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Title Specific volume and viscosity of methanol-water mixturesunder high pressure
Author(s) Kubota, Hironobu; Tsuda, Sadahiro; Murata, Masahiro;Yamamoto, Takeshi; Tanaka, Yoshiyuki; Makita, Tadashi
Citation The Review of Physical Chemistry of Japan (1980), 49(2): 59-69
Issue Date 1980-02-20
URL http://hdl.handle.net/2433/47079
Right
Type Departmental Bulletin Paper
Textversion publisher
Kyoto University
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
THE REVIE\V OP PHYSICAL CHEDSISTRY OF JAPAS, VOL. 49, No. 2, 1979 59
SPECIFIC VOLUME AND VISCOSITY OF METHANOL-WATER
MIXTURES UNDER HIGH PRESSURE
BY HIRONOBU KUBOTA, SADAHIRO TSUDA, IIASAHIRO h'lURATA
TAI:ESHI YAa[A]SOTO, YOSHIYUKI TANASA A\D TADASHI itSAIiITA
New experimental data on the specific 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 tempera-
ture range and pressures up to 700 bar.
The specific volume of this system is found to decrease monotonously with increas-
ing 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 compressibilities and
the excess volumes are also determined from the experimental data. It is found that
n definite minimum appears on the isothermal compressibility versus composition iso-
bars at temperatures lower than 1i°C. The excess volumes are always negative and
increase with increasing pressure ar lowering temperature.
The viscosity of pure methanol and its water mixtures is found to increase almost
linearly wi[b increasing pressure, whereas that of water decreases with pressure at 10'C
and 25'C within the present experimental conditions. The viscosity isotherms 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 on all isobars at each temperature. The maximum shifts
slightly to higher methanol fraction with increasing temperature or pressure.
Introduction
It is well known that alcohol molecules is aqueous solutions give strong influence on the water
structure 1.2> and that alcohol-water systems show consequently some anomalies in various physical
properties.
Recently, the reliable experimental data of these systems on various physical properties aze
required for both theoretical works and engineering calculations. Although a number of measure-
ments at atmospheric pressure have been reported, a few are available under high pressure.
This paper provides extensive and accurate data on PVT relations and viscosity for methanol-
water binary mixtures as functions of temperature, pressure and composition. Numerical data have
(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)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
60 A. Rubota, 5. Tsuda, '.N. Murata, T. Yamamo[a, Y. Taaaka and T. Makita
been determined at temperatures ranging from 10°C to 75°C, and pressures up to 2000 bar for the
specific volume, and to 700 bar for the viscosity, employing a modified piezometer and afalling-
cylinder viscometer. Empirical correlation formulas have also been presented for both properties
using;the present results.
Experimentals
PVT measaremeats
The schematic diagram of the experimental apparatus is shown in Fig. 1. The sample liquid of
known weight is introduced into a high pressure vessel D and upper part of burette G. The pressure
is transmitted through mercury nlled in C and G from an oil pump A. The volume change of the
test liquid is detected from the displacement of a small iron goat on the surface of the mercury
column by means of a differential transformer. The high pressure vessel D consists of coaxial double
cylinders as shown in Fig. 2. The inner cylinder is athin-walled sample cell, to the outer wall of
which somewhat lower pressure is applied separately from the oil pump in order to minimize the
deformation of the cell a)
The vessel D and burette G are immersed in a liquid thermostat controlled within _0.01`C.
B1 Bz
~r
~VB-E~
H
~'ki~D
V~
Vx
iF
G-aaV~
Vz
.1
u~ F: Detai
Fig. 1
I
I
O-ring Armor-ring
Ou[ertylinder
Thin•walled sample.cell Oil inlet
O-ring
Vs ~) // J_paJ" Schematic diagram for PVT measuremen ~t
A Oil pump Fig. 2 Diagram of high pressure vessel 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
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)
Specific Volume and Viscosity of Methanol-R'ater Mixtures 61
The pressure is measured by Bourdon gauges calibrated against a pressure balance. The uncertainty
in pressure measurements is estimated to be less than 0.1 percent.
