TERNARY LIQUID-LIQUID AND MISCIBLE BINARY VAPOR-LIQUID EQUILIBRIUM DATA FOR THE TWO SYSTEMS n-HEXANE ETHANOL ACETONITRILE

AND WATER ACETONITRILE-ETHYL ACETATE

Hiroshi SUGI and Takashi KATAYAMA

Department of Chemical Engineering, Faculty oj Engineering Science, Osaka University, Toyonaka 560
Liquid-liquid equilibrium data are obtained for the two ternary systems -hexane-ethanolacetonitrile at 40C and water-acetonitrile-ethyl acetate at 60C. Vapor-liquid equilibria for the two miscible binaries of each ternary system are also determined. The measured ternary liquid-liquid equilibria are compared with those predicted from the constituent binary data alone by use of various activity coefficient equations.

Introduction

utilized to predict the two ternary liquid-liquid

data. 1. Experimental

ing operations. Several attempts based on thermodynamic relations and activity coefficient equations6'7)9'13'15'16) have been made for predicting and
correlating ternary liquid-liquid equilibria. In pre-

Good prediction of ternary liquid-liquid equilibria from constituent binary data alone is a difficult problem, but is required in design calculations of separat-

ria from the constituent binary data, and the predicted equilibria were compared with the experimental

equilib-

diction, generally, the parameters in an activity coefficient equation for a completely miscible binary are evaluated from vapor-liquid equilibrium data, while mutual solubility data are used for a partially miscible binary. However, the three binary data which constitute a ternary system are rarely available at the same

1. 1 Vapor-liquid equilibria The experimental apparatus used for the measurement of vapor-liquid equilibria was a Brownstill3\ The volume of the boiling flask is 250 cc. The diameter

of the Cottrell pumpis 10 mm.to facilitate

temperature, and this fact limits progress in predicting ternary liquid-liquid equilibria.
60C. For the former system, vapor-liquid equilib-

ment at lower pressures. At pressures lower than 120 mmHg, it was difficult to operate the still steadily. This was the main reason why the equilibria for the two ternaries were measured at different temperatures. The equilibrium temperature was measured by a cali-

measure-

In this work, liquid-liquid equilibria were measured for the two ternary systems w-hexane-ethanol-acetonitrile at 40C and water-acetonitrile-ethyl acetate at

brated thermister in a thermometer well and a Wheatstone bridge of Yokogawa Electric Co., Ltd. Adjustment in pressure by a two-liquid manostat was made
so as to maintain the temperature. After steady-state conditions were attained, the equilibrium pressure was measured by a calibrated AMPGauge of Tokyo
Aircraft Instrument Co., Ltd. (limit of error0.3

rium data at 40C were also determined for the two

miscible binaries n-hexane-ethanol and acetonitrile-

ethanol. For the immiscible binary system 72-hexaneacetonitrile, mutual solubilities were determined at the sametemperature. For the latter system, vaporliquid equilibria at 60C were measured for the two miscible binaries acetonitrile-water and ethyl acetateacetonitrile. Mutual solubilities were determined for the water-ethyl acetate system at the sametemperature.
Various activity coefficient equations1>8'12>18) were Received December2, 1977. Correspondence concerning this article should be addressed to T. Katayama.
VOL ll NO. 3 1978

mmHg), and liquid and liquefied vapor samples were withdrawn from liquid and vapor samplers, respectively. The samples were analyzed by a gas chromatograph connected to a digital computer HITAC-10II of Hitachi Seisakusho Co. A stainless steel column, 160cm long, packed with P.E.G. 20M was used for separating the three components for the system 77-hexane-ethanol-acetonitrile. A similar column

packed with Porapak-g was used for the system water167

Table 1 Physical properties of materials used

Material Acetonitrile Ethanol Ethyl acetate
w-Hexane

Density
Exptl.
0.77671
0.78563** 0. 89453 0.65472
0.78504 0.89455 0.65481

at 25C [g/cc]
0.7766

Lit.14)

Exptl.
171.8 367.9 134.9 418.2 279.7 149.4

Vaporpressure [mmHg]
170.6 368.00 134.3 418.ll 279.4 149.44

Lit.
(40C)n) (60C)4) (40C)2) (60C)14) (40C)2) (60C)2)

Second yirial * coefficient [cc/mol]

-4750 -3470 -2030 -1500 -1690 -1360 (40C) (60C) (40C) (60C) (40C) (60C)

Water

0.

