure
and 25'C within the present experimental
conditions.
The viscosity
isotherms
almost
at 10'C
can be
represented
by a quadratic
equation
of pressure within the experimental
errors.
As
for the composition
dependence of the viscosity, a distinct maximum
appears near 0.3
mole fraction of methanol
slightly to higher methanol
on all isobars at each temperature.
fraction with increasing temperature
The maximum
or pressure.
shifts
Introduction
It is well known that alcohol molecules
structure
1.2>and that alcohol-water
properties.
Recently,
required
the reliable
pressure
This paper provides
water binary mixtures
systems show consequently
experimental
for both theoretical
ments at atmospheric
is aqueous solutions
have been reported,
as functions
some anomalies
data of these systems
works and engineering
extensive
give strong influence on the water
and accurate
of temperature,
calculations.
on various
Although
a few are available
data on PVT relations
in various physical
physical
properties
aze
a number of measure-
under high pressure.
and viscosity
pressure and composition.
(Received Arovember I3, Ip7p)
1) F. Franks and D. J. G. Ives, Quart. Rev., 20, 1 (1966)
E) G. N6methy and H. A. Schecaga, !. Cbern. Phys., 36, 3382, 3401 (1962)
for methanol-
Numerical
data have
2 (1979)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
60
A. Rubota,5. Tsuda,'.N.Murata,T. Yamamo[a,Y. Taaakaand T. Makita
been determined at temperatures ranging from 10°C to 75°C, and pressures up to 2000bar for the
specific volume, and to 700 bar for the viscosity, employing a modified piezometer and afallingcylinder viscometer. Empirical correlation formulas have also been presented for both properties
using;the present results.
Experimentals
PVT measaremeats
The schematic
diagram of the experimental
known weight is introduced
is transmitted
through
test liquid is detected
mercury
nlled
of a small
transformer.
deformation
The
lower pressure
is applied
iron goat
The high pressure
as shown in Fig. 2. The inner cylinder
which somewhat
is shown in Fig. 1. The sample liquid of
in C and G from an oil pump A. The volume
from the displacement
column by means of a differential
cylinders
apparatus
into a high pressure vessel D and upper part of burette G. The pressure
is athin-walled
separately
change of the
on the surface of the mercury
vessel D consists of coaxial double
sample
cell, to the outer wall of
from the oil pump in order to minimize the
of the cell a)
vessel D and burette
G are immersed
in a liquid
thermostat
controlled
within _0.01`C.
~VB
B1
Bz
D
~'k
i~
-E~
O-ring
Armor-ring
Ou[ertylinder
Thin•walled
Oil inlet
I
H
~r
F
V~
-aa
V~
Vx
sample.cell
i
G
Vz
I
.1
u~
Fig. 1
O-ring
F: Detai
Vs
Schematic diagram for PVT measuremen
A Oil pump
Bte Bourdon gauge
C Mercury mservoir
D High pressure vessel
Ers Thermostat
F Differential transformer
G High pressure burette
H Ammeter
I Cathe[ometer
J Iron float
~)
// J_paJ"
~t
Fig. 2 Diagram of high pressure vessel
3) B. Le Neindre and B. Vadar (Ed.), "Experimental Thermodynamics", vol. II, p. 421, Butter
worths, London (1975)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
SpecificVolumeand Viscosityof Methanol-R'aterMixtures
61
The pressure is measured by Bourdongaugescalibrated against a pressure balance. The uncertainty
in pressure measurementsis estimated to be less than 0.1 percent.
Using [he displacement of the iron float, the specificvolume of the sample liquid is calculated
by the followingequation:
v=vo- ~y(dV.p~-(dY',nn+dVnar+dV«u))
(I )
where
vo:
dV.pp:
dVtun:
dVn,::
dl'~.u :
W:
specific volume in cros•g ' of the sample at pressure Ps bar,
apparent volume change in cm' of the sample at P bar,
volume change in cm' of the Connectingtube at P bar,
volume change in cros of the high pressure burette at P bar,
volume change in cm° of the thin-walled sample cell at P bar,
total weight in g of the sample.
dVr„e, dVson and dV~eu were calculated employing the elasticity theory. The uncertainty of the
present specificvolume values is estimated to be less than 0.05 percent.
Viscosity measurements
The viscosity is measured by afalling-cylinder
viscometer. The details of the viscometer were
described elsewhere4l.