Using [he displacement of the iron float, the specific volume of the sample liquid is calculated
by the following equation:
v=vo- ~y(dV.p~-(dY',nn+dVnar+dV«u)) (I )
where
vo: specific volume in cros•g ' of the sample at pressure Ps bar,
dV.pp: apparent volume change in cm' of the sample at P bar,
dVtun : volume change in cm' of the Connecting tube at P bar,
dVn,:: volume change in cros of the high pressure burette at P bar,
dl'~.u : volume change in cm° of the thin-walled sample cell at P bar,
W: total weight in g of the sample.
dVr„e, dVson and dV~eu were calculated employing the elasticity theory. The uncertainty of the
present specific volume 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 pres-
sure 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 elet-
Ironic 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 mea-
sured 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 from Wako Pure Chemical Industries Ltd. The reported purity is
more than 99.56 in volume. Methanol and water were purified several times by the fractional
distillation.
The mixtures of methanol and water were prepared by weighing, using an analytical balance
4) Y. Taaaka, T.Yamamoto, Y. Satomi, H, Kubota and T. Makita, Rev. Phyr. Chem. Japan, 47, 12(1977)
The Review of Physical Chemistry of Japan Vol. 49 No 2 (1979)
62 H. %ubota, S. Tsnda, M. Murata, T. Yamamoto, Y. Taoakaand T. Makita
with a sensitivity of ±O.lmg. Therefore their composition, mole fraction of methanol,
substantially accurate within 0.01%.
Table 1 The SpecifirVolume of Metbaml-Water Mixtures in cm3/g
should be
Temp.
_~ x=6 0o x= 0 zs x= oso x= 0.75 x- 1.00
F P P n P
L0 I .0093 16 1 .0894 1.0 11214 ].0 1.1061 1.6 1.2466
174.4 9.9918 93.1 OSTB ]4.5 1.1285 a.fi L 1854 21.6 1.2489
343.'1 9.9945 ]88.9 t .0513 936.8 1.0999 ]82.8 ].1709 ]ST.S 1.za 92
61 T.e esT74 3416 t o4ae 598.5 1.8899 330.8 ].1559 929.9 1.2984
8986 9.9708 5]4.3 t _0388 881.2 1_osla 50 L9 1.1429 502.9 1.3934
883.6 o_sa41 607.7 1 oasa B53.2 L 9793 BT 8.7 1.1311 875.6 1.1793la 1895.8 0 9560 859.4 1 .023] 1029.9 1.6667 840 0 ].1205 Bi9.2 L Ifi TG
1208.9 9.9521 1029.7 1 .0178 ]397.9 1.8585 1020.0 1.1109 18123 L 1552
1380.6 9.9464 1199.A 1 _0115 ]370.7 1.9511 1193.8 1_]019 1188.6 1.1446
1549.G 9.9412 1379.0 1 .0054 1515.8 1.8464 1967.2 1.0999 1364.5 1.1340
1738.5 0.9358 155].6 9.9997 ITS5 1 1.0392 1711 e LoTTT 1443.4 1.1303
189 B.5 os314 1TZO.6 0.9995 1008 0 1.0334 ] BBS 3 10708 15325 1.1256
2079.8 0.9273 !891.9 9.9885 2085.8 1.92 TA 2955.0 ].8897 1695.7 1.1179
2065.0 0.9848 1883.3 1.t 991
2858 3 1.1815
25
198.9 0.9968
278.0 0.9BOB
418.8 0.9850
551.2 0.9T9B
693.2 0.9745
&71.8 0.9694
966.3 0.9647
1102.8 0.9601
1241.9 0.9655
