Computerized Design of Multicomponent Distillation Columns Using
the UNIFAC Group Contribution Method
for Calculation of Activity Coefficients
Aage Fredenslund," Jurgen Gmehling,2Michael L. Mlchelsen,' Peter Rasmussen,' and
John M. Prau~nitz"~
lnstituttet for Kemiteknik, The Technical University of Denmark, DK-2800 Lyngby, Denmark, Abteilung Chemietechnik, Lehrstuhi
Technische Chemie B, University of Dortmund, 46 Dortmund 50. West Germany, and Department of Chemical Engineering, University of
California, Berkeley, California 94720
The UNIFAC group-contribution method for estimating activity coefficients provides the process engineer with a
rapid and reliable method for predicting equilibrium conditions required in distillation-column design.
Introduction
A large part of chemical engineering design is concerned
with separation operations. Many of these are diffusional
operations of the phase-contacting type, and distillation,
absorption, and extraction are the most common. For rational
design of such separation processes, we require quantitative
information on phase equilibria in multicomponent mixtures.
Satisfactory experimental equilibrium data are only seldom
available for the particular conditions of temperature, pres-
sure, and composition required in a particular design problem.
It is therefore necessary to interpolate or extrapolate existing
mixture data or, when suitable data are lacking, to estimate
the desired equilibria from some appropriate correlation. A
very useful correlation for this purpose, UNIFAC, was recently
proposed. It is the aim of this work (1)to review the essential
ideas of IJNIFAC, to report extensive modifications and ex-
tensions of the UNIFAC parameters required for its use, and
to present illustrative examples that indicate the extent and
reliability of UNIFAC for making quantitative estimates of
phase equilibria; and (2) to show how UNIFAC, coupled with
material- and energy balances, may be used to design multi-
component distillation columns.
The UNIFAC Method
UNIFAC is an abbreviation that indicates Universal
quasichemical Functional Group Activity Coefficients. It is
based on the quasichemical theory of liquid solutions proposed
by Guggenheim (1952), generalized by Abrams and Prausnitz
(1975), and applied to functional groups within the molecules
(rather than the molecules themselves) by Fredenslund et al.
(1975).
In process design, the required phase equilibrium infor-
mation is commonly expressed by K factors
where y , is the mole fraction of component i in the vapor phase
and x , is the mole fraction of component i in the liquid phase.
Using standard thermodynamics
Tlfl O
K, = -
PlP
where y, is the liquid-phase activity coefficient, f L O is the
standard-state fugacity, pL is the vapor-phase fugacity coef-
ficient, and P is the total pressure. For condensable compo-
' Technical University of Denmark.
University of Dortmund.
University of California.
450 Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977
nents as considered here, fin is the fugacity of pure liquid i a t
system temperature T and pressure P ; as shown elsewhere
(Prausnitz, 1969) it is calculated from
(3)
where, for pure liquid i, Pis is the saturation (vapor) pressure,
pisis the fugacity coefficient a t saturation, and u, is the molar
liquid volume, all a t temperature T . Only pure-component
data are required to evaluate f i n .
The fugacity coefficients cpi (in the mixture) and pIS(pure
i a t saturation) are found from vapor-phase volumetric
properties. Normally, a t the low pressures considered here,
these fugacity coefficients do not deviate much from unity.