9970474

(40C) (60C) (40C) (60C) (40C) (60C)

estimated by the method of Tsonopoulos1T). Water contamination of 0.22% was found by the Karl Fischer test.
Table 2 Vapor-liquid equilibrium data for the two systems

w-hexane (l)-ethanol (2) and acetonitrile

40C

(l)-ethanol (2) at
[-]

Table 3 Vapor-liquid equilibrium data for the two systems

acetonitrile (l)-water (2) at 60C
xi yi

(2) and ethyl acetate

P

(l)-acetonitrile

xi

yi

[-

[-]
(2)

[mmHg]
system 134.9 201.1 283. 1 312.8 338.8 356.6 367.1 370.5 372.3 373.7 374.2 374.5** 373.8 368.2 367.5 365.5 353.9 332.0 279.7

[-] r2

[-]

[-]

[mmHg]

[-]
9.889 7.335 5.310 3.660 2.810 1.801 1.567 1.314 1. 199

-Hexane (l)-ethanol (12= -870* cc/mol) 0.0000 0.0000 0.0291 0.3285 0.0927 0.5435 0.1364 0.6022 0.1951 0.6421 0.2641 0.6627 0.3665 0.6840 0.4655 0.6938 0.4948 0.6976 0.6129 0.7031 0. 6964 0.7094 0.708** 0.708** 0.7978 0.7193 0.8819 0.7369 0.9070 0.7436 0.9168 0.7477 0.9599 0.7761 0.9845 0.8330 1.0000 1.0000

Acetonitrile
8.251 5.968 4.947 3.982 3.189 2.439 1.965 1.867 1.524 1.355 1.198 1.094 1.071 1.060 1.018 1.001 1.0

(l)-water
cc/mol)

(2) system
149.4
254.0 322.9 367.2 392.0 401.3 410.9 414.1 418.2 420.2

CB12= -2250*

Acetonitrile
(512=
0.0000 0.0341 0.0748 0.1319 0.2115 0.3035 0.4377 0.5187 0.586** 0.5960 0.6670 0.7116 0.7686 0.8585 0.9169 0.9719 1.0000

(l)-ethanol
cc/mol)
0.0000 0.1336 0.2292 0.3313 0.4013 0.4656 0.5247 0.5624 0.586** 0.5885 0.6316 0.6558 0.6883 0.7565 0.8404 0.9337 1.0000

(2) system
134.9 150.9 164.2 181.4 193.5 201. 207.5 210.8 210.9** 210.7 210.1 208.8 205.7 199.6 191.9 180.2 171.8

-510*

3.576 3.020 2.710 2.170 1.813 1.455 1.333 1.212 1.157 1.118 1.070 1.020 1.019 1.006

1.0 0.0000 0.0000 1.026 0.0300 0.4209 1.048 0.0654 0.5418 1.060 0.1127 0.5989 1.108 0.1844 0.6355 1.202 0.2530 0.6550 1.347 0.4147 0.6732 1.562 0.4843 0.6792 1.640 0. 5940 0. 6922 2.110 0.6720 0.7111 2.638 0.728** 0.728** 0.7489 0.7354 3.824 0.8004 0.7563 6.052 0.8786 0.8099 7.478 0.9471 0.8939 8.183 1.0000 1.0000 14.620 Ethyl acetate (l)-acetonitrile 26.574 (12 = -2430* cc/mol) 0.0000 0. 0000 0.0487 0.0768 0.0887 0. 1345 0.1500 0.2101 1.0 0.2234 0.2906 1.002 1.013 0.3089 0.3701 0.4040 0.4488 1.037 0.4984 0.5276 1.092 1.150 0.5735 0.5893 0.6384 0.6426 1.312 0.653** 0.653** 1.437 0.7073 0. 6977 0.7779 0.7592 1.612 0.8410 0.8208 1.752 1.882 0.8963 0.8764 0.9593 0.9483 2.098 1.0000 1.0000 2.615 2.826 3.285