The apparatus consists of a precisely bored Pyrex glass tube equipped coaaially in a high pressure vessel and a glass cylindrical plummet with hemispherical ends. The plummet is provided with
four small projecting lugs at each end of [he cylindrical part, which acts as a guide to keep plummet
concentric when it falls. The falling time of the plummet is determined within-1-0.1 ms by an eletIronic time-in[en~al counter using a He-Ne gas laser beam passed through a pair of optical windows
and a phototransister.
The temperature
of the sample is maintained constant within -!-0.05°C by
circulating a thermostatic fluid through the jacket around the pressure vessel. The pressure is measured by a Bourdon gauge with the same accuracy as in the case of PVT measurements.
The instrument constant and its change with both temperature and pressure are calibrated with
the aid of the experimental viscosity values under atmospheric pressure obtained by an Ostwald
viscometer and of the reference viscosity of water correlated by the International Association for
[he Properties of Steam (1974). The uncertainty of the present viscosity values is estimated to be
less than 2.0 percent.
Materials
Methanol
used was obtained
more than 99.56
in volume.
from Wako Pure Chemical
Industries
Methanol
and water were purified
and water
were prepared
Ltd.
several
The reported
times
purity is
by the fractional
distillation.
The mixtures of methanol
4) Y. Taaaka, T.Yamamoto,
by weighing,
using an analytical
balance
Y. Satomi, H, Kubota and T. Makita, Rev. Phyr. Chem. Japan, 47, 12(1977)
The
62
Review
of Physical
Chemistry
H. %ubota, S. Tsnda, M. Murata, T. Yamamoto, Y. Taoakaand
with a sensitivity
substantially
of ±O.lmg.
accurate
Therefore
their composition,
mole fraction
T. Makita
of methanol,
within 0.01%.
Table 1 The SpecifirVolume
of Metbaml-Water
Mixtures in cm3/g
Temp.
_~
x=6
0o
x=
zs
x=
16
93.1
]88.9
3416
5]4.3
1
883.6
1895.8
1208.9
1380.6
1549.G
o_sa41
607.7
1
0
859.4
1
oasa
.023]
9.9521
9.9464
9.9412
1029.7
1199.A
1379.0
1
.0178
1738.5
189 B.5
2079.8
0.9358
os314
0.9273
155].6
1TZO.6
!891.9
9.9997
2065.0
0.9848
9560
oso
x=
t
t
.0894
OSTB
.0513
o4ae
t _0388
1 _0115
1 .0054
0.75
x-
n
P
I .0093
9.9918
9.9945
esT74
9.9708
L0
174.4
343.'1
61 T.e
8986
la
0
P
F
11214
1.1285
1.0999
1.8899
1.0
]4.5
936.8
598.5
881.2
B53.2
1029.9
1_osla
L 9793
1.6667
]397.9
]370.7
1515.8
1.1061
1.6
25
50
TS
0.9968
0.9BOB
0.9850
0.9T9B
693.2
&71.8
966.3
1102.8
0.9745
0.9694
0.9647
0.9601
1241.9
1303.1
1522.2
1652.7
1798.8
0.9655
0.9511
0.9487
0.942R
0.9986
1937.1
207 i.]
