Activity Coefficient Relations in Miscible

and Partially Miscible Multicomponent Systems

Solke Bruin
Laboratory for Physical Technology, Eindhoven Uniuersity of Technology, Eindhoven, Netherlands

Based on a quasilattice model of a multicomponent solution, three equations are derived relating component
activity coefficients to the composition of a liquid mixture. The equations also apply to systems showing
limited miscibility. Temperature dependence of activity coefficients i s built in. The equations were tested for
16 binary systems, 5 of which show limited miscibility, and for 4 ternary systems. The enthalpic Wilson
equation, one of the three, gives the best prediction of binary vapor-liquid equilibrium. Both the enthalpic
Wilson equation and the Orye equations give good results of comparable accuracy for the ternary systems.

PREDICTION

of thermodynamic properties of mixtures from

pure component properties is the main goal of thermodynamics of liquid mixtures. Progress in this field has made
it possible to calculate the properties of a mixture of n components from the pure component properties supplemented with
experimental vapor-liquid equilibrium (VLE) data for all the
binary systems that can be constructed out of the n components: a total of l / 2 n ( n - 1) (Irausnitz et al., 1967). The
starting points of these computational methods are thermodynamic models of multicomponent mixtures, which provide
calculational procedures to predict the vapor-liquid equilibrium of the mixture from data on the binary systems. From
such models relations between the activity coefficients, y
and the composition of the liquid are derived. I n such relations, parameters characteristic of interactions between
pairs of molecules of different kind appear. Formally, such
activity coefficient relations have the form

Values for the interaction parameters, Pi, and P 3 ( , can be

calculated from VLE data on the binary system of components i and j .
The best known activity coefficient equations are, undoubtedly, the van Laar equations. These equations have
proved t o be very useful for binary systems but less satisfactory for multicomponent systems (Neretnieks, 1968; Orye,
1965; Orye and Prausniti, 1965; Prausnitz et al., 1967). The
two-parameter Wilson equation gives better results than the
van Laar equations for many binary and multicomponent
mixtures (Nagel and Sinn, 1966, 1967; Prausnitz et al., 1967;
Wilson, 1964a, b). No ternary or higher parameters are needed
in the generalization to multicomponent systems. Temperature dependence is t o some extent built into the Wilson
equations, making them suited to, for example, the isobaric
vapor-liquid equilibrium calculations commonly encountered
in distillation. An undesirable feature of the Wilson equations
is their inapplicability to partially miscible systems. The
modification of the equations that Wilson proposed to overcome this difficulty means introduction of a n extra parameter.
I n the present paper three activity coefficient equations
are discussed. These equations follow from the quasilattice

model of multicomponent liquid mixtures developed by

Guggenheim (1935, 1944a, b, 1952). This model yields a rather
general relation for the excess Gibbs f~inction,in which the
enthalpic and entropic contributions appear as separate
terms. Introduct>ion of van Laar or Wilson parameters into
this relation leads to a number of possible activity coefficient
equations including the van Laar and Wilson equations
themselves. I n Table I all poasible combinations of Wilson
paramet,ers (Aij), van Laar parameters (Aij), and Gibbs
function are given. The Orye equations (Orye, 1965) result
on introduction of Wilson parameters in the general relation
for the excess Gibbs function. Retaining only the enthalpy
part assuming the excess entropy to be ncgligible (regulm
solutions), yields enthalpic Kilson equations. The extended van Laar equations (EVL equations) result from
introduction of van Laar parameters into the general Gibbs
function, as indicated in Table I. Introduction of van Laar
parameters into the entropy part, assuming the ent,halpy to
be negligible (athermal solutions), gives equations unable to
predict partial miscibility (Bruin, 1969), and therefore is not
discussed.
The Orye, enthalpic Wilson, and EVL equations are
derived and discussed. The derivation of the Orye equations
here differs from that given originally by Orye. Subsequently,
the equations are generalized to multicomponent systems.
The equations were tested by application to 16 binary and four
ternary systems, prediction of parameters from infinite
dilution activity coefficients, and prediction of temperature
dependence of activity coefficients.
Binary Systems

The activity coefficient, yl, in a binary liquid mixture of

components 1 and 2 is given by the exact thermodynamic
relationship
In y1

947 10

[2-

(1)

dnl ( N g E / R T ) ]T , P , n %

where N is the total number of moles: N = nl

nz. The
molar excess Gibbs free energy of mixing, g E , in Equation 1 is
related to the excess molar entropy and enthalpy according t o
=

Present address, Western Utilization Research and Development Division, Agricultural Research Service, .4lbany, Calif.

hE

TsE =

UM

+ PvM

TsE

(2)

Adopting the quasilattice model for liquid mixtures of molecules of different size, a s developed by Guggenheim (1935,
Ind. Eng. Chem. Fundam., Vol. 9, No. 3, 1970

305

Table I.

