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Title Specific volume and viscosity of ethanol-water mixtures underhigh pressure
Author(s) Tanaka, Yoshiyuki; Yamamoto, Takeshi; Satomi, Yoshimasa;Kubota, Hironobu; Makita, Tadashi
Citation The Review of Physical Chemistry of Japan (1977), 47(1): 12-24
Issue Date 1977-07-20
URL http://hdl.handle.net/2433/47042
Right
Type Departmental Bulletin Paper
Textversion publisher
Kyoto University
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
12 TLC I2E\9EN' OF PHYSICAL CHEII1$TRT OF JAPAN, V01.. 47, ~O. I, 1977
SPECIFIC VOLUME AND VISCOSITY OF ETHANOL-WATER
MIXTURES UNDER HIGH PRESSURE
13v YOSHIVL'RI T,a\ARa, TA6 ESHI ~:fyLt at0T0. S USHIa[.tSA $ATOa[I,
HlaoNOau 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 pres-sure 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 tempera-tures.
Introduction
The physico-chemical properties of aqueous solutions of alcohols are of interest in many fields
of science. The solutions often show some anomalies in various physical properties such as partial
molar volume, compressibility, velocity of sound, sound absorption, viscosity and so on. which have
been yet inadequately understood. Such properties of mixtures in a wide region of temperature and
pressure are important both in chemical engineering designs and in theoretical investigations of
excess thermodynamic properties. However there have been only a few measurements on these
properties, especially under high pressure.
The present investigation was undertaken to provide extensive and accurate P-I'-T and viscosi-
ty data under high pressure for ethanol-water mi-elutes. Numerical data have been determined at 25'
and 30'C under pressures up to 3200 bar for specific volume and 800 bar for viscosity, employing a
modified Adams piezometer and afalling-cylinder viscometer. Empirical correlation formulas have
also been presented for both properties from the experimental results.
(Received /t/ay ?i, 1977)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific Volume and Viscosity of Ethanol-R'aler Mixtures under u;gh 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 sche-
matic diagram is given in Fig. 1 and the typical dimensions are summarized in Table 1. The volumes
of the piezometer and the capillary stem were determined by weighing them filled with distilled water
or mercury. The piezometer was set in a high pressure vessel equipped with a pair of optical win-
dows which enable us to observe and control precisely the mercury le\•el in the capillary stem. The
high pressure vessel u•as immersed i¢ a thermostat bath controlled within --X0.01°C. The pressure
was measured by Heise Bourdon gauges calibrated against a pressure balance. The uncertainty in
pressure measuremenu is estimated to be less than QI o.
The mercury trapped in the piezometer was gashed with ethanol and weighed alter drying.
A
Fib. 1
G
~r~~
~,
i~
E~~
.I°I
z
Q L, 21 D.
z
a
a
i
s
fO~° 9 Schematic diagram of Fig. 1 Schematic diagram of falling-cylinder viscometer modified Adams piezo• 1. Pyrex glass tuhe 6. Thermister meter 2. Falling rylinder 7. Pivot
3. Laser beam 8. O-ring a. Optical window 9. Sample inlet
5. High pressure vessel
H. Adams, 1.:Luer. C/rem. Sar., 53, 3769 (1931) T1. :~ewitt and K. E. ~i'eale, !. Chem. Soc., 3092 (1951)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
14 Y. Tanakn, T. 1'omamoto, 1'. Satomi, H, Kuhota and T.
Table 1 Dimensions of Instruments used
14akita
Piezometer Length
Outer diameter Inner diameter Total volume Volume of capill
V iscome[er Glass tube
Length Outer diameter
Inner diameter Plummet
Length Diameter 11'eight Volume Density
sn•
a[ 25'C
16.7 cm
1.G cm
].4 cm
t 8.2215 cms
0.03616 cmr
at 29'C
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 specific volume of the sample liquid aas calculated by the following equation
= 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 at Ibar in cm',
Pc :inner volume of the capillary at Ibar in cma.
lime :weight of mercury trapped in g,
pa :density of [he liquid at 16ar in g•cm-",
pue :density of mercury at P bar in g•cm''.
ke :compression of Pyres g]ass at P bar.
The values of kx and pFte mere cfted from the results of ~damsll and Grindley et a!_a) respectively.