1.0
1.009 1.049 1.097 1.157 1.223 1.514 1.699 2.091 2.442

421.7** 421.1 419.5 412.0 394.0 367.9

1.114 1.068 1.025 1.006 1.0 2.928 3.380 4.262 5.231 -

(2) system
367.9 380.6 391.2 403.0 418.2 428.1 435.6 440.6 440. 7 440.9 441.0** 440.4 438.1 435.0 430.7 425.1 4 18.2

- 1.0 1.442 1.002 1.423 1.006 1.353 1.012 1.302 1.030 1.226 1.050 1.156 1.083 1.114 1.115 1.081 1.140 1.060 1.171 1.037 1.021 1.014 1.006 1.004
1.0

1.223 1.277 1.319 1.383 1.456

1.0

estimated by the method of Tsonopoulos17) estimated value of azeotrope

rc-hexane-acetonitrile at 40C and for the

estimated by the method of Tsonopoulos17) estimated value of azeotrope

system

acetonitrile-ethyl 1. 2 Liquid-liquid

acetate. equilibria

Mutual solubilities of the two binary systems and the solubility curves of the two ternary systems were determined by a cloud-point method reported previously1^. Mutual solubilities
168

were measured for the

system water-ethyl acetate at 60C. Solubility curves were determined for the ternary systems ra-hexaneethanol-acetonitrile at 40C and water-acetonitrileethyl acetate at 60C. Tie-lines were determined by gas chromatographic analysis of liquid samples drawn from the two liquid phases at equilibrium. The two-phase liquid mixture
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Fig. 3 Activity

coefficient-composition

curves

of acetonitrile
Fig. 1 Activity coefficient-composition curves

(l)-water

(2) system at 60C

of w-hexane (l)-ethanol

(2) system at 40C

Fig. 4

Activity

coefficient-composition

curves of

ethyl acetate (l)-acetonitrile

(2) system at 60C

MerckUvasol spectrograde chemicals of minimum purities 99.7 % 99.7 % and 99 %, respectively. Ethanol was spectrograde of minimum purity 99.5 % obtained from Nakarai Chemicals, Ltd. All organic materials
were used without
in an all-glass

further

purification.

The water
properties

Fig. 2 Activity coefficient-composition curves of acetonitrile (l)-ethanol (2) system at 40C

used in the experiment was deionized water distilled

distillation flask. Physical

of 20cc was shaken vigorously in a 30cc test tube immersed in a water bath. The water bath was regulated withinzbO.OFC with a Takara Thermostat model C-113. After the phases were separated completely, 2 cc samples were withdrawn from each layer with a preheated syringe and hypodermic needle and

of the materials used in this work are summarized in

1. 4 Experimental results 1) Vapor-liquid equilibria: The vapor-liquid equilibrium data at 40C for the two binary systems ft-hexane-ethanol and acetonitrile-ethanol are pre-

Table 1.

were immediately transferred to 5 cc tablet tubes. For

the /2-hexane-ethanol-acetonitrile system, they were

sented in Table 2, and the data at 60C for the two

binary systems acetonitrile-water and ethyl acetateacetonitrile are in Table 3. For each of the four systems, a minimum boiling azeotrope was found.

kept in an air bath at a temperature a little above the equilibrium temperature in order to avoid phasesplitting due to cooling. For the water-acetonitrileethyl acetate system, ethanol was added for the same reason. The homogeneous liquid mixture obtained was analyzed by gas chromatography, using the same method as for vapor-liquid equilibrium measurements.
1. 3 Materials Acetonitrile,
VOL ll NO. 3

Estimated values at each azeotrope are also given in Tables 2 and 3. Columns 4 and 5 of Tables 2 and 3 show the liquid-phase activity coefficients, and Figs. 1 to 4 show the relationships of activity coefficients vs. liquid mole fraction.
From the experimental P-x-y data, the activity coefficients were calculated by
169

ethyl
1978

acetate,

and

/z-hexane

were

Table 4

Solubility

data for the two ternary systems n-

hexane (A)-ethanol (B)-acetonitrile (C) at 40C and water (A)-acetonitrile (B)-ethyl acetate (C) at 60C
XA XB XA XB XA XB