0.9947
0.9309
1.2466
a.fi
]82.8
330.8
50 L9
L 1854
].1709
].1559
1.1429
BT 8.7
1.1311
840
].1205
1.1109
L 1552
1.0999
18123
1188.6
1364.5
1.1303
1.1256
1.1179
0
1.8585
1.9511
1.8464
1020.0
1193.8
1967.2
1_]019
e
21.6
]ST.S
929.9
502.9
1.2489
1.za 92
1.2984
1.3934
875.6
1.1793
Bi9.2
L Ifi TG
ITS5
1
1.0392
1711
LoTTT
1443.4
0.9995
1008
0
1.0334
] BBS 3
10708
15325
9.9885
2085.8
1.92 TA
2955.0
].8897
1695.7
1.1446
1.1340
1883.3
2858
198.9
278.0
418.8
551.2
1.00
P
].0
1.t 340
1.1241
Lt150
1.1069
1.0905
3.0913
135.2
276.8
41].7
55}.9
893.8
].1891
1.1762
1.16{8
1.15{]
1.1452
131.9
279.0
115.3
553.6
897.4
1.2509
1.2335
1.2189
1.2055
1.1930
830.2
970.6
1108.2
1.0921
1.0289
1.0218
1248.fi
138},1
!"x20.4
1660.0
1 T98.a
194z.a
1.01 TO
1. p124
1.0081
1.0098
0.9994
osssz
fl50.2
875 n
uDe.a
1243.0
]364.1
1.0837
1.0776
3.0719
3.0861
1.0603
831.2
967.8
1108.6
1245.8
1364.1
1.1364
].1zez
].1zos
1.1132
1.1064
837.1
983.0
]103.3
12?0.3
1361.4
1.1621
1.3727
1.3893
1.3547
1.19fi2
2073.6
0.9913
]518.3
]658.0
]803.8
]834.6
aDJZs
1.0552
1.0500
1.0448
3.0403
1.0355
1520.4
165 T.3
3797.0
1938.0
2o75A
].1990
1.0940
1.0880
1.0822
l.D7ss
1532.8
1658.7
1'.99.7
1949.8
2069.4
1.3380
1.13 t2
1.1242
3.1171
1.1119
3,D
128.3
2143
415.9
556.6
691.9
929.1
972.0
1107.5
]29 "a.l
]361.1
]525.9
1859.9
1734.0
1928.3
2078.0
1.1606
1.1495
1.1383
1.1286
l.D
139.fi
273.5
413.9
1.2367
1.2198
1.2063
1.0
131.0
276.3
1.3311
1.2859
12646
1.1196
3.1116
L 1041
1.0966
1.0900
sso.e
691.2
634.3
9]4.T
1114.4
1.1921
1.1005
L 3697
1.3691
1.1502
413.9
5}89
693.9
12416
12324
1.2181
LOSa6
1.0773
1.0]12
10859
1.0629
1.0558
1.0502
1248.fi
1380.0
1524.3
1856.6
1 eD1.e
1.3418
1.13x0
1.1268
].1195
].1131
1.1x64
892.3
967.1
1106.1
1245.{
1364.1
1519.7
1636.6
17932
1.2068
3.39{9
1.1845
1.1797
1.16"a7
3.1575
7.7477
1.1423
19}3.6
2215.4
1.]002
].0090
1938.7
2075.0
1.1347
1.1262
34.5
184.!
930.9
505.4
678.7
3.3487
1.3230
1.2956
1.2726
1.2532
Bi8.0
1004.9
1191.)
1365.1
1538.5
1706,6
1647.4
1920.5
1990.5
2058.3
1.2960.
3.2223
1.2078
1.1952
1.1836
1.1731
1.1649
1.1607
1.1368
1.1330
1.0131
l.aosD
1.0003
D.994B
1.0
137.9
200.4
415.3
1.0862
1.0786
1.0713
1.0641
564.3
702.9
835.0
97n„7
1109.7
Dsesz
0.9830
0.9790
0.9742
D.9890
366.7
696.7
892.3
970.8
1108.1
1.0577
1.0521
1.0484
1.0408
LOS58
1247.2
]379.3
1533.5
1859A
1799.0
]93{,8
30759
0.9653
0.9612
0.9584
0.8527
0.9488
0.9448
0.9408
12}2.3
1384.1
1518.3
1856.6
IT99.0
1938.0
2078.4
1.0306
1.0288
1.0210
1.0184
LOIIJ
1.OOJ1
1.002 )
1.0
174.4
342.1
513.3
688.1
BSfi.3
].0250
7.0180
1.0100
1.0039
0.9964
0.9899
34.5
169.8
337.1
610.2
i 09.5
854.9
1.1051
1.0973
1.0873
1.0780
10679
1.0611
95.1
167,2
393.7
soS.D
667.0
769.9
1.1842
1.!728
L 1584
1.1463
1.1340
1.1280
1029.0
1202.6
13 i 0.3
1649.fi
1132.3
1895.0
2067.4
0.9835
0.9774
0.9715
osssa
Dssm
0.9556
0.9502
1027.0
1196.2
1370.7
1644.4
3.0535
1.0464
1.0395
1.0329
1.1226
11128
!.1036
1.09fi9
17 V.1
1890.2
2081.9
1.0267
1.0208
1.0149
661.1
]021.9
1194.8
1324.6
1692.7
17]4.7
]B95A
2080.3
1.0865
10790
10719
1.0651
es
163.0
330.9
506.1
616.0
B4 T.T
1020,6
1192.1
1352.0
1593.7
1710.9
1806.0
2058.4
1.2037
].z6ss
1.246]
1.2257
1.2088
].1909
].]787
1.1636
1.1522
1.1420
1.1311
].1219
1.1131
1.3048
1.0
991
1.1815
L0
735.2
275.6
4zD.1
537.0
898.0
1.0
138.G
276.3
412.5
1.0
1.t
3
1.0883
1.0611
1.05?6
].o4as
1.0}30
1.0988
1.8
134.5
28}.6
4zo.1
559.8
T 14.7
2 (1979)
Vol. 49 No
of Japan
1.2]08
should
be
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Specific
Volume
and Viscosity
Results
and
of Methanol-Water
63
Mixtures
Discussion
Specific rolu+ne
A part of experimental
results is given in Table 1 `, where P, v and X denote pressure in bar,
specific volume is cm'/g and mole fraction of methanol in the mixtures, respectively.