The densities of mixtures under the atmospheric pressure were determined experimentally by a
pycnome[er and partly cited from the handhookS%
Viscosity measurements
The viscosity has been measured by a talking-cylinder viscometer. The viscosity n•as deter
mined principally based on the Stokes ]aw on a rigid sphere falling in an infinite homogeneous
fluid. The details of the theoretical basis are described by Swift et af.5 %>
The schematic diagram of the viscometer employed is given in Fig. 2. The apparatus consists
of a precisely bored Pyrex glass tube equipped coasially in a high pressure 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)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific Volume and 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 gas
laser beam passed through a pair of optical windows and a phototransister. 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;)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
l6 T. Tanaka, T. Yamamoto,
be substantially accurate within 0.01 %.
Y. Satomi, H. Kubota and T. Makfta
Uncertainty of experimental results
The numerical data of the specific volume and the viscosity obtained contain a definite uncer-
tainty 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 .0.1 %
Pressure =0.01 % Composition of mixture ±0.02%
Falling time x-0.5%
Density x-0.01
Instrument constant, li -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 and Discussions
P-V-T data
Table 2 lists the measured P-C-T relations for ethanol-water mixtures at 25' and 50'C under
pressures up to 3200 bar. X is the mole fraction of ethanol in the mixtures. The results are also
plotted in Figs. 3 and 4 together with the previously published data for pure water and
mixtures for comparison. The specific volume decreases monotonously with increasing
pressure throughout [he experimental conditions at each compwitiop of mixtures. .4t 25'C, the
present results agree quite well with the values given 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) G. S. Kell and E. 1Vhalley, Phit. Trans. Roy. Soc. London, A258, 565 (1965) 10) A. L. bfoesveld, Z. Pbys. Cke,n., t0.5, 450 (1923)
If) M. Yusa, G. P. Wathur and R. A. Stager, J. Cbem. Eng..Dala, 22, 32 (1971) a This report was published recently after the completion of experimental part of this study.
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific ~bfume and Viscosit}
Table 2 The Specific
• of Ethano]-1Vater Mixtures under
Volume oT Ethanol-Water Mixtures
High Pressure li
P(bar)
2i°C i0°C
n(cm3/g) P(bar) v(cm3/B)
2~ C
P(bar) v(cm3/g)
50'C
P(har) nr(cm3/g)
25'C
P(har) v(cm3/gJ
50`C
P(bar) (cm3/g)
l.o 91. 7
172, ] 250. 1
331.9 102.0 675.3 763. 6
899. 9 10322 1313.2 1917. 9 1762. T 2107.4 2452.? 2796.9 3136. 6
1.0 63.9
1 i5. T 223. 5
288, 1 345.9 914. 0 480. B
555.1 625.2 690.5 695. 7 723.1 831. T 903- B
1043.6 I OT3,2 1177.3 1318.0 2073. 0 2245, 3 2421. 2 2590. 1 2796.9 2934.8
X-0.00
1.00293 L 0 0.99881 14],e 0.99515 226.6 0.99193 310.5 0.98412 341.2 0.98177 41].1 0. 9T543 4]8.2 0.97256 488.9 0.96770 515.8 0.96281 56;.4 0.95343 623-1 0.95008 631.8 0.93976 668.0 0.9315] 692.2 0.92176 ]23.] 0.91390 832,} 0.90665 931.3
1039. ] 1110.9
1242.1 123},] 1345.5 1348.3 1555.8 1 T2}.8 1 ifi2.7 1 soo. s
2IO i.4 2245.3
3452.2 2586.fi 2963.9 3138.2
X=0.10
1.03812 1.0 L. 03513 207.3 1.03185 286.} 1.02866 341.3 1.02609 122.3 1.02393 483.0 1.0218] 554.4 L OIB82 622. 8 1.01619 690.5 1.01347 940.1 1.01092 1073.2 1.01110 1084.1 L OI014 1210.6 L 00693 1 ]62. ] 1.00483 IB97.1 0.99990 2107.4 D. 99tl tl3 2}}B, ] 0.99,529 2798.5 0.99166 3138.2 0.98929 9.9661} 0.96069 0.85702 0.95178 0.94871
1. olz l9 1.00621 1.00286 0.99988 0. B98T i 0. 99623 0. 99500 0. 99335 0. 99215 0. 98943 0.98791 0,98T50 0.98579 0.9 B4fi9 0.98404 0.98049 D. s7sss D. 97328 0.97010 0.96804 0.96604 D-96369 0. 9G369 o. 9sits 0.95257
0. 95Da3 0: 99720 0: 991 B4 0. 93]d1 0. 93321 0.93950 D. 92211 0.91853
1.05713 1. 04839 1.0450] ].04200 1,03915 1.03663 1.03366 1.03065 ].02802 1.02052 ]. O16T5 ].01598 1.01262 0. 993flfl 0.99032 0.98619 0.9]125 0.96835 0.95!51
l.o 6;. o
m 1.1 xs1.2 339.9 ;21.3 485,J 128.9 762. 8 90>. 5 042. 4
1173.2 1175. 9 1316.9 1917.9 1162.7 1900.6 2073. 0 2295.3 2466. B 2796.9 293;.6 3141.7
L0 90. 3
196.4 261.9 360.6 ; B6. 8
55;. 1 622.8
69J.i 767.0 901.7
1039.0 1073.2 1177.3 1211.1 1316.9 1762. i 210 T. ; 2436.2 2796.9 3145.1 3J 96.4
t, o
75.7
146.;
205.9
286. 6
380.6
486.1
624. 5
700.5
902.4
1037.2
1073.2
1.