[-] [-] /z-Hexane (A)-ethanol

0.0857 0.0943 0.1077 0.0000 0.0410 0.0971

[-] [-] [-] (B)-acetonitrile (C) system

0.1966 0.2525 0.3040 0.2682 0.2884 0.2832 0.5118 0.5595 0.6092

[-]
0.2142 0.2005 0.1723 0.1255 0.0848 0.0000

0.1213 0.1181 0.1657

0.1614 0.2060 0.2414

0.3525 0.3845 0.4315

0.2680 0.2578 0.2422

0.6931 0.7587 0.9015

Water (A)-acetonitrile 0.2042 0.0000

0.2164 0.2299 0.2592 0.2724 0.2971 0.3243 0.0500 0.0938 0.1415 0.1701 0.2058 0.2171

(B)-ethyl acetate (C) system 0.3518 0.2358 0.6737

0.3878 0.4626 0.5154 0.5536 0.5877 0.6299 0.2568 0.2768 0.2777 0.2684 0.2576 0.2447 0.7341 0.7737 0.8164 0.8774 0.9882

0.2315 0.2034 0.1747 0.1480 0.1045 0.0000

Table 5 Tie-line

data for the two systems w-hexane (A)-

Fig. 5 Liquid-liquid

equilibria

of -hexane

(A)-

ethanol (B)-acetonitrile (C) at 40C and water (A)- acetonitrile (B)-ethyl acetate (C) at 60C

ethanol (B)-acetonitrile

ComponentA-rich phase 1 r1 XA XB
v

ComponentC-rich phase rll rll XA XB

0.0968 0. 1003

predicted results of the various activity coefficient equations

(C) system at 40C and the

_JH M w-Hexane (A)-ethanol (B)-acetonitrile

0.8831 0.8674 0.8546 0.8372 0.8101 0.7821 0.7272 0.6912 0.0166 0.0251 0.0332 0.0433 0.0567 0.0772 0. 1086 0. 1269

DH (C) system

[-]
0.0879 0.1299 0. 1622 0. 1942 0.2169 0.2331 0.2695 0.2748

0.1054 0. 1250 0.1367 0.1522 0.2053 0.2249

Water (A)-acetonitrile
0.9682 0.9584 0.9430

0.0210 0.0299 0.0452 0.0573 0.0706 0.0800 0.1154

(B)-ethyl

acetate (C) system

0.2492 0.2726 0.3445 0.3874 0.4340 0.4733 0.5840

0. 1277 0. 1774 0.2301 0.2572 0.2697 0.2749 0.2581

0.9306 0.9171 0.9049 0.8623

Fig.

Liquid-liquid

equilibria

of

water

(A)-

The vapor-phase fugacity coefficients were calculated from the virial equation truncated after the second term. The second virial coefficients for pure components and the cross-coefficients calculated by the Tsonopoulos correlation17} are listed in Tables 1, 2 and3. For the activity coefficients obtained, the conventional thermodynamic consistency test was applied. It is the well-known area test, by which the thermodynamic consistency of the data was confirmed for

acetonitrile

and the predicted results coefficient equations

(B)-ethyl acetate (C) system at 60C

of the various activity

acetonitrile at 40C and water-ethyl acetate at 60C are also included. The tie-line data of the two ternary systems are listed in Table 5. Figures 5 and 6 showthe experimental data of the two ternary systems. In the figures, circles are tie-line data and solid binodal curves are the smoothed ones of the solubility data in

each system within the limit of a practical guide10}.

2) Liquid-liquid equilibria: The solubility

Table 4.
2. Correlation and Prediction of Equilibria The correlation of the measured vapor-liquid equilibrium data were made by use of various activity coefficient equations. These are the Wilson equation193, the modified Wilson equation185, the twoJOURNAL OF CHEMICAL ENGINEERING OF JAPAN

data

for the two ternary systems n-hexane-ethanol-acetonitrile at 40C and water-acetonitrile-ethyl acetate at 60C are listed in Table 4. In the table, mutual solubility
170

data

for the two binary

systems rc-hexane-

Table 6 Parameters in various activity coefficient

System
Temp. Wilson eq.
A12 An 0.2691

equations

Modified Wilson
eq. A12 A21

2-parameter NRTL eq.

T12 t21 2^6714 1.5258 0.5499 0.8799 1.5525 1.7803 0.6750 1.8559 0. 1791 0.2391 4.3581 0. 1464
0
*"21

3 -parameter NRTL eq.