Summary of Relations for g E Resulting from Different Combinations of Quasilattice

Equations and Parameters
Type of Parameter
Aii
Aij

(Wilson)

included

(van Laar)

++
+-

1
2
3
4
5
6

gE

hE-term

++
4++

+++

1944a, b, 1952), we may write the following equation for the

energy of mixing, uM, and the excess entropy:
sE = -R(zl In {rl/(rlzl

r24)

+
22

UM

ln{rz/(rlzl+

rs2)

1)

(3)
(4)

x12u12

I n Equation 3 rl is the number of sites in the quasilattice

structure occupied by a molecule of type 1. u12 represents a n
interaction energy:
UIZ =

/2~N(2~12
-

(5)

~ 1 1 WZZ)

N is the Avogadro number, w12 denotes the contribution to

the potential energy by a pair of sites, one of which is occupied
by a n element of a molecule of type 1, the other by an element of a different molecule of type 2; and z is the number of
nearest neighbors to a site, the coordination number.
I n Equation 4 XI2 is defined as the number of pairs of neighboring sites occupied by different molecules, one of which is
of type 1 and the other of type 2, divided by the total number
of nearest neighbor sites. T o calculate X ~ ZGuggenheim
,
introduced the quasichemical approximation

which is the mass-action law for a reaction where a molecule

1 is brought from a pure liquid 1to a (1-2) liquid mixture and
simultaneously a molecule 2 is brought from pure 2-liquid to
the (1-2) liquid mixture. I n this reaction (zX11) and (zX,)
bonds are broken up, while 2 ( 2 X 1 2 ) bonds are formed. The
number of 1-1 pairs and 2-2 pairs can be expressed as
22x11 = z

(rlz1

XIS)

(64

22x22 = z

(rs2 -

X12)

(6b)

(r14(rza)/(r1x1

(rlzJ(rs2)ud(rlz1

rE-term
included

Name of Resulting Equation for y i

++
+
+

Wilson
van Laar
Orye
Enthalpic Wilson
Extended Van Laar (EVL)

Renon and Prausnitz (1968) recently developed a relation

for g E in which the condition u12+ 0 on Equation 5a was relaxed. Moreover, distinction was made between the transfer
of a molecule 1 into the (1-2) liquid mixture [giving (zX12)
bonds] and the transfer of a molecule 2 into the (1-2) liquid
mixture [giving (zX2,) bonds]. The resulting relations for the
activity coefficients (NRTL equations) were shown to give
excellent representation of a wide variety of binary and
ternary liquid mixtures.
I n the present paper Equation 9 is used as a starting point
to derive activity coefficient equations. Guggenheim (1944b)
showed that the inaccuracy of Equation 9 is theoretically of
the order of ( u ~ ~ / R T ) ~ .
If one assumes in Equation 2 that h E = 0 (athermal solutions; Flory, 1942; Huggins, 1942) one obtains for g
gE/RT

In

rlxl

+r1 rsr2) +

TZXZ)

(7)

When Equations 3 and 8 are substituted in 2 and

assumed to be zero, one obtains for g E

(8)
UM

+ ra2)

(10)

~1x1

(12)

(VI/VZ)

Another assumption is due to Carlson and Colburn, in their

modification of the van Laar parameters:

m/RT

= A12

(13)

rluzl/RT = m/RT = A 2 1
(rl/r2)

equals

(A21/A12)

(rl/rd + ( A d A d

(14)

is
Parameters A12 and A 2 1 are sometimes called effective
molar volumes (Hildebrand and Scott, 1950).
Wilson suggested another expression for (n/n), taking
into account nonrandomness effects by weighting (uI/u2) with
a Boltzmann factor containing interaction energies X :
(r1/r2)-+ (u1/v2) exp

306 Ind. Eng. Chern. Fundarn., Vol. 9, No. 3, 1970

In

Equations 9 to 11 give three relations for QE as a function of

liquid composition in terms of the quasilattice parameters,
rl and r2, and the interaction energy, u12. To obtain twoparameter equations for y1 and y2 from Equations 9 to 11,
rl, rz, and u12 have to be combined to two parameters.
Different suggestions have been made. The most obvious
assumes the ratio (rl/r2)to be equal in a first approximation
t o the ratio of molar volumes (ul/u2) :

while u12 = u21.

The implication is that
rg2)

xz

On the other hand, if s E = 0 (regular solutions, van Laar;

Black, 1959; Black and Derr, 1963a, b; Wohl, 1946) Q E is
given by

rZu12/RT f

For UM one obtains

UM

-T~E

(rl/rJ

I n the particular case where all energies of mixing are zercall u12 -c 0 (all molecules distributed a t random)-combination of 5a and 6 gives
X12

= hE

{-

(Al2

- hm)/RT) = Apl

(15a)

and similarly for

(r2/r1)

(r2/T1)

- All)/RT]

exp { -(Alz

(v2/u1)

The EVL equations (17), enthalpic Wilson equations (20),

and Orye equations (21) were tested by

:
5

A12

(15b)

One can expect A12, All, and A22 to be proportional to zw12,

zwl1, and zws2 in Equation 5 . Therefore

u12/RT + (2A12 - All - An)/RT

-In

(A12h)

(16)