~. 1.
1.
1.
1.
1.
1.
I.
1.
].
1.
1.
1.
1.
i.
0.
0.
0.
0.
a.
0.
t
t
1
7
I
1
1
1
3
1
1
1
1
1
1
1
1
1
1
1
1.
1.
1.
1.
1.
1.
1.
1.
1. 1.
1.
.Y=0.20
07120 1,0 1.09616 06686 277.7 1.08192 06128 319.0 1.0]900 05717 413.0 1. Oi971 05546 994.7 LDL 20 05153 661.3 1. Ofi 844 04879 636,9 1.06491 03935 696.4 1.06274 03766 831.0 1.0569] 03250 9]1.0 L D5043 02712 1073.2 1,04701 oz2zs 19fi6.1 1. wssT 02306 1207.6 1.04209 01797 1216.9 1.04214 01504 1329.4 1 03784 00495 1380.0 L D3492 00103 1552.4 1.02964 9ssso 11sz.1 1. oz4v salsa t9s7.1 ].m fins 98669 2241.9 1.00962 9 T16fi 2586.6 D. 99831 97440 313 fl:2 0.98536 96914
X=0.40
13699 1, 0 1. ]6660 12981 199.5 1.16560 12631 281.9 1.19651 11744 354.3 1.19113 11278 416.3 1.]3708 10546 499.0 1.]3219 10114 556.] 1.12]55 09737 624.5 1.12264 09333 f.9 tl.5 1.11836 09108 ]99.5 1.11195 O Bi18 923.9 1.10532 010]8 IOOCS L10148 07669 1211.9 1.09286 O 7289 1717.6 t-088]3 Oi124 1380.0 1.08566 DG731 1562.7 1.01949 OsOfiO IB9T.1 1.06623 03945 2G69.i L O6i57 02893 2686.6 1,09286 01900 2759:0 1.03590 00994 2531.1 1.03225 00209 3103.8 1.02641
.C=0.60
1893: I. D 1.22263 18262 193.0 1. 210fi2 17593 212.8 ].20436 I TI07 278.4 1.19923 16453 750.6 1.19298 15782 515.1 1,18818 14988 988.4 1.18280 14012 54x.1 1.11634 13668 628.3 1.17079 12667 x29.3 2.15128 13(127 868.2 1.14709 11851 1110.4 1.13813
]181.9
1314.7
1417.9
f 762.7
1931. 6
2307.4
2590.1
2796. 9
2939:8
3191.7
]. a 75. 0 t 53,0
213.9 274.6 41 s.e
9 ]9.i sl e.z
fi00.3 762.5 906.9
1037.2 1073.2 1176.0 1313, 8 ]417.9 1621.3 18921 2241.9 2452.2 2655.6 2796, 9 2934.0 3191.7 3486.4
1.D
7D. 1
139. 5
208.7
352.6
a 85,1
821. i
761.1
632.0
899.3
t 038.6
1176.2
1313.8
1317.9
1621.3
1762.]
1762.]