1303.1 0.9511
1522.2 0.9487
1652.7 0.942R
1798.8 0.9986
1937.1 0.9947
207 i.] 0.9309
1.8 1.0883
134.5 1.0611
28}.6 1.05?6
4zo.1 ].o4as
559.8 1.0}30
T 14.7 1.0988
830.2 1.0921
970.6 1.0289
1108.2 1.0218
1248.fi 1.01 TO
138},1 1. p124
!"x20.4 1.0081
1660.0 1.0098
1 T98.a 0.9994
194z.a osssz
2073.6 0.9913
L0
735.2
275.6
4zD.1
537.0
898.0
fl50.2
875 n
uDe.a
1243.0
]364.1
]518.3
]658.0
]803.8
]834.6
aDJZs
1.t 340
1.1241
Lt150
1.1069
1.0905
3.0913
1.0837
1.0776
3.0719
3.0861
1.0603
1.0552
1.0500
1.0448
3.0403
1.0355
1.0
135.2
276.8
41].7
55}.9
893.8
831.2
967.8
1108.6
1245.8
1364.1
1520.4
165 T.3
3797.0
1938.0
2o75A
1.2037
].1891
1.1762
1.16{8
1.15{]
1.1452
1.1364
].1zez
].1zos
1.1132
1.1064
].1990
1.0940
1.0880
1.0822
l.D7ss
1.0 1.2]08
131.9 1.2509
279.0 1.2335
115.3 1.2189
553.6 1.2055
897.4 1.1930
837.1 1.1621
983.0 1.3727
]103.3 1.3893
12?0.3 1.3547
1361.4 1.19fi2
1532.8 1.3380
1658.7 1.13 t2
1'.99.7 1.1242
1949.8 3.1171
2069.4 1.1119
50
1.0
138.G
276.3
412.5
564.3
702.9
835.0
97n„7
1109.7
1247.2
]379.3
1533.5
1859A
1799.0
]93{,8
30759
1.0131
l.aosD
1.0003
D.994B
Dsesz
0.9830
0.9790
0.9742
D.9890
0.9653
0.9612
0.9584
0.8527
0.9488
0.9448
0.9408
1.0 1.0862
137.9 1.0786
200.4 1.0713
415.3 1.0641
366.7 1.0577
696.7 1.0521
892.3 1.0484
970.8 1.0408
1108.1 LOS58
12}2.3 1.0306
1384.1 1.0288
1518.3 1.0210
1856.6 1.0184
IT99.0 LOIIJ
1938.0 1.OOJ1
2078.4 1.002 )
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
1.1196
3.1116
L 1041
1.0966
1.0900
LOSa6
1.0773
1.0]12
10859
1.0629
1.0558
1.0502
l.D
139.fi
273.5
413.9
sso.e
691.2
634.3
9 ]4.T
1114.4
1248.fi
1380.0
1524.3
1856.6
1 eD1.e
19}3.6 2215.4
1.2367
1.2198
1.2063
1.1921
1.1005
L 3697
1.3691
1.1502
1.3418
1.13x0
1.1268
].1195
].1131
1.1x64
1.]002 ].0090
1.0 1.3311
131.0 1.2859
276.3 12646
413.9 12416
5}89 12324
693.9 1.2181
892.3 1.2068
967.1 3.39{9
1106.1 1.1845
1245.{ 1.1797
1364.1 1.16"a7
1519.7 3.1575
1636.6 7.7477
17932 1.1423
1938.7 1.1347
2075.0 1.1262
TS
1.0
174.4
342.1
513.3
688.1
BSfi.3
1029.0
1202.6
13 i 0.3
1649.fi
1132.3
1895.0
2067.4
].0250
7.0180
1.0100
1.0039
0.9964
0.9899
0.9835
0.9774
0.9715
osssa
Dssm
0.9556
0.9502
34.5 1.1051
169.8 1.0973
337.1 1.0873
610.2 1.0780
i 09.5 10679
854.9 1.0611
1027.0 3.0535
1196.2 1.0464
1370.7 1.0395 1644.4 1.0329
17 V.1 1.0267
1890.2 1.0208
2081.9 1.0149
95.1
167,2
393.7
soS.D
667.0
769.9
661.1
]021.9
1194.8
1324.6
1692.7
17]4.7
]B95A
2080.3
1.1842
1.!728
L 1584
1.1463
1.1340
1.1280
1.1226
11128
!.1036 1.09fi9
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
].z6ss
1.246]
1.2257
1.2088
].1909
].]787
1.1636
1.1522
1.1420
1.1311
].1219
1.1131
1.3048
34.5 3.3487
184.! 1.3230
930.9 1.2956
505.4 1.2726
678.7 1.2532
Bi8.0 1.2960.