Equations 14 and 15 provide two reasonable choices (van

Laar and Wilson parameters, respectively) to introduce
parameters into Equations 9 to 11, giving six combinations.
I n Table I the combinations are indicated. Combining Equation 10 with Wilson parameters gives the Wilson equation.
Introducing van Laar parameters into Equation 11 gives the
van Laar equations. When van Laar parameters are introduced in Equation 10, a relation obtained is unable to predict
phase separation, in much the same way as the Wilson equation.
Extended van Laar (EVL) Equations. Substituting
A12parameters into Equation 9 and differentiating the resulting equation for gE according to Equation 1 gives for the activity coefficient, yl
In y1 = 1

- In (a

--

A1222/A21)

21

In

(22

+ A ~ ~ Z I / A I Z(17)) ~

(A1&)/(A21n

22)

r1

exp (-AdRT)
exp ( - A d R T )
xzvz exp (-A12lRT)

~1

y1 =

(21

22

In

(11121121)

A1252)(22

(19)

X
Azi~i)

For In y z the analogous expression results by rotation of

indices (1 + 2 + 1).
Orye Equations. Substitution of Kilson parameters in
Equation 9 gives equations for y derived by Orye (1965), who
used a different approach.
In

y1 =

Again, In

- In (zl + ~ ~ 2 x +
2 ) zz{ ~12/(zl+ A ~ ~z ~ )

y2

follows from rotation 1 + 2 + 1.

Table

II. literature Data for Systems Selected to Test

Activity Coefficient-Composition Equations
(Isobaric at 1 Atm)
Temp.
Range,

Comparison of Equations 19 and 15 illustrates that Equation

19 is exact only in the limit xl + 1. Substitution of Equation
19 in Equation 18 and differentiating gives
In

with m the number of data points. A nonlinear multiple

regression subroutine which adjusts the parameters of a
function being fitted to experimental data in such a manner
as to yield a least squares fit was written, following the
method of hfarquardt (1959). Details have been given (Bruin,
1969).
The results are summarized in Tables I11 to VII. Values

(18)

Postulating proportionality between the number of sites

occupied by a molecule of type 1 and the ratio between its
molar volume and a mean molar volume (weighted by interaction energies), one can write
VI

The EVL equations (17), enthalpic Wilson equations (20),

and Orye equations (21) were tested for 16 binary systems
listed in Table 11. All equilibria were isobaric (1 atm), in
order to test the built-in temperature dependence of the
equations; five systems show partial miscibility.
The fitting procedure proposed by Prausnitz et al. (1967)
was used. I n this procedure a correction for vapor-phase
nonideality is incorporated. The objective function, f, to be
minimized was defined as

Az1~2~

A122dA21

-r121zz

Comparison of Equations by Fitting Parameters

to Experimental Data on Binary Systems

The relation for In y~ results when indices are rotated in the

sequence 1 2
1. Equation 13 roughly predicts temperature dependence of A12 and A21,
Enthalpic Wilson Equations. Substituting Kilson parameters in Equation 11 gives

qE/RT =

Representation of 16 experimental binary vapor-liquid

equilibrium data from literature (T - 2 data a t constant P ) .
Prediction of parameter values for binary systems from activity coefficients a t infinite dilution.
Prediction of temperature dependence of activity coefficients a t infinite dilution (an extremely severe test).

System

"K

Reference

1. hIethano1-water

2. Ethanol-water
3. 1-Butanol-water
4. 2-Butanol-water
5. Acetone-water
6. Butanone-mater
7. Methyl acetatewater
8. Furfural-water
9. 2-Propanol-water
10. Icetone-methanol
11. Acetone-ethanol
12. Ethanol-2-propanol
13. Ethanol-benzene
( P = 750 mm
Hg)
14. Ethanol-methylc yclopentane
15. Methylcyclopentane benzene
16. hlethanol-ethanol

Uchida, 1934
Carey and Lewis, 1932
Stockhardt and Hull,
1931
Altsybeeva and
Belousov, 1964
Othmer et al., 1952
Othmer et al., 1952
hlarshall, 1906

338-69
351-68
372-84
364-66
330-61
330-61
329-60

International Critical
Tables, 1928
Wilson and Simons, 1952
Uchida et al., 1950
Hellwig and Van Winkle,
1953
Ballard and Van Winkle,
1952
Tyrer, 1912

371-432

342-47

Sinor and Weber, 1960

339-49

Griswold and Ludwig

1943
hmer et al., 1956

344-52

354-68
329-37
330-48
351-55

338-49

Ind. Eng. Chem. Fundam., Vol. 9, No. 3, 1970

307

Table Ill.

Fitting Results for Wilson Equations to Binary Systems

Parameters, col/mole

System

A12

Methanol-water
Ethanol-water
2-Propanol-water
Acetone-methanol
(isothermal)
Acetone-methanol
Acetone-ethanol
Acetone-water
llet'hanol-ethanol
Ethanol-2-propanol
Ethanol-benzene ( P =
750 mm Hg)
Ethanol-methylcyclopentane
Methylcyclopentane-benzene

Table IV.

