5) Cawood, W. and H. S. Patterson: J. Che?n. Soc.

, 1933, Metropolitan University, Tokyo, (1968)

p.619 15) Natl. Bur. Standards(U. S.) : Tables of Thermal Properties
6) 72,Collins,
283
S. C. and F.G. Keyes: Proc Am. Acad. Arts Set.,
(1938)
of Gases, Circ. 564 (Nov. 1, 1955)
16) O'Connell, J. P. and J. M. Prausnitz: bid. Eng. Chem.
7) Cox, J.D.: Trans. Faraday Soc, 57, 1674 (1961) Process Design and Development, 6, 245 (1967)
8) Eucken, A. and A.Z. Parts: Z. physik. Chem., B20, 184 17) Rowlinson, J.S. : Trans. Faraday Soc, 45, 974 (1949)
(1933) 18) Scott, D. W., J. P. McCullough, W. D. Good, J. F. Messerly,
9) Itterbeek, A. van and van, O. Paemel: Physica, 5, 145 (1938) R.E. Pennington, T. C. Kincheloe, I. A. Hcssenlopp, D.R.
10) Kogan, V.B., V.M. Fridman andV.V. Kafarov: Equilib- Douslin and G. Wadoington: J. Am. Chem. Soc, 78, 5457
(1956)
rium between liquid and vapor, Nauka, Moscow (1966)
ll) Lambert, J. D., G.A.H. Roberts, J.S. RowlinsonandV.J. 19) Stockmayer, W.H.: J. Chem. Phys., 9, 398 (1941)
20) The Society of Chemical Engineers, Japan: Bussei Teisu,
Wilkinson:
12) Landort,
Proc. Roy. Soc, A196, 113
H. and R. Bornstein:
(1949)
Physikalisch-Chemische Vol. 1, Maruzen, Tokyo (1963)
21) Ibid,: Bussei Teisu, Vol. 2, Maruzen, Tokyo (1964)
Tabellen, 5th ed., Vol. 2, Suppl 3, Sect. 78AW, J. Springer, 22) Ibid. : Bussei Teisu, Vol. 3, Maruzen, Tokyo (1965)
Berlin, 1935
23) Ibid,: Bussei Teisu, Vol. 4, Maruzen, Tokyo (1966)
13)cessing,
MacCallum,
40(5),
R.191N. (1963)
and J. J. McKetta: Hydrocarbon Pro- 24) Ibid,: Bussei Teisu, Vol. 5, Maruzen, Tokyo, (1967)
14) Nagahama, K. : M. thesis, Dept. of Technology, Tokyo

FORMULATION AND PREDICTION OF QUATERNARY VAPOR-

LIQUID EQUILIBRIA ACCOMPANIED BY ESTER1FICATION*
ISAO SUZUKI, HIROMASA KOMATSU AND MITSUHO HIRATA
Dept. of Ind. Chem., Faculty of Eng., Tokyo Metropolitan
University, Tokyo

Quaternary vapor-liquid equilibria with esterif)cation have been formulated mathematically. First,
activity coefficients have been related to liquid compositions with polynomial equations derived from the
Margules model, and second, the parameters B; defined in an equation of the vapor-liquid equilibrium ratio
with esteriflcation reported previously have been represented by polynomials. Both correlations are
adequate to describe the behavior of the given systems.
Vapor-liquid equilibrium with reaction of the system acetic acid-ethanol-water-ethyl acetate was
predicted from Wilson's parameters obtained from binary system data only. Association equilibrium
constants of dimerization and trimerization in acetic acid vapor were used to calculate modified activity
coefficients, and Wilson's parameters were determined from six binary data. The agreement of the
calculated and experimental data may be considered satisfactory for the practical use to design
multicomponent distillation column reactors.