Specific
volume values at 10°C and 75°C are also plotted in Figs. 3 and 4, together with the literature values
for pure water. The specific volume decreases monotonously with increasing pressure throughout
the experimental conditions at each composition.
At the experimental
temperatures except ii`C,
the present results of pure water is found to agree quite well with the values given by Chen et al.=~,
Kell et al.al and Grindley e[ al.~l The discrepancy between the present results and literature values
at 75`C is witbin 0.0945. For the mixtures, there exist reliable data only at 25°C and 1000 bar by
Gibsons>and 25`C and 1013 bar by ivforiyoshi e[ als> As for the compression, literature values differ
from the present results by less than 1.4646 and 0.9195, respectively.
For each temperature and composition, the specific volume data are correlated as a function of
pressure by the Tait equation
"°vev =C to B+P
~e
g BtPe
2
~~
1.3
t.3
~
m l.2
'
m 1.2
X
~sreo_x"
~o ,
Xn~x-
EV
~ ~.1
O
1.00
O.ii
0,50
w
0.25
c 1.0 H
6~ W
~"_moo.
0V
_
0.25
V
N LQ
0.00
0.00
0.9r
0
Fig.
3
1000
Pressure bar
- ~
?000
0.9~
0
1000
Pressure/bar
~
2000
Pressure dependence of the specific volume
Fig. 4 Pressure dependence of the specific volume
of Methano]•Wnter mixtures at 10'C
of \lethana4Water
mixtures at 75'C
~ :This work
Q ;This work
/:5)
/:3)
• Data of X-O .15, 0.30, 0.35 at IO°Cand 75'C, and of X-O.IO, 0.15, 0.35 at 25'C and 50'C are available
an request.
5) C. Chen, R.A. Fine and E J. Millero, J. Am. Chem. Sat., 57, 1551 (1935)
6) G. S. Bell and E. R'halley, PGiI. Tsans. Roy. Sot., A25S, 565 (1965)
7) T, Grindley and J. E. Lind, Jr., J. Chern. Pkys., 54, 3933 (1971)
8) R. E. Gibson, J. dnr. Chem. Sot., 57, 1551 (1935)
9) T. Moriyoshi, Y. Dforishi[a and H. Inubushi, J. CGem.Thermadynarnics, 9, 577 (1977)
iU
U
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
64
H.
Kuhota
S. Tsuda,
M, hiurata.
Table
Temp.
S
10
28
A
Comp.
•C
?
Ave
C
CoeBuients
I>ev
Nxx
Dev.
x
bu
T. Yamamoto,
a
Y. Tanaka
of the Tai[ £quatioo
Temp.
COmD.
•C
X
A
2366
0.2691
D.D2
D.Da
D.oD
3380
0.15
s liz
Dsvl
0.01
O.Oi
0.10
zszD
0.25
0.90
0.35
2 i3B
0.2896
0.01'
0.03
24]1
D.zssi
o.m
o.oz
zsal
2458
294]
D.zi4]
n.D6
o
0.15
0.25
0.35
oss
O. ]i
1563
0.22
n.Dz
0.05
D.6D
13es
us4
0.2392
0.0R
0.04
OA5
963
1.00
888
0.2295
O.Oz
0.03
L00
833
50
DI
Ave
C
Dev.