While various methods are available to calculate fugacity
coefficients, we have here used the method of Hayden and
O'Connell(l975) as briefly summarized in Appendix C.
T o determine K factors, the most difficult-to-estimate
quantity is the activity coefficient y. UNIFAC provides a
method for estimating activity coefficients in nonelectrolyte
liquid mixtures remote from critical conditions. T o use this
method, no experimental data are required for the particular
mixture of interest. In addition to the temperature and com-
position of the system, it is necessary only to know the mo-
lecular structure of every component in the mixture and the
necessary group parameters. A large number of group-inter-
action parameters is given here.
The large advantage of a group-contribution method is that
it enables systematic interpolation and extrapolation of
vapor-liquid equilibrium data simultaneously for many
chemically related mixtures. Most important, it provides a
reasonable method for predicting properties of mixtures where
no mixture data at all are available. For such mixtures it is not
necessary to measure the intermolecular interactions because
these can be calculated whenever appropriate group-inter-
action parameters are known. These, however, are found from
experimental data containing not the same molecules as those
in the mixture of interest, but containing the same groups. The
main advantage, then, is a form of "molecular scale-up." While
(2) there are many thousands of liquid nonelectrolyte mixtures
of interest in chemical technology, these mixtures can be
constituted from a much smaller (perhaps 50 or 100) number
of functional groups.
Langmuir (1925) suggested that physical (van der Waals)
interactions between polyfunctional molecules may be esti-
mated by summing interactions between the functional groups
that constitute the molecules. Typical functional groups might
Table I. Group Volume and Surface Area Parameters
Group name0 Rk Qk Sample group assignment
0.9011 0.848 Butane: 2 CH,, 2 CH,
“CH,” 0.6744 0.540
0.4469 0.228 i-Butane: 3 CH,, 1 CH
0.2195 0.000 2,2-Dimethylpropane 4 CH,, 1 C
CH,=CH 1.3454 1.176 1-Hexene: 1 CH,, 3 CH,
1 CH,=CH
CH=CH 1.1167 0.867 2-Hexene: 2 CH,, 2 CH,,
“C=C”
1 CH=CH
CH=C 0.8886 0.676 2-Methylbutene-2: 3 CH,, 1 CH=C
1.1173 0.988 2-Methylbutene-1: 2 CH,, 1 CH,, 1 CH,=C
“ ACH”
0.5313 0.400 Benzene: 6 ACH
0.3652 0.120 Styrene: 1 CH,=CH, 5 ACH, 1 AC
ACCH, 1.2663 0.968 Toluene: 5 ACH, 1 ACCH,
“ACCH,” ACCH, 1.0396 0.660 Ethylbenzene: 1 CH,, 5 ACH, 1 ACCH,
0.8121 0.348 Cumene: 2 CH,, 5 ACH, 1 ACCH
1.8788 1.664 1-Propanol: 1 CH,, 1 CH,CH,OH
1.8780 1.660 2-Butanol: 1 CH,, 1 CH,, 1 CHOHCH,
“CCOH” CHOHCH, 1.6513 1.352 3-Octanol: 2 CH,, 4 CH,, 1 CHOHCH,
CH,CH,OH 2.1055 1.972 Ethanol: 1 CH,CH,OH
CHCH,OH 1.6513 1.352 Isobutanol: 2 CH,, 1 CHCH,OH
CH,OH 1.4311 1.432 Methanol: 1 CH,OH
H,O 0.92 1.40 Water: 1 H,O
ACOH 0.8952 0.680 Phenol: 5 ACH, 1 ACOH
CH,CO 1.6724 1.488 Ketone group is 2nd carbon;
2-Butanone: 1 CH,, 1 CH,, 1 CH,CO
“CH ,C0” CH,CO 1.4457 1.180 Ketone group is any other carbon;
3-Pentanone: 2 CH,, 1 CH,, 1 CH,CO
CHO 0.9980 0.948 Acetaldehyde: 1 CH,, 1 CHO
CH,COO 1.9031 1.728 Butyl acetate: 1 CH,, 3 CH,, 1 CH,COO
“COOC” CH,COO 1.6764 1.420 Butyl propanoate: 2 CH,, 3 CH,,
1 CH,COO
1.1450 1.088 Dimethyl ether: 1 CH,, 1 CH,O
“CH,O” 0.9183 0.780 Diethyl ether: 2 CH,, 1 CH,, 1 CH,O
0.6908 0.468 Diisopropyl ether: 4 CH,, 1 CH, 1 CH-0
0.9183 (1.1) Tetrahydrofuran: 3 CH,, 1 FCH,O
CH,NH, 1.5959 1.544 Methylamine: 1 CH,NH,
“CNH,” 1.3692 1.236 n-Propylamine: 1 CH,, 1 CH,, 1 CH,NH,
1.1417 0.924 Isopropylamine: 2 CH,, 1 CHNH,