- A11

A12

42.11
63.98
82.48
76.83

18.79
18.78
18,77
41.24

369.55
368.65
368.32
323.15

0.3612
1.1578
2.155
0.3442

. - 93.454

489.719
440.50
1489.07
-264.02
-241.331
119.80

78.47
79.82
81.42
42.93
62.825
61.82

42,07
62.27
18.67
63.39
83.11
94.61

337.15
348,25
361.0
349.75
355.05
342.6

0.6474
0.804
2.700
1.279
1.246
0.627

118.82
95.89

339.45
352.79

1.884
0.5890

- 64,236

469.02
198.85
215.889
1540.28
2230.23
13.68

236.08
253.694

Error in P
Total, %

Ai2

Azi

0.8649
1,6601
2.4260
3.8772
3.5447
0.6166

0.5210
0.8643
1.1625
1,1759
1.1387
0.5442

0.5713
0,4549
2.3880
3,5045
3.0565
4,6895
-0.5629
-0.01381
1.8341

0.3521
0.7246
1,2026
3.3491
1.4795
0,3083

0,6410
0.5170
0,7340
0.5871
4.4151
1 ,4555
5.1996
1 ,6525
5,5212
1,8050
27.5862
1.1008
-0.0580
0.5691
-0.006945 1.462
1.2814
0,3565

2.7404

1.6889

2.771

0.3259

0.3505

0.5796

for (XIZ - AH), ( A ~ z - XZZ), 12, and 21 are computed a t the

temperatures indicated in the tables. As a reference, the Wilson and van Laar equations were also checked. General trends
are that EVL equations (17) give poor results when compared to the van Laar equations. A remarkable result is that
the enthalpic Wilson equation (20) gives very good represen-

Table V.
System

Methanol-water
Ethanol-water
1-Butanol-water
2-Butanol-water
Acetone-water
Butanone-water
Methyl acetate-water
Furfural-water

308

Error in P
Total, %

472.368
910.615
1358.35
472.74

Parameters

Methanol-water
Ethanol-a ater
2-Propanol-water
1-Butanol-water
2-Butanol-water
Acetone-methanol
(isothermal)
Acetone-methanol
Acetone-ethanol
Acetone-water
Butanone-water
Methyl acetate-water
Furfural-water
Methanol-ethanol
Ethanol-2-propanol
Ethanol-benzene
( P = 750 mm Hg)
E t hanol-methylcylopentane
hfethylcyclopentanebenzene

F, O K

198.113
380.315
543.845
-54.175

Fitting Results for van Laar Equations to

Binary Systems

System

Molar Volumes, Cm3/Mole

v1
V2

- A22

61.58
120.66

tation for most of the systems, in many cases bett,er than the
van Laar or Orye equations (21).
Prediction of Parameter Values from
Infinite Dilution Coefficients

For In yl a t infinite dilution of component 1 in a binary

mixture one can derive
For EVL Equations
In

ylm =

1 - In (AIz/AzI) - A Z ~ A I ZAZI

For Enthalpic Wilson Equations

In

ylm =

-In

(24)

(A12h)/An

For Orye Equations

In

ylm =

1 - In

111-2

AZI - In

(hlzA21)/Az1

Ail

0.6021
0.9875
1.5696
1.5093
1.4392
1.8041
1.6971
1 ,7366

1 ,0429
1.9225
4.6182
4.2917
2.5208
3.7793
3.1399
5.4891

Ind. Eng. Chem. Fundom., Vol. 9, No. 3, 1970

(25)

Similar relations follow for In yz" by letting 1 + 2 + 1.

If In ylmand In yZmare known-e.g., from Pierotti-Deal-Derr
correlations (Pierotti et al., 1959) or Helpinstill and Van
Winkle correlations (1968)-parameter values can be calculated.
Solving Equation 25 and the similar relation for yZmfor
A12 and A21 is tedious, requiring a double iteration scheme.
Therefore the Orye equations were not tested.
For the EVL and enthalpic Wilson equations convenient
computational methods have been discussed (Bruin, 1969).
Some results for the EVL equation are summarized in Table
VIII. I n Figures 1 to 3 y's and activities, a, are plotted for
acetone and water, 1-butanol and water, and 1-octanol and

Fitting Results for EVL Equations to Binary Systems

Ai2

(23)

Parameters
21, cal/mole

ell, col/mole

442.194
723.459
1162.336
1093.13
1032.47
1282.593
1214,279
1282.762

765,917
1408,405
3419.983
3108,21
1808.370
2686.815
2246.585
4054.630

r,

OK

369.55
368.65
372.65
364.45
361.00
361.00
360.05
371.71

Error in P
Total, %

0.3616
0,6503
4.0834
1.7815
5.2401
5.5858
6.3476
24.1892

Fitting Results for Enthalpic Wilson Equations

Table VI.