Although industrial esterification processes utilize frac- use of computer, and to estimate the above quaternary
tionating columns as continuous reactors, the approach vapor-liquid equilibrium data from parameters obtained
to their design and operation has been largely empirical. from binary system data only.
But many investigations have shown that the extent
of conversion at each stage could be predicted from reac- !. Formulation of the Quate mary Vapor-Liquid
tion-rate data, and that successive plate-to-plate design Equilibrium Data with Esterification
calculations could be made by utilizing experimental
vapor-liquid equilibrium data and kinetic and equilibrium This work was started with the Margules equation5}
relations. modified by Marek which might be applicable to express
Previously, the authors reported on vapor-liquid equi- the quaternary system vapor-liquid equilibrium data in
libria of quaternary systems with esterification, such as esterification. The Margules constants were evaluated
acetic acid-methanol-water-methyl acetate8\ acetic acid- so as to minimize the sum of the squares of the difference
ethanol-water-ethyl acetate7} and acetic acid-butanol- between the observed and fitted values of the excess
water-butyl acetate6\ and derived the relations with free energy suggested by Wohl, using experimental
graphical correlation for the above systems. quaternary data, and the validity in vapor compositions
In the present paper, we have tried to formulate wastested. But this system is far from ideality in
relations between the liquid and vapor compositions or liquid phase, so this trial failed to obtain good relations.
graphical correlations for solving the complexequations Wethen tried to rearrange the Margulesequation as a
of multicomponent distillation column reactor design by polynominal series in mole fractions of the components
in the mixture. The corresponding equation for its
* Received on August 8, 1969 coefficient can be rearranged to the form

152 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 log7*1

Coefficients

VOL.3
Q
Tt
= A1X22 + A2X32 + Azx 2 + A4X2X3 + A^xiXi
+ AqXsXa + A7X1X22 + AsXiXs2 + A9X1X42
+ ^4.10X1X2X3
+ A13X4X1X2
+ A6x3x42

in good agreement with

* (°C)
Standard

yt {mo\ %)
* In this

NO.2
+ -A11X2X3X4

and A\ through Ai§ are constants which are determined

by quaternary equilibrium data. The expressions for

be obtained by a cyclic permutation of the indicies;

l-*2->3->4->l.

Eq. (l) is the linear function for A\ through A\%and

an optimumset of these values was determined by the
least-squares fit to Eq. (l),

system in the practical use to design a multicomponent

distillation column reactor.
Further, some similar polynomial equations with more

0.

0. 102712
-0.
-0.
-0.
0.

0.

paper,
0.

1970
+.A12X3X4X1
+ Al4X2XB2 + ^Ll5X2X42
(1)
where xt represents the mole fraction of the z-th com-
ponent in the liquid phase, Ti is the activity coefficient

the activity coefficient of the remaining components can

The constants of the Antoine equation used to calculate

the vapor pressure of pure liquid are listed in Table 1.
Computed regression

than sixteen constants were tested to get a moreaccurate

relation, but the results showed little difference. Then
it may be concluded
our purpose.

2. Formulation of the Graphical Correlations

The authors
that Eq. (l)

suggested6~8)
the reacting system varied continuously with the change
using

experimental

Acetic acid
-0.565327
-0. 272620 El
-0.141799E2
-0.296412El
174107
0. 953302
0. 820185
0.281103
0. 188169
EO

El
El
EO
El
E2
E2
359400 E2
567641 El
930224 El
768782
0.381214
828829

errors in all data

0.015899
053854
0.93162

1.0148
El
E2
EO
that

"Ea" indicates
a digital

coefficients of each component

for Eq. (1) and estimated standard errors in Q function
suggested by Redlich and Kister, activity coefficients,
temperature and vapor compositionsfor the three systems
are shown in Tables 2, 3 and 4. Calculated values are

the

10a
computer.

data for

is most suitable

x-y relation

Table 2 Computed regression coefficients

Tii */ Yi f°r tne system acetic
each

for

of
of liquid
the variation
definitely
or 1.

acid-methanol-water-methyl

-0.691180
-0. 255861
-0. 118730
Methanol
0. 220421
0. 121955
-0. 167642
-0. 289375