“CNH” { CH,NH
CH,NH
CHNH
1.4337
1.2070
0.9795
1.244
0.936
0.624
Dimethylamine: 1 CH,, 1 CH,NH
Diethylamine: 2 CH,, 1 CH,, 1 CH,NH
Diisopropylamine: 4 CH,, 1 CH, 1 CHNH
’ ACNH, 1.0600 0.816 Aniline: 5 ACH, 1 ACNH,
CH,CN 1.8701 1.724 Acetonitrile: 1 CH,CN
“CCN”
{CH,CN 1.6434 1.416 Propionitrile: 1 CH,, 1 CH,CN
“COOH”
3COOH
HCOOH
1.3013
1.5280
1.4654
1.224
1.532
Acetic acid: 1 CH,, 1 COOH
Formic acid: 1 HCOOH
1.264 Butylchloride: 1 CH,, 2 CH,, 1 CH,Cl
“CC1” 1.2380 0.952 Isopropyl chloride: 2 CH,, 1 CHCl
0.7910 0.7 24 tert-Butyl chloride: 3 CH,, 1 CC1
2.2564 1.988 Dichloromethane: 1 CH,Cl,
“ CCl, ” CHC1, 2.0606 1.684 1,l-Dichloroethane: 1 CH,, 1 CHC1,
1.8016 1.448 2,2-Dichloropropane: 2 CH,, 1 CCl,
1‘CCl ,” CHC1, 2.8700 2.410 Chloroform: 1 CHCl,
2.6401 2.184 l,l,l-Trichloroethane: 1 CH,, 1 CC1,
cc1, 3.3900 2.910 Carbon tetrachloride: 1 CC1,
ACCl 1.1562 0.844 Chlorobenzene: 5 ACH, 1 ACCl
CH,NO, 2.0086 1.868 Nitromethane: 1 CH,NO,
“CNO, ” CH,NO, 1.7818 1.560 1-Nitropropane: 1 CH,, 1 CH,, 1 CH,NO,
CHNO, 1.5544 1.248 2-Nitropropane: 2 CH,, 1 CHNO,
ACNO, 1.4199 1.104 Nitrobenzene: 5 ACH, 1 ACNO,
CS 2 2.057 (1.65) Carbon disulfide: 1 CS,
a Note: Subgroups (for example CH,=CH and CH=CH) within the same main group (here C=C) have different values
for R k and Q k but identical group interaction parameters, a w n . b Not t o be used with oxygen-containing hydrocarbons or
amines .