193 L 6
2107.4
2102 4
2276.9
2314, 3
2655.6
1247.2
3320.7
1380. 0
1552.4
189].1
2069.5
22{1.9
2414,3
2566..6
2759. 0
2931.4
3]03.9
1.11178
1.10564
1.10045
1.08713
1. D7992
1.07573
].05954
1.05212
1.04668
1.04173
r-o.6a
1.23352 1.0 1.22518 210.7 1.21645 279.5 1.21105 348.5 1.zoa7T a]s.e 1.1 szD5 aei.s 1.166]5 557.2 ].18407 626.9 1.17811 699.5 1. 16775 793.6 1.15864 921.8 1.15069 968.2 1.14846 1062.5 1.14274 110],6 1.13548 1236.4 !. !3025 1337.3 1.12114 IT24.B 1. ID BD4 189 i.i 1.09553 2241.3 L. 08841 2414.3 L 08158 2566.6 L 07764 2759.0 1.07325 2931.4 1.06874 3]03.8 1.05685
X=1.00
1. 0 141. 9 211.1
263. 6 397. B 421.3
983.3 551. 0
625.2 694.3 762, 5
]039.0 !175.9 1317.6 1552.4 1897.1 2069.5 2247.9 2414.3 2588.8 2759.0 2931.9 3103.6
1.27353
1.26193
1.25663
1.24833
1.23711
Lzls3e 1.20631
1.19750
1.19235
1.18818
1.17es7
1.16965
1.16192
1.15518
L 13523
L 13943
1.13961
L 13212
1.1273}
1.12}38
L 11Ta9
L l 1268
1.10236
1.13121
1.12]41
1. lzzze
1.11543
1. wssl
1.09238
1. OB6i8
1,08144
1.0"440
1. 0702
1;06175
1.05931
t. 27115
1.24579
1. 23797
1.23114
]. zzv7
l.vm
1.21196
1.20{65
1. 19987
1.192]4
L 16502
1.17942
L IT379
1.172]2
1.16505
1.15908
L 13888
1.13709
].11583
1.10959
1.102]5
1.09635
1.09006
1.08704
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
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
18 1'. Tanaka, T. I'amamato, S, 5atomi, H. Iiubota and T. btak ita
1.30
0i.2
1.10
1.00
-~
E v E
0
a
0.90
00
° o o, d'Q'
50 0° ~oo
O °b c e 0 P° °~a oQ
0 °o ° Q a
oa °o
° o °p~b
b °°E
° oOo °° •o~ ° o
•opO [Va~
er ~ .
~. o~
~,,
,~ .
P 4~
0
0
0
4
a
40
zs•c
x EIOll l
.0 o °
°• °
° 0.8 o °°
° °
4 • O.fi 0
0 o° 0.4 ° o
~ 0.2 ' ° o ° 0.1 ° ° .o~
o • o
0 1000 2000 3000
Pressure/har
3 Pressure dependence of the specific volume of ethanol-water mixtures
at 2i C
C: This work, *: 3), ~: 9), x:10), /:I1)
Table 3 Coefficients of the 5~
r'=A~ t.
~m
E u E 0
~e .V a n
1.30
t.1a
1.I0
1.00
0.90
°o °°^° ~~6
a~ o~ °°
~ e °O~
o° ° o , °^
° °oPo° °° ° o°
° o° ° °~
°Do °OpOpo°a
°° o ~° °
Wdtef °<,e~ ~ ° °
°p o
a°
Pig. 3
50'C
x £tnx 1
.0
°°° °
° ° ° °
O° O.g° ° 06° °
0.4° ° o 0
° ° 0 .2 = 0,1 °
0°°+Oa •a°
Fig. 4
0 IOOD 1000 3000
Pressure/bar
Pressure dependence of the specific .•olume of ethauof-water mixtures
at i0'C C1; This work. *: 3), ~: 9)
Coefficients of the Specific Volume Isotherms (Pin
i'=At tA2Pt.faP~+A~P3 t asP+
harj
Temp. (°C)
~~ :12k 10~ :12 % 10a :Il X (012 ~'IF X IQI6Ave. Dev,
~~~Afas. llev,
~~o~
25
so
0
o.~o
o.zo
o.ao
0.60
0.80
1.00
0 0.10
0.20
0.40 0.60
0.60 L00
1002799
1.03802fi
1.071118
1.136153
1.13933(
1.232849
1.273663
1.012369
1.057173
1096419
1.167762
1.213160
1.271486
1.311651
-0 .443342 -0 .436395 -0 .497623
-0 .144170
-0.943990
-1.103108
-1 .303024
-0 .4252248
-0 .460342
-0 .558459
0.553410
-0.903382
-1.343178
-1571652
0.62fi552
0.89155
0.856201
2.320940
3.22?030
3.181940
4.16.938
0.54"835
0.836348
1.121898
?.400286
1.101615
5.624636
6.942738
- 0.87462 - 2.45fi6i - 0.95734
- 6.04088
- 7.910364
- 9.09383
- O.SSi i2
- 1.20089
- 1.10525
- 3.64916
2,52140 -16 .81337
-20 .77829
0.8722b
3.2101
6.701070
7.73$71
9.1 / 881
11.0980
1.26276
1.91894
-7.12415
20.78308
25.21906
0.023
0.022
0.024
0.025
0.031
0.043
0.028
0.031
O.OiI
0.038
0.092
0.052
0.039
0.069
0.084
0.079
0.071
0.07A
0.114
0.124
O.OHi
O.Oi 1
0.143
0.099
0.279
0.203
O.1I0
0.224
to 0.4% at high ethanol mole fractions and high pressures. As for 60`C, the present results for pure
water are in good agreement leith the values of Kell et aJS> and Grindley et al.31 However [here
exists no data on mixtures available in literature for direct comparison with the present worl.