1004.9 3.2223
1191.) 1.2078
1365.1 1.1952
1538.5 1.1836
1706,6 1.1731
1647.4 1.1649
1920.5 1.1607
1990.5 1.1368
2058.3 1.1330
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Specific Volume and Viscosity of Methanol-Water Mixtures 63
Results and 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 2
~e g BtPe ~ ~
1.3
~m l.2
E V ~ ~.1 O
c 1.0 H
Xn~x-1.00
O.ii
0,50 w
0.25
0.00
t.3
'm 1.2
6 ~ W
0 V
V N LQ
Fig. 3
X
~sreo_x- "~o ,
~"_moo.
_ 0.25
0.00
0.9r - ~ 0.9~ ~ 0 1000 ?000 0 1000 2000
Pressure bar Pressure/bar
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°C and 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)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
64 H. Kuhota S. Tsuda, M, hiurata. T. Yamamoto, Y. Tanaka and T. Makita
Table ? CoeBuients of the Tai[ £quatioo
Temp. Comp. A C Ave I>ev Nxx Dev. Temp. COmD. A C Ave Dev. 1{R Lilev.
•C S bu x a •C X bsr
D.D9 2366 0.2691 D.D2 D.Da D.oD 3380 0.34 pfi 0.02 D.D60.15 s liz Dsvl 0.01 O.Oi 0.10 zszD 0.3055 0.00 D.m
0.25 2 i3B 0.2896 0.01' 0.03 0.15 zsal 0.303] 0.01 0.01
10 0.90 24]1 D.zssi o.m o.oz 50 0.25 2458 0.2888 0.01 0.09
0.35 294] D.zi4] n.D6 o DI 0.35 l flil 0.2583 0.0] D.oz
oss 1563 0.22 A5 n.Dz 0.05 D.6D 13es 0.2308 0.02 O. DSO. ]i us4 0.2392 0.0R 0.04 OA5 963 0.23 p] 0.02 n.a
1.00 888 0.2295 O.Oz 0.03 L00 833 D.zxt4 0.02 0.05
0 zs9A D2D69 0.01 a.Dz 6 3268 0.346] O.DI 0.03
O.ID 3214 D5233 0.00 0.01 D.15 2911 0.2885 O.OI 0.09
0.15 9168 0.3196 0.01 0.03 D.as 19as 0.2699 0.01 0.04
28 0.25 2686 0.2904 D.O1 0.06 ]5 0.30 159fi 0.2450 0.01 0.03
0.35 a lDs D.zsoe 0.01 D.Dz 0.35 1ss3 0.2840 0.01 0.03
0.56 I65B D24]n 0.02 D.Ds 050 1211 02419 0.01 0.02
D.]5 lnse Dszsa D.Dz D.D] O.iS ]49 02338 0.01 0.02
l.Ds 815 D2283 0.02 D.Da 1.D6 592 0.2309 0.03 n.Ds
1.5
i. a
0 1.0 r
a u a c 0.5
U
L0 bar
500
iooo
zaoo
1.5
,~
a 0 1.0
s
`o.
e O.a
U
1.0 bay i
of
i~ i i~
i
P ~ 500
# ' 1000
.O,A~O O . ~ Op O
~ o ,,~A~~ -o~
150
0 0.25 Oa0 O.i> 1.00 0 0.25 0,50 0.75 1,00 Dfole fraction of :Ifetbanol Mole fraction of Methanol
Fig. 5 Composition dependence of the isother- Fig. 6 Composition dependence of Che isother- mal compressibility at IO'C mal compressibility at 75'C
where vo is the specific volume at a pressure Po, and B and C are constants. The obtained Tait
equations could reproduce experimental data with an average deviation of 0.03%. The coefficients
for the Tait equation are listed in Table 2.