1{R Lilev.
bsr
D.D9
A5
and T. Makita
l flil
0.34 pfi
0.3055
0.303]
0.2888
0.2583
0.02
0.00
0.01
0.01
0.0]
D.D6
0.2308
0.23 p]
D.zxt4
0.02
O. DS
n.a
0.05
D.m
0.01
0.09
D.oz
0.02
0.02
0
zs9A
D2D69
0.01
a.Dz
6
3268
0.346]
O.DI
O.ID
3214
D5233
0.00
0.01
D.15
2911
0.2885
O.OI
0.15
9168
2686
0.3196
0.2904
0.01
D.as
19as
0.2699
0.01
0.03
0.09
0.04
0.30
0.01
0.03
D.zsoe
0.01
0.35
159fi
1ss3
0.2450
a lDs
0.03
0.06
D.Dz
0.2840
0.01
I65B
D24]n
0.02
D.Ds
050
1211
02419
0.01
0.03
0.02
lnse
Dszsa
D.Dz
D.D]
O.iS
]49
02338
0.01
0.02
D2283
0.02
D.Da
1.D6
592
0.2309
0.03
n.Ds
0.25
0.35
0.56
D.]5
l.Ds
815
D.O1
]5
1.5
1.5
1.0 bay i
of
i. a
,
~
0 1.0
r
a
u
a
c 0.5
Fig. 5
s
500
`
o.
iooo
0.25
Oa0
O.i>
Dfole fraction of :Ifetbanol
e O.a . ~
~ o
1.00
Composition dependence of the isothermal compressibility at IO'C
where vo is the specific volume
equations
i~
a 0 1.0
zaoo
0
i~
i
L0 bar
could reproduce
for the Tait equation
The isothermal
at a pressure
experimental
0
Fig. 6
.O,A~O
Op
,,~A~~
0.25
0,50
0.75
Mole fraction of Methanol
1,00
Composition dependence of Che isothermal compressibility at 75'C
deviation
The obtained
of 0.03%.
Tait
The coefficients
are listed in Table 2.
compressibilities
;
tqr-- v~a /7•
calcttlaled
-o~
Po, and B and C are constants.
data with an average
O
O
150
using the Tait equation,
nol in Figs. i and 6, respectively.
~3)
at 10'C and 75'C, are plotted against the mole fraction of methaIt is found that a definite minimum
and IS°C, but these minima fade out gradually
as the temperature
exists near X=0.15
increases.
at 10°C
At 75°C these minima
0
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
i
Specific Volume and Viscosity of Metbanol-Water Mixtures
disappear completely.
65
This anomaly was also found in the ethanol-water system as reported in
previous paper<>.
Excess volumes are also calculated at each experimental temperature by the following equation
S'"=l'mi:-
{ Vv.ou•Xt V~.,.dl -~)
(4)
The results of 25°C and 75°C are given in Figs. 7 and 8, respectively. At all the experimental conditions, excess volumes obtained are always negative, and it seems that pressure makes the excess
volumes less negative and, in a sense, the mixture appcoaches the ideal solution with increasing
pressure. At 25°C, the present results agree well with the literature valuesto),
Mole fractim of Methanol
0.25
0.50
0.75
0
,~
Jfole fraction of Methanol
0.25
0.50
O.7i
0
~~
~
~u
1.00
,~
,~ /°
°~o s~
Eu
E
a0
a
o
loo
~~o
-i
.o
VV
MW
v
1.0 bat
V
~/
I
0e
E
v9
y
0
c
2000
\ ~
-os
e E -os
0
0
d
1.00
~o
`
~` ~ °~O
r~
-i
°
i
500 °
b\„ ~d
100
.a
~
X
._,°_
i~
.
1.0 bar
-u
-Li
Fig. 7
Composition dependence of the excess volame of Methanol-Water
mixtures at
25'C
Q ;This work
~ : t0)
Fig. 8
Composition dependence of [he excess
volume of Methaml-Water
mixtures at
7i C
Viseosfty
The experimental
are plotted
plotted
results are tabulated
as a function
for comparison.
0.35. Agreement
of composition
Each viscosity
with the available
among [hem is somewhat
in Table 3. The data obtained
in Fig. 9, where other
isotherm
bas a maximum
data is satisfactory
experimental
data11-ts)
at a composition
at 10°C and 23`C. However
notable at 50`C, where [he largest deviation
al.tx> and those of Traubela7 fs about 11% near the maximum.