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific Volume and Viscosity of Elhanol•Nater Mixtures under
Table 4 Coefficients of the Tait Equation
High Pressure t9
Temp. (•C)
R (bar) C(-JAve. Dec.
(4i)\fax. Dec.
(,.°o)
25
i0
0.00
0.10
0.20
0.40
0.60
0.80
1.00
0.00
0.10
0.20
0.40
0.60
0.80
1.00
2751
3121
2283
1552
I l3i
nR9
7iR
3311
1952
2401
1331
I ilO
92l
i90
0.2911
0.2989
0.2511
0.2308
0.2f79
0.21 i9
01061
0.3241
0.2881
0.2792
0.2504
0.2686
0.2282
0.2279
For each temperature and composition the specific volume data are n
pressure by the following quartic equation
and the Tait equation
where ~o is the specific volume at the atmospheric pressure and P the press
coefficients were determined 6y the least squares method as given in Tab
the average and the maximum deviations of the experimental data from th
polynomial equation gives a better fit to the data in general, the isothermal
liT=- v ~ 0 ~T is calculated by the Tait equation because the polynomial equation som
behaviors by the diiieren[iation. The functional dependences of the isoth
composition are shown in Figs. 5 and 6 at 25° and 50`C, respectively. It
minimum exists near x=O.l on the lower pressure isobars than 2000 tzar. ~1
of pure water. the isothermal compressibility has a minimum near 50'C /
2000 bar. This anomaly could be seen in the range o; low ethanol composi
increasing composition near x=0.1, where the isothermal compressibility is
tore under each pressure. Furthermore, it seems that another inflection mi
fraction of ethanol near x=0.7 on the low pressure isobars. (Concerning th.
detailed experimental results will be reported in the near future.) Yusa et al,
o.w
o.oa
o.os
O.Oa
0.07
0.03
0.06
O.Oa
0.03
O.Oa
0.09
0.07
0.05
0.03
daL3
0.07
o.lo
o.lo
0.18
0.19
O.OR
0.13
0.08
0.11
O.li
0.11
0.19
O.li
0.1 i
correlated as a function of
(3)
Clogl 8}t ~ (4)
is pressure and P the pressure in bar. The empirical
es method as given in Tables 3 and 4 together with
experimental data from the formulas. although the
~ in general, the isothermal compressibility
v ~ o ~T (~) polynomial equation sometimes gives unexpected 1 dependences of the isothermal compressibility nn
and i0`C, respectively. It is found [hat a detinite
re isobars than 2000 har. As well known in the case
as a minimum near 50'C on the isobars lower than
age o; low ethanol composition, and disappears a~i[h
othermal compressihility is independent of tempera-
s that another inflection might occur at higher mole
sre isobars. (Concerning this second inflection, more
the near future.) Yusa e! a/!» have found the similar
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
?a
,~ r
0 T a d n E a
n E s 0
1'. Tanaka, T. Famamoto. Y. Satomi, H, Kubota and
bac
T. Makita
I0.0
5.0
0
25°C
~I f•~
J
_ ,.