The isothermal compressibilities ;
tqr-- v ~ a /7• ~3) calcttlaled using the Tait equation, at 10'C and 75'C, are plotted against the mole fraction of metha-
nol in Figs. i and 6, respectively. It is found that a definite minimum exists near X=0.15 at 10°C
and IS°C, but these minima fade out gradually as the temperature increases. At 75°C these minima
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Specific Volume and Viscosity of Metbanol-Water Mixtures 65
disappear completely. 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 equa-
tion
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 con-
ditions, 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 Jfole fraction of Methanol 0 0.25 0.50 0.75 1.00 0 0.25 0.50 O.7i 1.00
~u
e E
E u E a 0
V V M W
-os
-i .o
-Li
,~ ~~
0
~ ,~ /°
° s~ c ~o
a
o loo ~~o
1.0 bat
d 0 e E v 9 y 0
v V X
-os
-i .a
-u
,~ 0
02000
\ ~ ° ~o
~̀̀ ~ °~O 500 ° r~ b \„ ~d
100
i ~ ~
._,°_ .
1.0 bar
I
i ~/
i
Fig. 7 Composition dependence of the excess vo- Fig. 8 Composition dependence of [he excess lame of Methanol-Water mixtures at volume of Methaml-Water mixtures at
25'C Q ;This work 7i C
~ : t0)
Viseosfty
The experimental results are tabulated in Table 3. The data obtained at atmospheric pressure
are plotted as a function of composition in Fig. 9, where other experimental data11-ts) are also
plotted for comparison. Each viscosity isotherm bas a maximum at a composition near X=0.30
0.35. Agreement with the available data is satisfactory at 10°C and 23`C. However the discrepancy
among [hem is somewhat notable at 50`C, where [he largest deviation between the data of Sabeis et
al.tx> and those of Traubela7 fs about 11% near the maximum. The present data agree quite well
10) M. L. \tcGlashan and A. G. N'illiamson, J. Chern. Eng. Data, 2I, 196 (1976) ll) S. Z. dlikhail and W. R. Kimel, J. Chern. Eag. Dafa, 6, 533 (1961)
12) T. N. Yergavi<h, G. LV. Swift and F. Kurata, J. Che+u. Eng. DNa, 16, 222 (1971) 13) S. N. Sabnis, W. V. Bhagwat and A. B. Ranugo, !, hrdian Chern, Soc., 25, 575 (1948)
14) J. Traube, Bar., 19, 871 (1886)
The Review of Physical Chemistry of Japan Vol. 49 No 2 (1979)
6fi H. Kubota, S. Tsuda, M, Murata. T. Yamamota ,Y. Tanaka and T. Makita
Table 3 The Viscosity of Me[banol-Water Mixtures in 10'a Pass
Temp.
.C
Y
Lee.\"=O. UU X=0.15 X=0?6 X • 0.30 X=0.35 S= 0.60 C•OAS .\' • LD
10
1.0
99.1
197.2
295.2
]93.3
491.4
589.4
68T.5
1.311 4].301
I.292
1.z84
1 ~ia
1.2701.268
].284
2.360
2.36i
2.37A
2.381
2.399
2.40E2.428
2.449
2.551
2.588
2.63i
2.667
2.:08
2.733
2.ii6
2592
2,600
2,Sii
2,fi 16
2,656
R,i3T
2,:93
2, 848
2.902
2,419
2.491
2.563
2.6Z4
3.689
2.i67
2.895
2.908
1.9 Tf
2.044
2.095
z.lsa
z.azs
z.a7s
2.3462.3B4
1.2721 .]2i1 .9 T41.4261.472lsze1.6811.823
0.8953
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0.861I
o.ee39
0.9164
0.9508
25
L099.1
I9T.2295.299],3491.4589.4687s
0.8911+
0.8895
0.8882
0.8872
0.8866
0.8864
0.8066
O.BBT2
1 A61
L 464I a69
L468
Lii9
1.495
1.503
1.508
1.581
1.611
].626
1.6i6
l .fi 6i
1.686
1.:061. i3!