Parameters, CaI/Mole

- xi1

XlZ

System

Methanol-water
Ethanol-water
2-Propanol-water
1-Butanol-water
2-Butanol-water
Acetone-methanol
Acetone-ethanol
Acetone-water
Butanone-water
Methyl acetate-water
Furfural-n-ater
Methanol-ethanol
Ethanol-2-propanol
Ethanol-benzene ( P =
750 mm Hg)
Ethanol-methylcyclopentane
Methylcyclopentane-benzene

Molar Volumes, Crn3/Mole

- A22

XlZ

-208.7681
- 325,7964
- 423.065
-357.8748
- 279.327
-216.966
-116.696
-436.468
-396.248
-419.1093
-202.367
188.7053
-1329.7304
745.400

571.3078
897.1059
1150.147
1229.9084
1098,612
506.093
399.150
1185.436
1307.900
1290.6923
1158.676
-3290.622
1267.75
- 76.970

1006.585
- 35.740

- 182.718
238.011

Parameters, CaI/Mole
A12

Methanol-Tyater
Ethanol-water
2-Propanol-water
1-Butanol-water
2-Butanol-water
Acetone-methanol
Acetone-ethanol
Acetone-water
Butanone-water
Methyl acetate-water
Furfural-water
Methanol-ethanol
Ethanol-2-propanol
Ethanol-benzene
( P = 750 mm Hg)
Ethanol-methylcyclopentane
Methylcyclopentane-benzene

- XI1

A12

450.860
747,2929
962.733
1043.374
921.84
408.528
- 84,774
1023.049
1122.348
1290.692
970.618
1,2133
213,857
- 197.128

-211.440
-348.018
-435.954
-369.779
- 279,327
- 235.9306
243.84
-479.035
-435.140
-419.1093
-231.3797
- 7.4205
- 179.812
654.954

-330.439

931 ,4907

- 53,107

167.237

~~

1, O K

System

Table IX.

44,548
63.977
82.48
98.366
85.668
78.47
79.82
81 ,420
89.533
87.373
82.899
42.94
62.82
61.82
61.58
120.66

18.792
18,779
18.77
18.837
18.721
42.07
62.27
18.675
18,633
18.663
18.823
62.39
81.43
94.61
118.82
95.89

1, O K

Error in P
Total, %

369.55
368.65
368.32
372.65
364.45
337.15
348,25
361.00
361.00
329.63
371.71
349.75
355,05
342.6

0.3473
0.6506
1.1245
4.1245
1.6216
0.654
0.8046
3,2695
4.1933
3.4580
23.0276
0,4790
0.3871
0.3938

339.45
352.79

2.3874
0.5921

Molar Volumes, Cm3/Mole

- A22

v1

r,

v2

18.791
18.779
18.77
18.837
18.721
42,07
62.27
18.675
18.633
18,663
18.823
62.392
81.43
94,61

44,548
63,977
82,47
98.366
85.688
78.47
79.82
81,420
89.533
87.373
82.899
42,935
62.82
61.23
61,58
120.66

118.82
95.89

OK

Error in P
Total, %

369.55
368.65
368.32
372.65
364.45
337.15
348.25
361.00
357.75
329.63
371,71
349.75
355.05
342.60

0.3479
0.7323
1.1650
4,4161
1,7331
0.6566
3.380
4.0037
4.9331
4.4630
23,2258
1.3748
1.372
0.4385

339.45
352.79

2.7651
0.6113

~~

Table VIII.
A-Parameters Estimated from Infinite
Dilution Values for Activity Coefficients

Acetone-\\ atera
373 15
2-Heptanone-waterb
298 15
1-Butanol-water*
298 15
1-Octanol-waterb
298 15
Acetone-1-octanolb
373 15
l-Butanol-1373 15
octanolc
2-Heptanone-l373 15
octanolb
Othmer, 1952* Pierrotti,
1959. c Wilson and Deal, 1962.

V2

Fitting Results for Orye Equations to Binary Systems

Table VII.
System

v1

An

Ai2

1 5745
2 1590
1 6545
2 2763
3 6702
3 5548

5228
8669
6425
6137
8224
6639

8
7
7
7
6
6

0 8354

2
9
4
11
0
1

1 8025

No. of
Iterations

water. Results for acetone and water are compared with the
data of Othmer (1952). Phase separation is predicted for 1butanol and water and 1-octanol and water a t approximately
the right liquid compositions, as can be seen from the activitycomposition plots.
The enthalpic Wilson equation was tested using methanol
and water, ethanol and water, and 1-butanol and water.
Table IX gives values for (Alz - All) and (A12 - h 2 2 ) computed
from ylmand y 2 " . Reasonable agreement exists between values
computed from Equation 24 and those given in Table VI.
I n Figure 4 a graph is given for binary systems with positive
deviations from ideality, from which A 1 2 and Azl follow
directly when ylm and 7 2 " are known. The procedure is
illustrated for methanol (1)
water (2): In ylm = 0.521,
In yz" = 0.865. FromFigure 4: A12 = 0.60 (point 1). Interchange of indices gives coordinates of point 2: A21 = 1-00.

and Derr

Estimated A Parameters for Enthalpic Wilson Equations (20) from Activity Coefficients at Infinite Dilution
(ENTLAM program)
System

Aiz

Azi

(A12

- Azz)

(Xi2

1. Methanol-water. (338-72K)
0.5990
0.9944
- 257.553
2. Ethanol-water. (351-72'K)
0.4832
0.9280
- 364.712
3. 1-Butanol-waterb (372-80K)
0.3049
1.0054
- 344.979
a Stockhardt and Hull, 1931. Pierrotti, Deal, and Derr correlations, 1959.