0. 706607
-0. 103195El
0. 227980
0. 509270
0. 335891

-0.
0.232413
267237
0. 457576
0. 271497

0.
El
E2
EO
EO
El
E2
E2
El

El
E2
El
E2
E2
El
E2

068103

0. 82866
acetate
Number of data points
compositions

by the relation
by reaction,
of x-y relation

The following equations summarize the above work.

used;

0. 507431
-0.993873
0. 585876
-0. 824075
-0.862661

0. 106578
0. 179496
-0. 762537
0. 117444
0. 862398
0. 842563
-0. 228941

0.

1.3678
Water

0.111392
-0. 770021
-0. 882569
0. 958974

016527
170

E2
E-l
EO
E2
E2
El
E2
EO
EO
E3
E3
El
E3
E2
E2
EO
2
and the path of
might be determined
at hypothetical conversion 0

Vapor-liquid equilibrium ratio, Ki, is shown as follows

logKt = - 2.30x103(t^)
But, for acetic acid, Ki is given by
Ki =2.25xl(T2*
Ki =0.001
+ Bt

-
(2)

where Bi is function of the liquid components at hypo-

thetical conversion
kinds of graphs.
For reduction
and B42, to equations,
0 or 1, and has been shown as six

of these graphs,.623, B24, B31, B32, Ba

a preliminary
that polynomials in two variables might be suitable.
Weassumed the following functional relationship

composition.
Bij =f(Fu F2)
where Fi and F2 are the dependent variables of liquid

Further analysis of several trial regressions

-
(3)

led to
some modifications in the terms in the regression equa-
tion to obtain a better fit with the arbitrary limitation

Substance
methanol
ethanol
Table

72-butanol
acetic acid
methyl acetate
ethyl acetate
butyl acetate
water
I

7. 87863
7.83124
8. 27488
7.55960
7.20211
7.09808
7. 12530
7.96681
Antoine constants used in this

1644.
a
1473. ll
1440.
1873.

1232.83
1238.71
1426.90
1668.21
52
90
05
230. 0

.605112228.0

values determined from the data of reference

authors

for Eq. (l) and standard errors of estimate in Q,

217.0

13.524
3230.0
2.71
1.666

b
t>74.0
t<74.0

analysis indicated

0.822

Methyl
-0. 176293
c

0. 257847
-0. 170627
0. 178298
-0. 200939
0. 336902
-0. 373925
-0.311324
0. 610441
0. 162085
-0.467115
-0. 322066
-0. 332442
0. 944822
0. 649635
0. 800948

0. 078420
paper
Data
reference
)ll(
)9(
)9(
)2(
)ll(
)ll(
)9(

(10)

acetate
EO
EO
El
EO
EO
El
EO
El
El
El
El
El
El
EO
El
EO
by

153
 Table 3 Computed regression coefficients for Eq.(l) and standard errors of estimate in Q,
7it */ Yi f°r tne system acetic acid-ethanol-water-ethyl acetate
Number of data point used; 247
Coefficients Acetic acid Ethanol Water Ethyl acetate
-0. 554296 EO 0. 581778 EO 0. 688636 EO -0.601367 E-l
-0. 324357 EO 0. 209245 EO 0.243031 E-l 0. 229575 EO
-0. 103685 EO -0.257329 EO 0. 375534 EO 0. 186575 El
-0. 705455 EO -0.562636 EO 0. 127548 El 0. 355191 EO
-0.201335El -0. 314853 EO 0. 177863 El 0. 468416 EO
-0.225362El 0. 451732 EO 0. 696279 EO 0.151110 El
0. 837926 EO -0.115411 EO 0. 936722 EO -0. 599682 E-l
0. 523760 EO 0. 695310 E-l 0. 449356 EO 0. 673994 E-l
0. 434061 EO 0. 740529 E-l 0. 717790 EO -0. 315997 El
-0. 534056 EO 0. 187010 EO 0. 144973 El 0. 941858 EO
-0. 325231 El -0. 369985 EO -0.211099 El -0. 192225 El
0. 590329 El -0. 823390 E-l 0. 746905 EO -0.755731 EO
0. 335400 El -0. 409472 EO 0.112914 El 0. 103791 El
0. 197296 EO 0. 109247 El 0. 120436 EO 0. 365254 EO
-0. 452660 EO 0. 192416 EO -0. 164268 El -0. 136587 El
0. 147152 E-l -0. 172565 EO 0. 330018 EO -0.213818 El
Standard errors in all data
0. 018585
0. 064442 0. 060124 0. 16398 0. 29487
1. 2089
1.2061 0.7899 1.2903 1. 3252