10)
ll)
12)
13)
14)
at atmospheric
between
The present
pressure
are also
near X=0.30
the discrepancy
the data of Sabeis et
data agree quite
M. L. \tcGlashan and A. G. N'illiamson, J. Chern. Eng. Data, 2I, 196 (1976)
S. Z. dlikhail and W. R. Kimel, J. Chern. Eag. Dafa, 6, 533 (1961)
T. N. Yergavi<h, G. LV.Swift and F. Kurata, J. Che+u.Eng. DNa, 16, 222 (1971)
S. N. Sabnis, W. V. Bhagwat and A. B. Ranugo, !, hrdian Chern, Soc., 25, 575 (1948)
J. Traube, Bar., 19, 871 (1886)
well
7
The
6fi
H. Kubota,
S. Tsuda,
Table
Temp.
Y
.C
Lee
5D
The
Viscosity
X=0.15
.\"=O. UU
of Me[banol-Water
X=0?6
X
• 0.30
X=0.35
I.292
1.z84
1 ~ia
2.37A
2.381
2.399
1.270
1.268
].284
2.40E
2.428
L0
99.1
I9T.2
295.2
99],3
491.4
589.4
687s
0.8911+
0.8895
0.8882
1 A61
0.8872
0.8866
0.8864
0.8066
O.BBT2
L468
Lii9
1.495
1.503
1.508
1.6i6
l .fi 6i
1.686
1.:06
1. i3!
L698
I.i23
L i4i
].0
99.1
197.Z
295.2
399.3
49I A
O. S460+
0.5486
0.5504
0.5523
0.S S4i
0.5581
DRBI]
o.aao2
0.8103
0.818T
0.93i5
0.849T
e.as2t
0.8882
0.8923
D.BS55
D.as3e
0.8920
58TA
68i.5
O.SSB3
0.5805
0.~13
o. a?Bi
0.8307
D.8340
0.8i54
0.88i0
0.8951
0.9096
0.9002
0.9149
0.9205
0.9302
1.0
89.1
19i
295:
393!3
491.4
589.4
8aT.5
0.3783+
0.9808
0.9832
0.3857
D.495N
O.i02;i
O.SLSi
O.i939
0.5555
0.3882
0.3908
0.9999
D.9seD
D.i235
0.5341
O.SiI?
0.645d
0.5iifi
0.5 Bifi
0.6977
0.6089
~
2.449
[APS
L 464
I a69
2.551
2.588
2.63i
2.667
2.:08
2,600
2,Sii
2,fi 16
2,656
R,i3T
2.733
2.ii6
2592
2,:93
2, 848
2.902
1.581
1.611
].626
LSii
1, 53fi
L61T
1.631
1.637
1.6i4
1.620
1, 634
L6i5
0.5610
0.56fi2
2,419
2.491
2.563
2.6Z4
3.689
2.i67
2.895
2.908
1.710
1. T63
1.788
L 918
0,56iT
D.57ae
D.6909
0.6029
D,6141
0.636D
Chemistry
0.0335
0.8962
0.8i33
of Japan
Vol. 49 No
and T. Makita
Tanaka
Mixtures
1.311
].301
4
of Physical
,Y.
1.0
99.1
i6
2.360
2.36i
T. Yamamota
197.2
295.2
]93.3
491.4
589.4
68T.5
10
25
3
M, Murata.
Review
in 10'a Pass
S=
0.60
1.9 Tf
C•OAS
.\' • LD
0.8953
O.i394
0.7841
2.346
2.3B4
1.272
1 .]2i
1 .9 T4
1.426
1.472
lsze
1.681
1.823
1.325
1.362
0.9031
0.9TT0
0.5959
1.909
1.93T
1.902
1.529
1 .ST2
1.61i
1.012
1.048
1.087
1.124
1.189
O.T551
O.iTBD
0.5780
0.6012
O.61T8
0.6318
Ds4TT
O.BT10
0.6649
2.044
2.095
z.lsa
z.azs
z.a7s
0.8937
o.9ose
0.9192
0.9193
0.9364
0.7 BT5
0.8238
D. B3as
0.8561
D.BSaz
O.aa92
0.550T
0,5G40
0, 5762
0.5901
osaz4
0,6141
D_62TO
0.5220
0.53T7
O,SSOG
0, 5631
osiel
0.5929
0.6053
1.19T
0.8147
0.861I
o.ee39
0.9164
0.9508
0.59ST
O.Ba20
0.600
O.BT]O
0. T008
0. T3]0
0. T558
0.7074
0.394T
0.411 B
D.4zao
0.4481
0.4883
0.4 T9B
0.5090
0.6192
O.iOTT
0.4284
0.3130
0.3268
0.44 G4
0.4T25
o.4soT
0.50T5
Dszsfi
0.3421
0.3581
D.3 TZe
0.30T9
0.4038
(39]J]
o ma
2.5
9
a
IO'C
z.o
n
O
T
.o
Fig, 9
~8m~
1.5
2i'C
~.~
B°
o0c8.