^12
*"21

LEMF
eq.
r12

UNIQUAC
eq.
^12

Component1 Component 2 [C]

-Hexane Acetonitrile -Hexane Acet onitrile Ethyl acetate Water ethanol ethanol acetonitrile water acetonitrile ethyl acetate

0.0818

.47
0. 6406 0.1663

2.

7569

0.4925

0.0492 0.4308 0.4056 0.5677 0.5180 0.4159 - 0.1002 - 0.1641 0. 1309 0.4920 0.3555 0.3532 0.7924 0.6326 0.8228 1.2060 0.2802 0.6039

0.30 0.20 0.30 0.30 0.20

1.6449 0.6997 0.9045 1.0794 1.8857 0.2250 0.2419 -

0.9664 0.5464 0.4569 0.9345 0.9135 0.4625 0.8431 0.5814 1.166 0.1937 0.1765 0.6380 1. 1975 0.5394

1.8225 1.4657 0.3651 0.6146 0.6490 0.5461 1.2834 0.6174 0.4052

Wilson equation19) : GE/RT= -x In (xl+A12x2)-x2 Modified Wilson equation18) : GE/RT= -x In (xt+Azlx2)-x2 r-21exp(-av21) NRTL equation12) : GE/RT=x1x2 x1+x2Qxp(-az21)

In Cx2+Ai*i) In {A12xx+x2)+x
, z-12exp(-(xt12)

In {x+P2iX2)+x2

In (p12xx+x2)

' x2+x1exp(-aT12)

LEMF equation8)
UNIQUAC equation1)
9

: GE/RT=x1x2
: GE/RT=x1ln-^

r21 exp z-2i Xi+^exp rsi

Xi

r12 exp r12 Xs+Xi exp z-12

+x2ln-2

X'

' Z

In JL- -\rq2x2

In

-q1x1 In (01 +02*21)

-q2*2 In (#ir12+#2)

parameter NRTL equation12}, the three-parameter NRTL equation12), the LEMF equation8), and the UNIQUAC equation1]. The parameters of these

which give a slightly narrower solubility range than the experimental one. The UNIFAC model was not applicable to the water-ethyl acetate system since the

equations, listed in Table 6, were determined so as to

minimize the value of ZtCri/^expti.-Cri/^caic.]2. In Figs. 1 to 4, the activity coefficients calculated

group-interaction parameters between water and ester

groups are not available. The ternary liquid-liquid equilibria systems w-hexane-ethanol-acetonitrile for the two and water-

with the experimental ones. Applicability of the UNIFACmodel of Fredenslund et al.b) was examined for these binary systems and it was found that the model gives satisfactory results, as shown in Figs. 1 to 3. In the ethyl acetate-acetonitrile system, the prediction of activity coefficients could not be made by the UNIFAC model since the group-interaction
parameters available. between ester and nitrile groups are not

by the Wilson parameters in Table 6 are compared

acetonitrile-ethyl acetate were predicted by the various activity coefficient equations with the constituent binary parameters. The calculation was performed by
solving the following simultaneous (xtr(y=(Xirt)u equations.
(3)

/2-hexane-ethanol-acetonitrile,

For the ternary liquid-liquid

equilibria
the

experimental

of the system
the LEMF

re-

ft-hexane (A) - acetonitrile (C) and water (A) - ethyl acetate (C), the parameters of the modified Wilson
equation, the two-parameter NRTL equation, the LEMFequation and the UNIQUACequation were determined by solving the following simultaneous equations :
(xArA)I=(-^ArA)ll

From the mutual solubility data for the two systems

sults are compared in Fig. 5 with the results predicted

by the two-parameter NRTL equation,

equation, and the UNIFAC model. The predicted result (not shown) by the modified Wilson equation
was almost the same as that by the two-parameter NRTL equation. The predicted result (not shown)

(2)