Table 4 Computed regression coefficients for Eq. (l) and standard errors of estimate in Q,
Tir tr Yl ^or ^e system acetic acid-butanol-water-butyl acetate
Number of data points used; 97
Coefficients Acetic acid Bu tanol Water Butyl acetate
0. 621909 El 0. 109686 El 0. 537395 E2 -0. 809230 EO
-0. 467747 EO 0. 120872 E2 -0.674166 EO 0. 638384 E2
-0. 256615 El 0. 565434 EO 0. 198171 E3 -0. 501678 EO
-0. 264249 El 0. 250634 El -0. 192251 E3 0. 126996 E2
-0. 107039 E2 0. 559804 EO 0. 647689 E2 0. 499868 El
0. 374885 El -0. 172787 E2 0. 154656 E2 -0. 215444 E2
-0. 233394 El -0. 404033 El -0. 106354 E3 -0. 480678 El
0. 192890 EO -0. 300803 E2 -0. 404050 El -0. 140943 E3
0. 962654 El -0. 745638 El -0. 287382 E3 -0. 177893 El
0. 927400 EO 0. 309111 E2 0. 118859 E3 0. 143813 E2
-0. 132085 E2 0. 180904 EO 0. 429985 E3 -0. 597740 E2
0. 271947 El 0. 295925 E2 0. 343773 E2 -0. 161187 E2
-0. 499595 El -0. 140431 EO 0. 860108 E2 0. 574879 E2
-0. 846960 EO -0. 268435 E2 0. 173370 E3 -0. 110391 E3
0. 230523 E2 å 0.921191 EO -0. 650247 E3 -0. 313072 El
-0. 323718 El 0. 305518 E2 -0. 374382 E3 0. 266626 E2
standard errors in all data
0
0. 048361
Ti 0. 045144 0. 055327 0. 098601 0. 030941
t[°Cl 2. 8454
yt [mol 1.6560 3. 3294 3. 3955 1.6100

of Fi and F2. The results of analysis are shown in 3. Prediction of Quaternary Vapor-Liquid Equilibrium
Table 5 to 7. Data with Esterification from Binary Phase Equilibria
The equation finally accepted follows.
Bij = Ci + GFi + C3F1F2 + C4Fi2 + C5Fi2F2 For quaternary system vapor-liquid equilibria with
+ GFx3 + C7Fi3F, + C8FiiV + CFSF*2 esterification, it may be assumed that ordinary vapor-
+ C10Fi2F23 + CnFi3F22 + C12FiF23 liquid relations are used, if the system is nearly in the
+ CnFi'Fs8 (4) equilibrium state.
where Wilson's model12) is useful for calculating the activity
17_
^1-
X-*'
1 1 » P2-
ij,_ 1"^/ coefficient of any component in a quaternary solution
1+Xi' 2 1+xy
using only parameters obtained from binary vapor-liquid
Ci to C13 \ regression constants equilibrium data. The activity coefficient of any com-
The regression coefficients were evaluated, and the ponent is
results, as shown in Tables 7 and 8, are reasonably W*=-b[Lx,Axi\+i-S fiA* (5)
accurate fits to the experimental for the acetic acid-
ethanol-water-ethyl acetate system.