LSii
L61T
1.631
1.637
1.6i4
L698
I.i23L i4i
1, 53fi
1.620
1, 634
L6i5
1.710
1. T63
1.788
L 918
1.325
1.362
1.909
1.93T
1.902
1.529
1 .ST2
1.61i
0.9031
0.9TT0
1.012
1.048
1.087
1.124
1.189
1.19T
0.5959
0.59ST
O.Ba20
0.600
O.BT]O
0. T008
0. T3]0
0. T558
5D
].0
99.1
197.Z
295.2
399.3
49I A
58TA
68i.5
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0.5486
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O.SSB3
0.5805
DRBI]
o.aao2
0.8103
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0.~13
o. a?Bi
0.8307
D.8340
0.93i5
0.849T
e.as2t
0.8882
0.8i54
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0.8923
D.BS55
D.as3e
0.8920
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0.9149
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0.8962
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o.9ose
0.9192
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0.6649
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D.4zao
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1.089.1
19i295:393!3491.4589.48aT.5
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0.9808
0.9832
0.3857
0.3882
0.3908
0.9999
D.9seD
D.495N
O.i02;i
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0.5 Bifi
0.69770.6089
0.55550,56iT
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0.550T0,5G400, 57620.5901osaz40,6141D_62 TO
0.52200.53T7O, SSOG0, 5631osiel0.59290.6053
O.iOTT
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0.50T5
Dszsfi
0.3130
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0.3581
D.3 TZe
0.30T9
0.4038
~ [APS (39]J]
2.5
z.o
1.5
n
O T .o
7
~.~
O.i
a
a
o ma9
IO'C
~8m~
2i'C
o0c 8. ;o ~
50'CB°
a0 4
Fig, 9 Composition dependence of the aol-Hater mixtures at LO bar
Q :This work ) : 14) ~ : 11) p : l3) ~r : 12) ~ : t 6) •:13) ®:17)
visrnsity of
.~ o~
18) l9)
\tetha-
0 0.2
bfole
0,4
iractioo
O.fi 0,8
of Methanol
1.0
IS) 16)
A. E,
A. E.
Dunstnn, Z. Phys. C4am., 49,
Dunstan and F. B. T. Thole
590 (1904) !. Chern, $Oq, 95, 1556 (1909)
The Review of Physical Chemistry of Japan Vol. 49 No. 2 (1979)
Specific Volume and Viscosity of Methanol-Water Mixtures 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 modified Ostwald viscometer.
The pressure dependences of the viscosity of this mixture at 10-C and 75°C are 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. Although the overlap of experimental conditions is
limited, the consistence between 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, whereas the pres-
sure coefficient of viscosity, (8r,18P)T for pure water is slightly negative at 10`C and 25°C
within the present pressure range.
2) (8r~/r7P)T increases with the mole fraction of methanol at each temperature.
3) (8r~/8P)T decreases with rising temperature for the mixture of a constant composition.
0
.o
3.0
2.5
2.0
1.3
1.0
0.5
Xm~ox= 0.21
0.300.31 ~-~ 0.15 030 .