- A221

638.017
952.309
1220.01

Temp.,

OK

369.55
368.65
372.65

~~

Ind. Eng. Chem. Fundam., Vol. 9, No. 3, 1970

309

I-Butanol (1)-Water (2)

T = 298 O K

A 12" 1.6545

XI

Figure 2.
system

X,=aons

i,=0.540

xI+

Activity and activity coefficients for the 1-butanol (1)-water

Prediction of Temperature Dependence of ylmand yzm

The temperature dependence of activity coefficients is given

by the exact thermodynamic relation

(2

For the EVL equations one obtains by differentiation of

Equation 17 and taking the limit zl + 0,

assuming e12 and to be independent of temperature.

The enthalpic Wilson equation gives
where Hio is the enthalpy of component i in the standard
state and Riis the partial molar enthalpy of mixing. At
infinite dilution of component i,

310 Ind. Eng. Chem. Fundam., Vol. 9, No. 3, 1970

I\

2 k -t-

12Or-

AIZ= 2.2763

I I6137
T = 298'K

A21'
~

XI

Figure 3.
system

System

loo--

System
I-Octanol(l)+Water(2)

XI

Activity and activity coefficients for 1 -octanol (1)-water (2)

2.:
8

-x"
C

I*.(
1.5

I .c

0.5

0.0
In Yla,
for enthalpic Wilson equation from In ylm and In y2m
__c

Figure

4. Nomogram giving

.211

and

Ind. Eng. Chem. Fundom., Vol. 9, No. 3, 1970

31 1

The Orye equation yields

gives the predicted temperature dependence of In ylm and

water (2) for the EVL,
In yz" in the system methanol (1)
enthalpic Wilson, and Orye equations. Experimental data
from Perry (1963) are also given.
It is evident that the predicted temperature dependence is
poor for all equations. The enthalpic Wilson equation appears
to give results closer to the experimentally observed values for
the temperature dependence of In ylm than the Orye equation.
It must be admitted that the test of predicting temperature
dependence of activity coefficients is extremely severe. The
conclusion is that ( ~ I Z- A l l ) and (A12 - A l l ) must have some
dependence on temperature.

Rotation of indices in the sequence 1 2 1 gives similar

relations for the temperature dependence of In 72". Figure 5
-)r

WILSON EWATIONS FOR FOUR TERNARY SYSTEMS

I' + acetone ; x methanol; w t e r
II: acetone ; * methand;. ethonol
o ethanol ; 1%-popanol : water
E: uethanol ; imethylcyclopentane: o benzene

m:

"1I

0.6

Yexp.

0.5 -

0.4

0.3-

3.0

2.5

4.0

3.5
( '/T)XIO~

(OK-')

Figure 5. Predicted temperature dependence of In yim

for system methanol (1)-water (2)

Ycolc

Figure 7.

-- Enthalpic Wilson equation

-*

- O r y e equation

Fit of Wilson equation to ternary VLE data

0 Experimental d a t a

_ - _ -EVL equations

ENTHALRC WILSON EOUATONS FOR FOUE TE3hARY SYTER'S

1: + acetone: x methanol; e water
II: acetone : tr methanol; ethanol
E:o ethanol ; iso-propanol;* water
E: ethonol ; * methylcyclopentane : o benzene

li

VAN LA& EQJATIOK FOR FOUR TERNARY SYSTEMS

I: + ccetone; x methanol; e w t e r
II: acetone ; li methanol: ethanol
a: oethanol ; is0 ptopanol;* water
o,8- E:o ethanol ; * methylcyclopentone; o benzene
@"-

0.6

Yexp.
0

0.6
0'7:

0.5 -

0.4

//
0 0 6 .

*f
0,

0.2

312

02

03

0.4

0.5

06

07

08
YCOlC

Figure 6.

0.3-

0
0

Yexp.

09

Fit of van Laar equations to ternary VLE data

Ind. Chem. Fundam., Vol. 9, No. 3, 1970

0.1

I0

Figure 8.
data

0.2

0.3

0.4

0.5

06

0.7

0.8

0.9

I!

kale
Fit of enthalpic Wilson equations to ternary VLE

I I
-

EQUA';!OP.IS

CRYE

FOR FOJR TERNARY SYSTEMS

Table X. Ternary Systems Used to Test Enthalpic

Wilson and Orye Equations (Isobaric at 1 Atm)

I. + acetzne; x retnono ; e wo:er

G.9 II. ccetoie ; tr rneinmol; ethanol
m:oetccnc! : + is0 D ~ O ~ G C O ~wafer
:+
O,s-E.
oehcnol ; * rnethylcyclopentane; o benzene