;o
50'C
a
Composition dependence of the visrnsity of \tethaaol-Hater mixtures at LO bar
Q :This work
) : 14)
.~ 18)
~ : 11)
p : l3)
o~ l9)
~r : 12)
~ : t 6)
•:13)
®:17)
~
a
0
4
O.i
0
IS)
16)
0.2
0,4
bfole iractioo
A. E, Dunstnn,
A. E. Dunstan
O.fi
0,8
of Methanol
1.0
Z. Phys. C4am., 49, 590 (1904)
and F. B. T. Thole
!. Chern, $Oq, 95, 1556 (1909)
2 (1979)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
SpecificVolumeand Viscosityof Methanol-WaterMixtures
67
with the results of Yergovich et al.t9 at 10°C and those of Mikhail et aLttl at 25°C and SO°C
obtained by the modifiedOstwald viscometer.
The pressure dependences of the viscosity of this mixture at 10-C and 75°Care shown in Fig.
10. So far as we know, there exist no experimental viscosity data for this binary system under high
pressure. On the other hand, three sets of experimental data are found in IiteratureTO`~for pure
methanol under pressures as shown in Fig. 11. Althoughthe overlap of experimental conditions is
limited, the consistencebetween our data and others is reasonable in view of the distances between
[he viscosity isotherms and their gradients.
The viscosity isotherms both is Fig. 10 and Table 3 show the following Features:
1) The viscosity of mixtures always increases with pressure almost linearly, whereasthe pressure coefficientof viscosity, (8r,18P)Tfor pure water is slightly negative at 10`Cand 25°C
within the present pressure range.
2) (8r~/r7P)Tincreases with the mole fraction of methanol at each temperature.
3) (8r~/8P)Tdecreases with rising temperature for the mixture of a constant composition.
3.0
Xm~ox=
0.21
1.0
2.5
0.300.31
~-~
0.15
030
.
10°C
0.8
2.0
23°C
0
.o
A os
0T
~ D.a ~
~OH,,~
g~' 0.150;50
0.5
0.2
0
Fig. !0
l7)
18)
t9)
20)
21)
22)
.40'C
; . 60•C
. :~80C
\Se
HzO 1fe0H 0.75
200
400
Pressure bar
e~30°C
e
HzO
1.0
.20'C~ o~
~
O.7i
1.3
600
Pressure dependence of the viscosity of
Methanol-Water mixtures at 10'C and
75'C
~ : 10°C
~ : 7SC
,
0
Fig, l1
So•c
73'C
• 120'C
200
400
Pressure/bar
600
Pressure dependence of the viscosity of
Tiethaaol
~ ;This work
p : 21)
~ : 20)
• ~ 22)
E. C. Bingham, G. F. White, A. Thomas and J. L. Cadwell, Z. Pkys. Chem., 83, 641 (1913)
H. Schott, 1. Ckem. Eng. Deta, 14, 237 (1969)
M. Kikuchi and E. Oikawa, rVippon Kogaku Zwshi, 88, 1259 (1961)
P. W, Bridgman, P~oc. Am. Acad. Arfs. Sci., 61, 57 (1926)
S, Hawley, J, Allegra and G. Holton, J. Acausr. Soc. Anr., 47, 137 (1970)
N. P. Isakowa and L. A. Oshueva, Zh. Fiz. Khim., 40, 1130 (1966)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Ii. Kubota, 5. Tsuda, M. Murata,
68
Table
Coefficients of Equation ($) fox the Viscosity in
30_a Pa•s
4
z
Temp.