154 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Table 5 Definitions of quantities used in regression Eq. (3)
Btj= d +C2Fl 4-C^F, +C4F,F22+C5F,2 +C^F, +C7F12F22
Bij = Ci + C2F1 + C3F1F2 + CAFl2 +C5F12F2 + C6Fi3 + C7Fi3F2
Biy=d+C2Fx +C3FiF2 +C4F12 +C5F12F22+C6F2+C7F22
Biy- d +.C2F1 +C3F!F2+C4F!2 +CsFii^2 +C6F!2F2+C7F12F22 +C8Fi3 +C9F!3F2 +doFiW
J5<y =d + C2Fx + C3F1F2+C4F!2+C5F!2F22+C6F2+C7F22 +C8FiF22+CF.F,* +doFi2F2+diFi3F2
5O-= d +C2FX4-C3F!F2+C4F!2+C5Fl2F2+CeFx3 4-GF^F,+ C8FiF224-C9Fi2F22 4- doFi2F23 + diFi3F224-d2FiF23 4-d3Fi3F23

where Fi and F2 are defined as follows;

1
Xi

6
Xj
2
l+Xt Xj

7
l-xt Xi+Xj
3
l+Xi

8
4
Xj

Xi
5
9
1-Xi l-Xr2

Table 6 Comparison of standard errors of estimate in 841, 831, 832 for the equations of Table 5
Figure used as source of data
Bn
£31 Bx

Bn Bz-

A-l 0. 2022 0. 1104 0. 0775 D-l 9. 8395 2. 2143 1. 7772

A-2 0. 1895 0. 1054 0. 0767 D-2 4. 3970 1. 1994 1.4984
A-3 0. 0603 0. 0385 0.0153 D-3 1. 3849 3. 2936 2. 7848
A-4 0. 1788 0. 0886 0.0665 D-4 59. 0840 0. 3863 2. 2167
A-5 0. 1261 0. 0486 0.0969 D-5 4. 4660 1.5311 7. 9903
A-6 0.1155 0. 0444 0.0173 D-6 7. 5533 1. 5494 7. 4093
A-7 0. 3009 0. 2375 0. 1902 D-7 14. 6489 10. 6241 40. 9145
A-8 0. 2363 0. 1581 0. 1696 D-8 23. 9443 2. 7290 3. 9732
A-9 0. 1876 0. 0550 0.0716 D-9 2. 0339 0.3812 4.5541
B-l 0. 2034 0. 1051 0. 0748 E-l 2. 4826 0. 3766 0. 9044
B-2 0. 1707 0. 1014 0. 0722 E-2 1. 4673 0. 8989 1. 1487
B-3 0. 0607 0. 0460 0. 0199 E-3 1. 0670 0. 5189 0. 8950
B-4 0. 1847 0. 0699 0. 0558 E-4 27. 1133 7. 8596 6. 5803
B-5 0. 0872 0. 0432 0. 0968 E-5 8.4856 3. 6029 19. 3417
B-6 0.0913 0. 0384 0. 0187 E-6 1.6614 3.2811 10. 6566
B-7 0. 3009 0. 2375 0. 1903 E-7 14. 5146 23. 7552 18. 6266
B-8 0. 2477 0. 1576 0. 1694 E-8 2. 4435 4.4261 4.0371
B-9 0. 0992 0. 0457 0. 0766 E-9 1. 9540 3. 0439 6.3141
C-l 0. 0720 0. 0358 0.0162 F-l 0. 1350 0. 0958 0. 0728
C-2 0. 0578 0. 0347 0. 0170 F-2 0. 1216 0. 0929 0.0712
C-3 0. 0579 0. 0321 0. 0099 F-3 0. 0580 0. 0284 0. 0093
C-4 0. 2929 0. 0653 0, 0547 F-4 0. 1376 0. 0569 0. 0472
C-5 0. 0846 0. 0400 0. 0969 F-5 0. 0778 0. 0382 0. 0965
C-6 0. 0760 0. 0408 0.0198 F-6 0. 0755 0. 0337 0. 0128
C-7 0. 2416 0. 2170 0. 1778 F-7 0. 2437 0. 2339 0. 1902
C-8 0. 1652 0. 1306 0. 1579 F-8 0. 1927 0.1531 0. 1692
C-9 0. 0831 0. 0406 0.0713 F-9 0. 1034 0. 0415 0. 0681