System

1. Acetone-methanol-water
2. hcetone-methanolethanol
3. Ethanol-2-propanolwater
4. Ethanol-methylcyclopentane-benzene

0.7tt

C.,

G2

0.3

04

05

G.7

06

0.8

0.9

kaic

Figure

9. Fit of Orye equations to ternary VLE data

Multicomponent Systems

The EVL equations (17), enthalpic Wilson equations (20),

and Orye equations (21) can be readily extended t o multicomponent systems. I n fact, the quasilattice model of Guggenheim (1944a, b, 1952) was developed for multicomponent
systems. I n the zeroth approximation only two-body interactions are taken into account and therefore the Gibbs free
energy is obtained by a summation procedure.
The EVL equation is not discussed here, as it is clear from
Table V that this equation gives rather poor results. The
enthalpic Wilson equation for a multicomponent mixture
becomes
25 111 (A15Aji)
ff4j

xjxm

Reference

1n (AjrnArnj)
aiim

(31)

a#j#m

Griswold arid Buford, 1949

hmer, Paxton, and Van
Winkle, 1956
Kojima, Ochi, and Sakawaza,
1969
Sinor and Weber, 1960

eters A i j and A j i (Tables I11 to VII), and the values obtairied

were used in bubble temperature calculatioiis using the
programs described by Prausnitz et al. (1967). Pure component properties were t.aken from the literature. Critical
pressures and temperatures were taken from the literature or
in some cases calculated with Lyderseri correlations (Reid
and Sherwood, 1958). Acentric factors, dipoles, and vapor
pressure data were taken froni Prausnitz et nl. (1967) and
O'Connell and Prausnitz (1964).
I n Figures 6 to 9 the computed vapor compositions for a
number of liquid compositions for each syst.ern are compared
wit,h t,he experimental compositions as reported in the references given in Table IX. As a reference, the results for the
van Laar and Wilson equations for the same four ternaries
are also given.
Conclusions are that the enthalpic Wilsori and the Orye
equations give a considerably better fit of vapor-liquid equilibrium in ternary systems than the van Laar equat'ions. The
van Laar equation gives a good fit for t'he acetone-methanolwater system, but poor results for the ethanol-methylcyclopentane-benzene and ethanol-2-propanol-water syst.ems.
The Wilson equation gives a very good fit of VLE data for the
ethanolmethylcyclopentane-benzene system. The results for
the ethanol-2-propanol-water syst.ern, however, are approximately of the same accuracy as t'he enthalpic Wilson and
Orye equations. For syst'ems near to phase separation or for
systems showing phase separation, the enthalpic or Orye
equations are recommended. For other systems, the Wilson
equations are attractive to use.
Acknowledgment

The Orye equations for a multicomponent mixture are

In Y i

1 - In

(,

)-Z($q-

Aipxp

The author is grateful to the Computer Center of the

Eindhoven University of Technology for the use of its facilities. Especially the assistance of Marijke ter Morsche is gratefully acknowledged.
Literature Cited

Amer, H. H., Paxton, R. R., Van Winkle, RI., Znd. Eng. Chem.
48. 142 f18.56).
\ - - - - , -