be CH3, OH, C1, N02, “ 2 , COOH, etc. Langmuir stated that able model, t o estimate thermodynamic properties, in par-
if it is possible t o characterize quantitatively the physical in- ticular, activity coefficients. UNIFAC provides such a
teractions between such groups, it should then be possible t o model.
estimate intermolecular interactions and finally, with a suit- Langmuir’s suggestion received little attention until Wilson

Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977 451
and Deal (1962), Derr and Deal (1969), and Ronc and Ratcliff
(1975) proposed the ASOG model, which is similar to UNI-
FAC in principle but not in detail. From the user’s point of
view, UNIFAC provides three advantages: (1)flexibility, be-
cause UNIFAC, provides a priori estimates of sizes and surface
areas; (2) simplicity, because UNIFAC parameters, unlike
ASOG parameters, are essentially independent of temperature
for the temperature range considered here, typically 30-125
OC; and finally (3) due to results reported in this work, UNI-
FAC parameters are now available for a considerably larger
number of functional groups than ASOG parameters; there-
fore, the range of applicability for UNIFAC is larger.
All group-contribution methods are necessarily approxi-
mations because any group within a molecule is not completely
independent of the other groups within that molecule. But it
is precisely this independence which is the essential basis of
every group-contribution method. We can allow for interde-
pendence of groups within a molecule by our definition of what
atoms constitute a group. Increasing distinction of groups,
however, also increases the number of group interactions that
must be characterized. Ultimately, if we carry group distinc-
tion to the limit, we recover the individual molecules. In that
event, the advantage of the group-contribution method is lost.
Judgment and experience must tell us how to define func-
tional groups so as to achieve a compromise between accuracy
of prediction and engineering utility.
Advances in UNIFAC Prediction of Activity
Coefficients
The UNIFAC group-contribution method is summarized
in Appendix A. Fredenslund et al. (1975) showed that the
UNIFAC method may be used to predict fluid-phase equi-
libria in systems containing hydrocarbons (saturated, un-
saturated, and aromatic), alcohols, water, ketones, esters,
ethers, chlorinated hydrocarbons, amines, and nitriles. The
original work considered 25 different functional groups. Since
then, work on the UNIFAC method has continued in an effort
to extend reliability and applicability for separation-process
design.
We have now determined UNIFAC group-interaction pa-
rameters for more than 50 different groups. The basis of the
UNIFAC method now covers 70% of all published vapor-liq-
uid equilibrium data for nonelectrolyte mixtures a t low to
moderate pressures.
The revised table of group-interaction parameters is based
on vapor-liquid equilibrium data for roughly 2500 binary
systems. The data were chosen from a data set of more than
4000 binary systems stored on magnetic tape and collected a t
the University of Dortmund (Gmehling and Onken, 1977).
These data are, where appropriate, supplemented with data
from Wichterle et al. (1973).
The availability of this large data base has enabled us to
obtain more reliable values for group-interaction parameters
than those published originally. I t has also made it possible
better to ascertain which choice of functional groups results
in the best correlation.
The determination of group-interaction parameters from
the data base proceeds as follows.
(1) For thermodynamically consistent data (Christiansen
and Fredenslund, 1975), activity coefficients are calculated
from isothermal P-x, or isobaric T-x,-y, data. Vapor-phase
nonidealities are accounted for as shown by Hayden and
O’Connell (1975).
(2) A pair of group-interaction parameters, e.g., U C O O H , C H ~
and U C H ~ , C O O Hare
, obtained from a collection of all available,
consistent, relevant experimental data, in this case for systems
with alkanes (including isomers) and organic acids. The
simplex method (Nelder and Mead, 1965) is used to fit the
452 Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977
1 ATM. A
l
0 .2 .4 .6 .% 1.0
Mole Fraction W a t e r , x
H 20
Figure 1. Experimental and calculated activity coefficients for organic
acid-water systems exhibit both positive and negative deviations from
Raoult’s law: calculated, -; experimental: formic acid (1) 0-water
(4) 0 , Ito and Yoshida (1963); acetic acid (2) 0-water (4) m, Sebas-
tiani et al. (1957); propionic acid (3) A-Water (4)A ,Ito and Yoshida
(1963).
model to the experimental activity coefficients. The values
of U C O O H , C H and
~ UCH~,COOHmust be known prior to obtaining
U H ~ O , C O O Hand U C O O H , H ~ Ofrom data on systems containing
organic acids and water. In some cases it is advantageous to
evaluate several pairs of parameters, e.g., U C H ~ , C O O H ,
U C O O H , C H ~U, C O O H , H ~ O and
, ~H~O,COOH simultaneously
, from
the sum of the two sets of data.
The new UNIFAC parameters are given in Tables I and 11.
Organic acids, secondary alcohols, methanol, most of the
chlorinated hydrocarbons, carbon disulfide, and compounds
with the nitro group were not included previously. The re-
maining parts of these tables indicate the revised parameters.
Note that the ketone, ester, ether, secondary amines, and al-
cohol groups are redefined by the addition of another meth-
ylene group.
Prediction of Activity Coefficients. A detailed account
of the agreement between experimental and calculated ac-
tivity coefficients for all of the groups included in UNIFAC
will be published elsewhere (Fredenslund et al., 1977). In this
section we only give a few examples of activity coefficients
predicted by the UNIFAC method.
Tables 111-VI show some of the results from the data cor-
relation. We show typical experimental and calculated activity
coefficients in the dilute regions for several of the binary
systems. Tables 111-VI clearly show UNIFAC’s ability to
represent a wide range of mixtures with only few parameters.
For example, activity coefficients at infinite dilution for binary
systems of alkanes and aliphatic ethers with one, two, or three
ether groups or dioxane or tetrahydrofuran (Table 111) are all
correlated extremely well using only two parameters. For those
systems, the infinite-dilution activity coefficients range from
roughly 1.1to 3.5. Similarly, Table IV shows that no more than
two parameters are needed to represent the phase equilibria
of alkanes with ketones ranging from acetone to nonanone.
Tables V and VI show excellent agreement between predicted
and observed equilibria in, respectively, alkane-alcohol and
alkane-amine systems, Figure 1 shows results for systems
containing water and the lower organic acids. Again, only two
h