Table 7 Computed regression coefficients for the Eq. (4) and standard error of estimate in Bij
of the system acetc acid-ethanol-ethyl acetate
Equation ; Bij= d +C2Fi +CzFiF2 +CF12 +CsFl2F2+GiV +C7F1*F2 +C8FiF22 +C9Fi2i^22+ C10F12F23 +C11Fl3F22
+ C12F1F23 + C13F1IF23
1-3* F- t-XJ
yhere Fi = 1+Xi 2 1+Xj
B2i
Bu

0. 6547 E 0. 6499
l 0.
6550 El 0.6149 El 0.6166 El El 0 >6557 El
E 0.9418 0. 2721
-0. 8590 O 0.2145

El -0.2666 El -0.1731 El EO El
0. 2593 -o. 8176 El 0.4999 El 0.4697 El -0.9598 El -o. 3385 El
0.4030 3615 El 0.5322 El 0.5475 El -0.3208 El 5165 El
-o. -o.
-0.5310 0. 1272 E2 0.3065 El -0.2381 El 0. 4407 E2 4144 El
-o.
-0. 2526 0. 1798 El -0.2480 El -0.3283 El 0. 2379 El 0. 2805 El
-0.2511 -0. 5253 El -0.8912 El -0.5258 El -0.4009 E2 0.9514 El
-0. 2538 0. 1172 E2 -0.1457 El -0.3692 El 0.2571 E2 -o. 1084 El
-0.3799 -o. 1385 E2 -0.1321 E2 0.1978 El -0. 1169 E3 0. 1007 E2
0. 1105 0. 1350 El 0.1586 E2 0.1252 El 0.1106 E3 0. 3226 EO
0. 9007 -0. 5594 El 0.1660 E0 0.1498 El -0.1602 E2 0. 2722 El
0.7680 0. 0.7521
3864 El 0.4473 El -0.4705 El E2 -0. 1530 El
-0.5543 0. 2558 El -0.4116 El 0.7155 El -0.7146 E2 -0. 1139 E2
Standard errors in all data
0. 03414 0. 00976 0. 02842 0. 00934 0. 05798 0. 06296

VOL.3
1970

NO.2 155
 Table 8 Standard errors of estimate in f, yi using Eq. (4) From the above equations, rjl can be obtained.
for the system acetic acid-ethanol-water-ethyl acetate For the case of pure acetic acid, similar equations
Number of data points used; 247 can also be derived.
errors of vapor composition in all data [mol %~\ r]2A = K2aPa%A2
*[°C] yi yi ys
Vza = KsaPa'Via3
1 and
.95
1.87
1.46

Via+r]2A+7)za=1

Table 9 Parameters of the Wilson equations obtained from

binary data and standard errors of vapor compositions
3^1^ is calculated from Eqs. (8) and (9).
Then the activity coefficient is
Wilson's parameter Standard Ta=
System error Data Ti=
A12 Ai\ y[%~\ reference _ 7T#i (10)
Pa% a<J>a
acetic acid-ethanol 2.28180 1.93 Pi'Xi
acetic acid-water 1.22642 0.93
acetic acid-ethyl 0.89277 1.93 where vapor-phase fugacity coefficient (f>i is calculated
acetate by the Redlich and Kwongequation.
ethanol -water
ethyl acetate-ethanol
0.92038
0.76670 1.
1.28
61 A comparison of calculated and experimental results
ethyl acetate-water 0.14907 1.80 is given in Table 10. The agreement of the calculated
values determined from our experimental data and experimental data with esterification may be con-
sidered satisfactory, particularly if we remember that
Table IO Standard errors of estimate in t, yi using only binary equilibrium data with no reaction are used
Wilson's parameters obtained from binary data only for
the system acetic acid-ethanol-water-ethyl acetate for the prediction, and that the Wilson's constants are
considered independent of temperature in the range of
Number of data points used; 247 temperature studied. Then it is sufficient to express
errors of vapor composition in all data [mol %\
*[°C] yl
this quaternary system with esterification by the Wilson
equation if some further procedure may be considered
yi y* y*