Altsib&va, A. I., Belousov, V. P., Russian J . Phys. Chem. 38 ( 5 ) ,

676-8 (1964).
Ballard, L. H., Van Winkle, >I., Znd. Eng. Chem. 44, 2450 (1952).
Black, C., Znd. Eng. Chem. 51, 211 (1959).
Black, C., Derr, E. L., Papadopoulos, 31.N., Znd. Eng. Chem.
55 f81.
40
~.,,
~.il863a1.
~~~..~.,.

Equat>ions31 and 32 were tested on four ternary systems

listed in Table IX. Binary VLE data were reduced to param-

Black, C., Derr, E. L., Papadopoulos, hI. N., Znd. Eng. Chem.
55 (9), 38 (1963b).
Bruin, S., doctoral thesis, Agric. University Wageriirigen; Publication 48, L. E. B. Foundation, 1960.
Carey, J. S., Lewis, W. K., Znd. Eng. Chem 23, 882-83 (1932).
Flory, P. J.,J. Chem. Phys. 10, 51-61 (1942).
Griswold, J., Buford, C. B., Znd. Eng. Chern. 41, 2347 (1949).
Griswold, J., Ludwig, E. E., Ind. Eng. Chem. 35, 117 (1043).
Guggenheim, E. A., Proc. Roy. SOC.A 148,304-12 (t935).
Guggenheim, E. A., Proc. Roy. SOC.A 183,203-12 (1944a).
Ind. Eng. Chem. Fundam., Vol. 9, No. 3, 1970

313

Guggenheim, E. A,, Proc. Roy. SOC.A 183,213-27 (1944b).

Guggenheim, E. A., Mixtures, Chap. XI, Clarendon Press,
London, 1952.
Hellwig, L. R., Van Winkle, hl., Znd. Eng. Chem. 45, 624 (1953).
Helpinstill, J. G., Van Winkle, M., Ind. Eng. Chem. Process

Pierrotti, G. J., Deal, C. H., Derr, E. L., Znd. Eng. Chem. 51 ( l ) ,

Hildebrand, J. H., Scott, R. L., Solubility of Non-electrolytes,

3rd ed. 133, Dover Publications, New York, 1950.
Huggins, I%., Ann. N . Y . Acad. Sci. 43, art. 1, 1-32 (1942).
International Critical Tables, McGraw-Hill, New York, 1928.
Kojima, K., Ochi, K., Nakawaza, Y., Intern. Chem. Eng. 9 (2),

Rejdy R , C., Sherwood, T. K., Properties of Gases and Liquids,

pp. 7-25, PvlcGraw-Hill, New York, 1958.
Renon. H.. Prausnitz, J. hI., A.Z.Ch.E. J . 14 ( l ) ,135-44 (1968).
Sinor, J. E., Weber, J: H., J : Chem. Eng. Data 5,244 (1960).
Stockhardt, J. S., Hull, C. M., Znd. Eng. Chem. 23, 1438-40

Design Develop. 7, 213-20 (1968).

342 (1969).

Merquardt, D. W., Chem. Eng. Progr. 55 (6), 65-70 (1959).

Marshall, N., J . Chem. SOC.89, 1350 (1906).
Nagel, O., Sinn, R., Chem. Ing. Techn., 38 (lo), 265 (1966).
Nagel, O., Sinn, R., Chem. Zng. Techn. 39 ( l l ) , 671-6, 275-82
(1967).

Neretnieks, I., Ind. Eng. Chem. Process Design Develop. 7, 335-9

(1968).

OConnell, J. P., Prausnitz, J. M., IND.

ENG.CHEM.FUNDAM.
3,
347 (1964).

Og% R. V., Ph.D. dissertation, University of California,

erkeley, Calif., 1965.
Orye, R. V., Prausnitz, J. M., Znd. Eng. Chem. 57 ( 5 ) , 18 (1965).
Othmer, D. F., Znd. Eng. Chem. 44, 1872 (1952).
Othmer, D. F., Chudgar, M. M., Levy, S. L., Znd. Eng. Chem.
44, 1872-8 (1952).
Perry, J., ed., Chemical Engineers Handbook, 4th ed., Chap.
13, New York, 1963.

95-102 (1959).

Prausnitz, J. R.I., Eckert, C. A., Orye, R. V., OConnell, J. P.,

Com uter Calculations for Multicomponent Vapor-Liquid
Equiligria, Chap. 1-6, Prentice-Hall, Englewood Cliffs, N. J.,
1m

(1931).

Tyrer, D., J . Chem. SOC.,101, 1104 (1912).

Uchida, S., Chemical Engineers Handbook, J. Perry, ed.,
Chap. 13, 4th ed., McGraw-Hill, New York, 1934.
Jchida, S.,.
Ogawa,S., Yamagusti, M., J CIpan. Sci. Rev. Ser. Z.
Eng.Sci, 1,No. 2, 41 (1950):

Wilson, A., Simons, E. L., Znd. Eng. Chem. 44,2214 (1952).

Wilson. G. Pvl.. J . Amer. Chem. SOC.84. 127-33 (1964a).
Wilson: G. M.; J . Amer. Chem. SOC.84; 133-7 (1964b).
Wilson, G. >I., Ileal, C. H., IND.ENG.CHEWFUNDAM.
1, 20-3
(1962).

Wohl, K., Trans. Amer. Inst. Chem. Engrs. 42, 215 (1946).
RECEIVED
for review December 23, 1968
ACCEPTEDMay 1, 1970
Work supported by the L. E. B. Foundation, Wageningen.

Thermal Reaction of Propylene

Kinetics
Taiseki Kunugi, Tomoya Sakai, Kazuhiko Soma, and Yaichi Sasaki
Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo, Hongo, Tokyo, J a p a n

Kinetics of the thermal reaction of propylene was studied at temperatures ranging from 703 to 854C.,
atmospheric pressure, and residence times from 0.078 to 3.3 seconds with and without nitrogen dilution.
Main primary products were ethylene, methane, hydrogen, butenes, and butadiene in the approximate
ratio of 5 : 3 : 1 : 1 : 1 at initial stages of the reaction. Other primary products were methylcyclopqntene,
hexadienes, acetylene, and ethane. Secondary products were cyclopentadiene, benzene, polycyclic
aromatics, cyclopentene, and toluene. Selectivities of formation of these products, except acetylene and
ethane, showed little dependence on temperature. At higher partial pressure of propylene, the selectivities of ethylene and methane formation decreased to some extent. The effect of partial pressure
of propylene on the rate of propylene disappearance leads to a three-halves-order equation. The rate
constant is given as

k = 105*06

of propylene has been studied extensively (Amano and Uchiyama, 1963; Kallend et aZ., 1967;
Laidler and Wojciechowski, 1960; Sakakibara, 1964; Wheeler
and Wood, 1930). A few experiments at temperatures from
700 to 850 and atmospheric pressure cover the conditions
of the industrial manufacture of olefins and aromatics by
cracking hydrocarbon feedstocks. Analyses of the products
have been limited to lighter hydrocarbons below CCor the
products formed in narrow ranges of temperatures and conversions. Lack of clear discrimination between the primary
and secondary products is due t o these limited analyses of
the products.
T H E R M A L REACTION

3 14

Ind. Eng. Chem. Fundam., Vol. 9,

No. 3, 1970

cc>/z/(mote/z sec.).

Reaction products were analyzed in detail to differentiate

the primary from the secondary products. The kinetics of the
thermal reaction of propylene was discussed in comparison
with that of ethylene. I n a following paper mechanisms of the
reaction and of formation of higher hydrocarbons above CS
are to be discussed.
Experimental

Feed propylene was 99.35 mole % pure by gas chromatographic analysis, used without further purification. The impurity was propane, 0.65 mole yo.Oxygen content was less
than 1 p.p.m. by weight. Commercially available nitrogen