bOpbar ~ 1000 atbatb
or
201N1 bar
o3000 bar
0 0.7 o.a
fraction
0.6 0.8
of ethanol
t.a
Fig, i Composition dependence of [he
isothermal rompressibilit}• of
ethanol•n~atermistures a[ 2i`C
under high pressure
Mole
a
0
T
L
v 6
s 0
A e
v A O
10.0
5.0
0
50'C
o' .~~
°J~~o 11
bar
600 bar
1000 ab l
2000 bar
o-~c 0 3000 har
Fi¢. fi
" 0 0.2 0.4 0.6 0.8 1.0 Bole fraction of ethanol
phenomenon in his isothermal compression versus composition
attributed to complex interactions between the hydrogen-bonded
alcohol molecules.12~131
Composition dependence of the
isothermal compressibility of
ethanol-water mis[ures at 50°C
under high pressure
isobars.
n•ater and
These anomaly
the bifunctiohal
would be
nature of
Viscosity
The viscosity of ethanol-water mixtures has been measured at 25` and 50`C up to 800 bar.
raw data are tabulated in Table 5. Values of the tdscosity obtained at the atmospheric pressure
compared as a function of composition to other data available in literaturel+`~7 in Pig. 7. The
l2) F. Franks and D. J. G. Ives, Oxarl. Rev., 3Q I (19fi6) l3) G. Ne'methy and H. R. Scheraga, 7. Chern. Phys., 36, 3382 (1962); ihui., 36, 3401 (1962)
l4) J. Tranbe, sar., i9, sn (lass) 15) .a. E. Dunstan. Z. Plrys. Cheru., 49, 590 (1904)
16) E. C. Bingham. G. F. White. A. Thomas and J. L. Cadwell, Z. Plrys. Chem., 83, 641 (1913) l7) V4'. Herz and E. illartin, Z. anorg, allgem. Chem., 132, 41 (1924)
IS) 5. W. Sabnis, W. V. Bbagwat and R B. tanugo, J. Indian Chere. Soc., 25, SiS (1948) l9) 31. Kikuchi and E. Oikawa, Nippon ICagaha Zarshi, 88, 7259 (1961)
20) R. L. ICay, J. Solafim+ Chenr., 5, Si (1976) 21) E. L, Lederer, (Coll. Reih., 34, 270 (1932)
22) :1. 9basaade, V. A. Agaev and A. DI. Cierimov, Rxtt. J. Plryt. Gram., 45, 1517 (19i 1)
The
are
cis-
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific \`nlume
Table i
and Viscosity of E[hanol-Naler Df ixlures under High Pressure
The Viscosity of Ethanol-1Va[er '.Mixtures (10-sPa~s=cP)
21
1` Temp. ('CJ
F (bar)_>i
0.0050 25
0.2050 15
0.30 0.40 50 25 50
1
98
196
29a
392
490
589
686
iS5
0.8911
0.8891
0.8882
0.3872
0.8866
0.8864
0.8866
0.3322
0.8881
O.i468
0.3456
0.5104
O.ii22
O.iial
OSi6l
O.ii83
2.331
1.400
2.461
2.SOG
IS6i
1.601
2.666
2.701
2.771
1.060
1.134
1.136
1.17 i
LIST
L200
1.131
2.314
2.407
2.481
2,159
2.638
2.703
2.171
2.845
2.939
1.108
1.155
1.1 h8
1.211
1.249
1.275
1.341
1.148
2.249
2:352
z.as9
2.527
2.611
2.102
2.779
2.88a
1,072
1.146
1.166
1x14
L26a
L 293
1.333
.Y Temp, (°C)
P (bar) 25O.GO
i00.78 25
1.423
1.513
1.614
1.703
1.300
l.ais
1966
2.052
2.IOi
osa so 25
,.~i!)