2
.05
2.97
4.15
1.17

to express it more accurately by other equations.

4. Conclusion
where Aij is Wilson's constant.
The binary systems, which contain acetic acid, were
Quaternary vapor-liquid equilibria with esterification
treated with the consideration that dimers and trimers have been formulated, first using Margules model.
were present in acetic acid vapor, and the modified
activity coefficients175 were calculated using equilibrium
Activity coefficient may be related to liquid compositions,
constants of dimerization, K2 and of trimerization,
and second vapor-liquid equilibrium ratio maybe related
to temperature and liquid compositions used in our
Kz which were given by Potter and Ritter13). Wilson's graphical relationship reported previously.
parameters were calculated from these modified activity Both correlation of vapor-liquid equilibrium with
coefficients for the six binary systems. esterification on quaternary systems gives a reasonable
Table 9 presents the standard errors of calculated representation of the given system.
vapor compositions for the six binary systems. In all Next we tested Wilson equation for the system acetic
cases we found that the Wilson equation was in good acid-ethanol-water-ethyl acetate using the activity coef-
agreement with the experimental data. ficient, which is modified with association equilibrium
The extension of the binary system model to mixtures constants of dimerization and trimerization in acetic
containing more than two components follows in a acid vapor, and have come to the conclusion that it
straightforward way and does not require any additivity provides an excellent basis for a calculation of quaternary
assumptions. vapor-liquid equilibrium with esterification using only
The following equations represent the calculating
method for a quaternary system containing acetic acid.
experimental data for binary mixtures.
Between apparent vapor composition yi obtained from Nomenclature
the experiment and true composition r]k modified by
considering the association in acetic acid vapor, the Ak = regression coefficients denned by Eq. (l)
following relation may be derived17) Bi, Bij = constant defined by Eq. (2), i andj indicate com-
Vi+2?2+3^3 ponent and parameter, respectively.
Cic - regression coefficients defined by Eq. (4)
Fi, F2 - independent variables
(6) Ki = vapor-liquid equilibrium ratio of z-th component
K2, K3 = dimerization and trimerization equilibrium constants
y*= of acetic acid
Vi+2^2+3Vi
+Z Vjc K2A, Ksa = dimerization and trimerization equilibrium constants
d k=b of acetic acid in pure acetic acid
As with Eq. (6) Pi0 = vapor pressure in pure substance
3?2 = Knzr)? Q = Q function (=SxtInft)
(7) Xi = mole fraction in liquid phase
1)3 = KlTzW yt = mole fraction in vapor phase
156 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
T = absolute temperature (°K) 5) Hara, E., et al. : "Vapor-Liquid Equilibrium", Pergamon
t = temperature (°C) Press. (1958)
An = Wilson's parameter 6) (1966)
Hirata, M. and H. Komatsu: Kagaku Kogaku, 30, 129
Vt - true mole fraction in vapor phase
tu = total pressure 7) Hirata, M. and H. Komatsu: ibid., 30, 989 (1966)
Ti - activity coefficient 8) Hirata, M. and H. Komatsu: ibid., 31, 1184 (1967)
Subscripts 9)
10)
"International
"Kagaku Binran",
Critical
Maruzen (1952)
Tables", Vol. 3, McGraw-Hill
1, 2, 3 = monomer, dimer and trimer of acetic acid vapor in
Eqs. (6) to (10) ll) Lange, N. A., "Handbook of Chemistry", 10th Ed.
(1967)
A, B, C, D = acetic acid, alcohol, water and ester, respectively 12) Orye, R.V. and J.M. Prausnitz: bid. Eng. Chem., 57(5),
1A, 2A, 3A = monomer, dimer and trimer in pure acetic acid 18 (1965)
13) Potter, A. R, Jr., P. Bender and H. L. Ritter: J. Phys.
Literature cited Chem., 59, 250 (1955)
14) Redlich, O. and J.N.S.Kwong: Chem. Review, 44, 233
(1949)
1) Che?n.,
Altsheler,43, W.B., E.D. Unger and P. Kolachov : Ind. Eng.
2559 (1951) 15)10, Rius,
105
A.,
(1959)
J.L. Otero and A. Macarron: Chem. Eng. Sci.,
2) "Bussei Josuu", Vol. 13, P. 7, Maruzen (1965)
3) Ellis, S.R.H. andR.D. Carbett : Ind. Eng. Ckem.,52, 1385 16) Sebastiani, E. andL. Lacquaniti: Chem. Eng. Sci.,22, 1155
(1960) (1967)

