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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)


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)


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


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)


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 isothermal 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


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

O.i394

0.7841

0.8147

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

O. S460+

0.5486

0.5504

0.5523

0.S S4i

0.5581

O.SSB3

0.5805

DRBI]

o.aao2

0.8103

0.818T

0.~13

o. a?Bi

0.8307

D.8340

0.93i5

0.849T

e.as2t

0.8882

0.8i54

0.88i0

0.8951

0.9096

0.8923

D.BS55

D.as3e

0.8920

0.9002

0.9149

0.9205

0.9302

0.0335

0.8962

0.8i33

0.8937

o.9ose

0.9192

0.9193

0.9364

O.T551O.iTBD

0.7 BT5

0.8238

D. B3as

0.8561

D.BSaz

O.aa92

0.5780

0.6012

O.61T8

0.6318

Ds4TT

O.BT10

0.6649

0.7074

0.394T

0.411 B

D.4zao

0.4481

0.4883

0.4 T9B

0.5090

0.6192

i6

1.089.1

19i295:393!3491.4589.48aT.5

0.3783+

0.9808

0.9832

0.3857

0.3882

0.3908

0.9999

D.9seD

D.495N

O.i02;i

O.SLSi

D.i235

0.5341

O.SiI?

0.645d

O.i939

0.5610

0.56fi2

0.5iifi

0.5 Bifi

0.69770.6089

0.55550,56iT

D.57ae

D.6909

0.6029D,6141

0.636D

0.550T0,5G400, 57620.5901osaz40,6141D_62 TO

0.52200.53T7O, SSOG0, 5631osiel0.59290.6053

O.iOTT

0.4284

0.44 G4

0.4T25

o.4soT

0.50T5

Dszsfi

0.3130

0.3268

0.3421

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)



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)


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-



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

title specific volume and viscosity of methanol-water mixtures … · 2019-03-29 · [he properties...

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