1
93
196
291
392
190
189
686
755
1.740
1,843
].9+t
2.031
2.131
2.220
2.330
2.389
2.131
0.9405
1.029
1-039
L113
1.166
LIS2
1.231
O.SIOI
O.Siii
0.8339
0.9397
0.9969
L.D13
1.051
1.081
1.110
1 ?46
1.326
1.397
L4ii
L517
1.6t3
1.691
0.6881
O.i 473
0.7758
0.3379
O.R800
0.9261
0.9682
3.0
:.a
~.~
a
e
T .e
7
a
re
9 ~ 2SC
~o ~w
50'C Q ~o g
~~ ~a~
,~
0 0.2 0.4 0.6 0.8 L0
dole fraction of ethanol
cosity data display a maximum at a composition from
temperature. Agreement of the. data among researchers
Fig- 7
0.2
is
Composition dependence of the vis-cosity o[ ethanol-water mixtures at 2i' aad 50'C at the atmospheric
pressure ~: This work, ~: ll), ~: Id),
~ : 19). O : 20).0: 20. O: 22)
to 0.3 mole fraction of ethanol at each
comparati.~ely good at 25°C, except the
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
22 l'. Tanaka, T. S'amamota, 1' . Satomi, H. Kubota and
2SC x X0.3 --"`~`
__-' ~~
-- -__ ~ U1 S ~ . _ - _- 0. ,r
0.4 p.8 __~_" "-__
,r'__ _
_~_.~I.U Ethanol
r
__.__ ~_-____e._____ ~
_______ _~_-Watery
T. \fakita
N W
O
T O
7
3.0
z.a
i.o
a soa
Pressure/bar
iooa isoa
FiR, b
°
x ~ O.a -
"o• y-'~
0.2 ~6 .~
Pressure dependence o1 Che xiscosit.• of ethanol-water mixtures at 25°C
~: 11), ~: 23)
1.5
1.0
A 0.
0 T
O
7
0.5
so•c
~~
;e~
_-
0
0.2
_-~ a
~-
Water
Fig. 9 Pressure dependence of the viscosity of ethanol-water mixtures at i0°C ;~: This work, ~: S), • : 22). ~ : 23)
0 500 1000
Pressure/bar
results reported be Yusa et al.,~~~ whose data are about -4 ~ higher than others near the maximum.
Inconsistency 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;. but that the discrepancy increases withincreasing
pressure.: serious inconsistency is found in the results for pure ethanol In the results of Yusa eE
23) I. F. Golubev and V. A. Petrov, Trudy GL1P, \o. ?, 5 p9i3)
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
Specific Volume and Viscosity of Ethanol-Water Mixtures under High Pressure ?3
af.,tt} the pressure coefficient of viscosity, ~ P ~., for ethanol is rather small at 25°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 (G)
where ~ is the viscosity in 10-'Ya•s (=cP) 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 to higher
ethanol fraction with increasing pressure or temperature.
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 hydroxy-
compounds, which are yeC inadequately 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, espe-cially as for the appearance of anomalies, as well as in the case of aqueous solutions of other alco-
hols.
Table 6 Coefficients of the Viscosity Isotherms: n=B,+BzP+N3Pr tP in bar)
Temp. ('C)
l" B, Liz x 10+ BB x 108Ave. Dev,
(,.°o)Alac. Dev.
(.°o)
25
50
0.20
0.30
0.40
0.60
0.78
1.00
0.20
0.30
0.40
0.60
0.80
1.00
2.34083
2.32078
2.li289
1.74644
1.41928
1.08861
1.08858
1.11481
1.Oi 846
0.94929
0.80963
0.690264
5.83501
8.15612
9.86471
10.0016
10.3408
8.16148
3.1009
1:644G8
1.2 t 148
6.1578
4.11241
5.07855
- 6.0312
- 1.31 i
- 3.620
- 3.1239
-18 ,7226 - 6.331
-13.262
18.153
-15 .191
-31 .312
6.664 - 5.883
0.25
0.25
0,24
0.41
0.24
0.16
0.74
0.60
0.53
O.Si
0.6G
0.44
o.4i
o_4i
0.3i
1.ZI
0.>3
0.3fi
1.49
1.13
].Si
1.i9
1.3fi
1.12
The Review of Physical Chemistry of Japan Vol. 47 No. 1 (1977)
2-0
A
0
.e
1'. Tanaka T. 1'amamMO, Y. Satomi, H, Rubola and T. ~lakila
3.0
2.0
1.0
` 9 ~~ R
\ 8J. ~a
8 ~
6 ?>'C ~\
3
z\o \ '6~~\~i0'C
>` i
5~ 3 a
0.21
Pa _8 ~ ~9 b
ar
Pb~ a
0 0.2 O.i 0.6 0.8
\lole fraction of ethanol
1.0
Fig. 10 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,
is 389 bar, 8: 686 bar, 9: 785 bar
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+rent of C4em ical Engirreerireg
Fatally of Engineering
Psabe i'uiaersity
%be 657, Japan