O.7i
HzO
\Se~OH,,~
g~' 0.15 0;50
HzO 1fe0H 0.75
1.0
0.8
A ~ os
0 T
~ D.a
0.2
.20'C~ o~
e
.40'C
10°C
~ ; . 60•C
. :~80C
, • 120'C
Fig. !0
l7) 18) t9) 20) 21) 22)
23°C
e~30°C
So•c
73'C
0 200 400 600 0 200 400 600 Pressure bar Pressure/bar
Pressure dependence of the viscosity of Fig, l1 Pressure dependence of the viscosity of Methanol-Water mixtures at 10'C and Tiethaaol 75'C ~ : 10°C ~ ;This work p : 21)
~ : 7SC ~ : 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)
68
Table 4
Ii. Kubota, 5. Tsuda,
Coefficients of Equation ($) fox 30_a Pa•s
M. Murata, T. Yamamoto. Y. Tamka and T. Makita
the Viscosity in3.0
Temp.
°C
xn
50
z 131 Bp x 104 B3 x 108 Ave.tlee Mex.ilev.
a p
O.li 2.35982
0.2v 2.5;964
0.30 2.50521
0.3i 2.41965
0.50 1.9:211
0.45 L2i304
1.00 O. G9599
0.15 148090
0.25 1.58:33
0.30 ].54~2R
0.35 1.54916
0.50 1.9264A
0.15 0.91291
1.00 0.55268
015 0.48984
0.2i 0,83912
0.30 0.03905
0.35 O.B?950
O.i9 9.433fi3
O. ii 0.5]920
1.00 9,39110
0.16 0.}621}
0.25 0.53041
0.30 0.5.363
0.:15 0.63 i21
OSO 0.508}e
0.4."+ 0.38381
1.00 0.29863
o.3sos
a.3as3
ss2oe
s.977a
s,5a;z
i.19t8
3.i?Ad
0.1983 2.0571 5.::93 9.7669 3.5679 5.1208 9..' 517
L32A1
0.953.;
].A339
5389
2,5314 1.8t1i 1.i61A
1.238A
1.?290
1.20]1
1.5680
].!282
S.Si~O
].97x7
]1.23? -15.8{6
^.801
1.3 i r - :^^-50
- O. SGS
-i^^-S5i
..3X8
osa~ - 3s9z
-13sos
ss4n
-t4,53o
- I96B
-10.{83
0.488
i.0i1 -14.8:3
- 5.408
0.402
1.4U i
4.51E
- ]?7i
- 0.150
- 0.9 i3
- 0."_{R
4.t E4
0930
0.1
0.2
0.3
0.1
0.9
0.?
Oa
o.z
o.z
0.3
O.a
0.1
0.6
G. i
0.3
G.2
0.~
0.~
0.5
0.6
os
0.3
0.2
0.03
o.o;
o.v
O.:t 0.1
G.z
0.3
OR
8.2
8.6
0.3
n. a
o.a
0.4
O.B
1.G
0.3
].6
LG
O.a
O.a
LG
0.8
].3
n.7
13
0.6
os
o.l
o.l
o.^_
0.8 0.3
2.5
n a z.o
0 T 0 1.5
i.a
os
io•c
zs°c
50°C
7SC
0
Fig. 11
* For 7SC isotherms. Eq. (S) is valid from 99 to G88 bar.
0,2 0.4 0.6 0.8 1.0 Mole fraction of Methanol
Composition dependence of the vis-cosity 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 experi-
mental 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 dimi-
nishes gradually with rising temperature.
Z) Each isobar has a maximum near the composition of X=0.300.35. The maximum shifts
slightly to higher methanol fraction with rising temperature 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 posi-
tive 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 Mixtures 69
bergs" of water molecules themselves and the association of alcohols. It is quite interesting that the
maximum of viscosity and the minimum of excess volume occuc at different compositions of mix-
tures.
The authors wish to thank 1Ir. Yasuhare Kimura, Kobe Agricultural and Forestry Products
Inspection Institute, for his careful experimental efforts in this worl•.
Department of Chemical Engineering
Faculty of Engineering
Xobe University
Katie 6i7, Japan