The parameters of these equations

(xcrcY = (xcrc)u

obtained

are also

listed in Table 6. In the table, the parameters of the

UNIQUAC equation for the ^z-hexane-acetonitrile system are not given, as the computer technique failed to converge. The mutual solubilities (x\-x")
by use of the UNIFAC model are (0.9335-0.0679),
VOL. ll NO. 3 1978

the three-parameter NRTL equation is not always superior to the two-parameter one. In the system, each predicted set of ternary liquid-liquid equilibria shows a larger immiscible region than the experimental set, except for that of the LEMF equation.
For the the ternary system water-acetonitrile-ethyl liquid-liquid equilibria predicted

by the NRTLequation with the three parameters for the constituent miscible binary systems gives an immiscible region as large as that of the UNIFAC model. This shows that in predicting a multicomponent system

of the rc-hexane (A)-acetonitrile

(C) system predicted

acetate, by the
171

UNIQUAC equation, the LEMF equation, and the modified Wilson equation are shown in Fig. 6 with the

experimental values. The predicted result (not shown)

by the two-parameter NRTLequation or the threeparameter NRTLequation lies in the region between
those of the UNIQUAC equation and the modified Wilson equation. In the system, all predicted results
give larger immiscible
one.

(j> = vapor-phase fugacity <Subscripts> calc. = calculated value exptl. = experimental value i = componenti

coefficient

[-]

regions than the experimental

<Superscripts> L = liquid phase = saturation

I s

Conclusion
equilibria

= component A-rich phase = component C-rich phase Literature Cited

II

Experimental data were obtained for liquid-liquid

for ft-hexane-ethanol-acetonitrile

1) Abrams, D. S. and J. M. Prausnitz:

AIChEJ., 21, 116 (1975).

at 40C

2) American Petroleum Institute Research Project 44, "Selected

and water-acetonitrile-ethyl acetate at 60C. Vaporliquid equilibrium data were also obtained for the two miscible binary systems of each ternary system. In comparison with the experimental data, applicabilities of the various activity coefficient equations were tested in predicting the ternary liquid-liquid equilibria from the constituent binary data alone. However,no satisfactory results were obtained for these ternary systems.

Values of Properties of Hydrocarbonsand Related Compounds", Thermodynamic Research Center, Texas A & M
Univ., Texas (1969). 3) Brown, I. : Austr. J. Sci. Res. Ser. A-Phys. Sci., 5, 530 (1952). 4) Brown, I. and F. Smith: Austr. J. Chem., 8, 62 (1955). 5) Fredenslund, A., R. L. Jones and J. M. Prausnitz: AIChE
J., 21, 1086 (1975).

The data presented in this work will be used to examinehowclosely an activity coefficient equation can predict ternary liquid-liquid equilibria from the constituent binary data alone.
Acknowledgments

6) Guffey, C. G. and A. H. Wehe: ibid., 18, 913 (1972). 7) Hiranuma, M. : Ind. Eng. Chem., Fundam., 13, 219 (1974). 8) Marina, J. M. and D. P. Tassios: Ind. Eng. Chem., Process Des. Dev., 12, 167 (1973). 9) Marina, J. M. and D. P. Tassios: ibid., 12, 271 (1973). 10) Prausnitz, J. M.: "Molecular Thermodynamics of Fluid
Phase Equilibria", (1969). Prentice-Hall, Englewood Cliffs,

N. J.

The authors thank the Computer Center, Osaka University, for the use of its facilities and Mr. Takashi Murayamafor his assistance in the experimental measurements.
Nomenclature
p

ll) Prausnitz, J. M., C. A. Eckert, R. V. Orye and J. P. O'Connell : "Computer Calculations for Multicomponent VaporLiquid Equilibria", Prentice-Hall, Englewood Cliffs, N. J.
(1967).

total pressure gas constant absolute temperature liquid molar volume liquid-phase mole fraction vapor-phase mole fraction

[mmHg] [cal/mol - K]
[K]

12) Renon, H. and J. M. Prausnitz: AIChEJ., 14, 135 (1968). 13) Renon, H. and J. M. Prausnitz: Ind. Eng. Chem., Process Des. Dev., 1, 220 (1968). 14) Riddick, J. A. and W. B. Bunger: "Organic Solvents", John Wiley & Sons, Inc., New York (1970).
15) Rod, V.: Chem. Eng. J., ll, 105 (1976). 16) Sugi, H., T. Nitta and T. Katayama: /. Chem. Eng. Japan,
9, 12 (1976).

[cc/mol [-] ]
r j

17) Tsonopoulos, C : AIChEJ., 20, 263 (1974). 18) Tsuboka, T. and T. Katayama: /. Chem. Eng. Japan, 8, 181
(1975).

= liquid-phase

activity

coefficient

[-]

19) Wilson,

G. M.: /. Amer. Chem. Soc.t 86, 127 (1964).

172

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