4) 709Furnas, C.C. and W. B. Leighton : Ind. Chem. Eng., 29, 17)Zasshi,

Suzuki,72, I.,2178 T. (1969)
Ishikawa and H. Komatsu: Kogyo Kagaku
(1937)

EVALUATION OF THE WILSON PARAMETERS

BY NOMOGRAPHS"
KOREATSU MIYAHARA, HIDEO SADOTOMO
AND KAZUHIKO KITAMURA
Mitsui Toatsu Che?nicals, Inc., Tokyo

To evaluate the Wilson parameters from the activity coefficients in an infinitely dilute binary solution,
nomographs have been prepared which show the following features of the Wilson equation,
i. In a system of positive deviations from ideal behaviour only I set of parameters exists.
ii. In a system of negative deviations, I through 3 sets of parameters satisfy the Wilson equation.
By these nomographs/ the authors have evaluated the Wilson parameters for the acetone-chloroform
system, which give a good representation of the data.

To calculate vapor-liquid equilibrium relationships, to calculate the parameters, their initial value can be
many equations have been proposed2'8'n\ based on guessed with no difficulties). On the other hand, the
various models. Without losing effectiveness, it is Wilson equation is not a linear combination of parameters,
desirable that these equations be used with as few therefore the determination of the initial value is not
parameters as possible so long as accuracy is not sacrificed. always an easy matter. For this problem, Prausnitz
The Margules, van Laar and Redlich-Kister equations proposed several methods. These are, however, not clear
are typical and have been employed for many systems. to assure the uniqueness and convergenceof the solutions.
A new equation by Wilson, based on the theory of The authors have tried to obtain the Wilson parame-
Flory-Huggins10), was proposed in 1964.
Prausnitz et al.7) have successfully applied this equa- ters by nomographs which relate the parameters to the
tion to almost seventy systems and have shown that it activity coefficients in infinitely dilute solution and have
found that the parameters determined are sufficiently
accurately represents vapor-liquid equilibrium relationships accurate compared with the rigorous solutions obtained
with only two parameters. by an electronic computer.
These typical equations used before the Wilson equa-
tion are either linear with respect to the parameters
(Margules, Redlich-Kister) or suitable to obtain the Design of Nomograph
parameters from activity coefficients by simple calcula- The Wilson equation for the coefficients in a binary
tionsAs (van Laar).
a result, the parameters can be evaluated with
vapor-liquid equilibrium is as follows :
\nYi = - lnCri + ^i2x2)
ease (even if nonlinear estimation procedure is applied Al2 All
#21
* Received on September 1, 1969 Xi + A12X2 A21X1 + Xt

VOL.3 NO;2 1970