Bp x 104 B3 x 108
131
°C
xn
50
* For
T. Yamamoto.
O.li
0.2v
2.35982
2.5;964
0.30
0.3i
0.50
0.45
1.00
2.50521
2.41965
1.9:211
L2i304
O. G9599
0.15
0.25
148090
1.58:33
0.30
0.35
0.50
0.15
1.00
].54~2R
1.54916
1.9264A
0.91291
0.55268
015
0.2i
0.48984
0,83912
0.30
0.35
O.i9
O. ii
1.00
0.03905
O.B?950
9.433fi3
0.5]920
9,39110
0.16
0.25
0.}621}
0.53041
1.238A
1.?290
0.30
0.:15
OSO
0.4."+
1.00
0.5.363
0.63 i21
0.508}e
0.38381
0.29863
1.20]1
1.5680
].!282
S.Si~O
].97x7
7SC
isotherms
o.3sos
a.3as3
ss2oe
s.977a
s,5a;z
i.19t8
3.i?Ad
]1.23?
-15.8{6
^.801
1.3 i r
:^^-50
-
- O. SGS
-i^^-S5i
0.1983
2.0571
5.::93
9.7669
3.5679
5.1208
9..' 517
..3X8
osa~
- 3s9z
-13sos
L32A1
0.953.;
].A339
5389
-10.{83
2,5314
ss4n
-t4,53o
- I96B
0.488
i.0i1
-14.8:3
.
p
0.1
G.z
0.2
0.3
0.1
0.9
0.?
Oa
0.3
OR
8.2
8.6
0.3
n. a
o.z
o.z
0.3
o.a
0.4
O.B
O.a
0.1
0.6
G. i
1.G
0.3
].6
LG
0.3
G.2
0.~
O.a
O.a
0.402
1.4U i
0.~
0.5
0.6
os
4.51E
]?7i
0.150
0.9 i3
0."_{R
0.3
0.2
0.03
o.o;
o.v
0.6
os
o.l
o.l
o.^_
4.t E4
0930
O.:t
0.1
0.8
0.3
- 5.408
Eq. (S) is valid from 99 to G88bar.
and T. Makita
3.0
Mex.ilev.
a
LG
0.8
].3
n.7
13
1.8t1i
1.i61A
-
Ave.tlee
Y. Tamka
io•c
2.5
na z
.o
0T
0 1.5
i.a
zs°c
50°C
7SC
os
0
Fig. 11
0,2
0.4
0.6
0.8
1.0
Mole fraction of Methanol
Composition dependence of the viscosity of Methanol-Water mixtures
at various temperatures
Q :600 har
~ :200 bar
O :400 bar
~ : 1.0 bar
The viscosity isotherms can be represented by a quadratic equation of pressure:
tl=Br t BsPt BsIJ°
(3)
where n is the viscosity in 10_s Pa•s (=cP) and.P [he pressure in bar. The empirical coefficients for
each mixture are listed in Table 4, with the average and the maximum deviations of the experimental data from the equation.
The composition dependence of the viscosity under high pressure is shown in Fig. 12. The
viscosity isobars have the following features:
1) The composition dependence of the viscosity is evident at low temperatures, but it diminishes gradually with rising temperature.
Z) Each isobar has a maximum near the composition of X=0.300.35.
slightly to higher methanol fraction with rising temperature
The maximum shifts
or increasing pressure. The
shift is more explicit at low temperatures.
These characteristic behaviors of viscosity for methanol-water mixtures under pressures are
quite similar to those of ethanol-water system as reported in our previous paper4>. The large positive departure in the viscosity-composition isobars from those of regular solutions, in which the
additive law is held approximately, shows that the interaction between unlike molecules is seriously
strong, as well as the behavior of the excess volume in Figs. 7 and S. Nater and alcohol molecules
form various complex "clusters" according to the composition of mixtures, in addition to the "ice-
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Specific Volume and Viscosity of Methanol-Water
bergs" of water molecules
maximum
of viscosity
themselves
and the association
and the minimum
of excess
volume
of alcohols.
Mixtures
69
It is quite interesting
occuc at different
compositions
that the
of mix-
tures.
The authors
Inspection
wish to thank
Institute,
1Ir. Yasuhare
for his careful experimental
Kimura,
Kobe Agricultural
and Forestry
efforts in this worl•.
Department
of Chemical Engineering
Faculty of Engineering
Xobe University
Katie 6i7, Japan
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