- 1
1 -I
-I

Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977 453
Table 111. Experimental and Calculated Activity Coefficients for Alkane-Ether Systems
Component 1 Component 2 T ,K x1 yl(expt1) yl(ca1cd)
n-Propyl ether n-Heptane 343.2 0 1.09 1.19
n-Heptane n-Propyl ether 343.2 0 1.08 1.19
Dimethoxyethane n-Heptane 343.2 0 2.32 2.16
Heptane Dimethoxyethane 343.2 0 2.11 2.45
Bis(2-methoxyethyl) ether n-Decane 393.2 0 2.62 2.94
n-Decane Bis(2-methoxyethyl) ether 393.2 0 3.06 3.46
Dioxane n-Hexane 353.2 0.024 2.67 2.13
n-Hexane Dioxane 353.2 0.030 2.94 3.11
Dioxane n-Octane 353.2 0.021 2.33 2.14
n-Octane Dioxane 353.2 0.046 3.32 2.93
Dioxane Cyclohexane 353.2 0 2.87 2.49
Cyclohexane Dioxane 353.2 0 2.55 2.58
Tetrahydrofuran Cyclohexane 298.2 0.1 1.77 1.75
Cyclohexane Tetrahydrofuran 298.2 0.1 1.70 1.71

Table IV. Experimental and Calculated Activity Coefficients for Alkane-Ketone Systems
Component 1 Component 2 T ,K x1 yl(expt1) 71(calcd)

Acetone n-Hexane 318.2 0.1 3.37 3.82

n-Hexane Acetone 318.2 0.1 3.40 3.76
2-Butanone n -Heptane 366.9 0.027 3.53 3.29
n-Heptane 2-Butanone 351.9 0.027 3.15 3.53
3-Pentanone n -Heptane 353.2 0.056 2.32 2.04
n-Heptane 3-Pentanone 353.2 0.051 2.24 1.98
5-Nonanone n-Hexane 333.2 0.1 1.68 1.69
n-Hexane 5-Nonanone 333.2 0.1 1.45 1.50

Table V. Experimental and Predicted Activity Coefficients for Alkane-Alcohol Systems"

Component 1 Component 2 T ,K x1 yl(expt1) yl(calcd)
n-Hexane 2-Butanol 333.15 0.094 3.34 3.27
2-Butanol n-Hexane 333.15 0.069 5.17 6.41
n-Heptane 1-Octanol 293.15 0.1 2.49 2.31
n-Heptane 2-Octanol 293.15 0.1 2.30 2.30
n-Heptane 3-Octanol 293.15 0.1 2.24 1.93
n-Heptane 4-Octanol 293.15 0.1 2.26 1.93
1-0ctanol n-Heptane 293.15 0.1 4.17 3.88
2-Octanol n-Heptane 293.15 0.1 3.69 3.87
3-Octanol n-Heptane 293.15 0.1 3.42 2.81
4-Octanol n-Heptane 293.15 0.1 3.41 2.81
Decane 1-Propanol 363.15 0.0503 5.01 6.11
1-Propanol Decane 363.15 0.214 2.82 3.49
n-Hexane Ethanol 298.15 0.1 5.92 5.35
Ethanol n -Hexane 298.15 0.1 7.13 8.01
Methanol n-Hexane 333.75 0.138 6.08 6.46
n-Hexane Methanol 333.05 0.054 12.21 13.06
0 NOTE: Of the systems shown here only ethanol-hexane was included in the data base.

Table VI. Experimental and Calculated Activity Coefficients for Alkane-Primary Amine Systems
Component 1 Component 2 T ,K X1 yl(expt1) yl(calcd)
Methylamine n -Nonane 293.2 0 3.55 3.72
n-Nonane Methylamine 293.2 0 7.90 7.97
Ethylamine n -Hexane 293.2 0 2.95 2.62
n-Hexane Ethylamine 293.2 0 2.64 2.80
n-Propylamine n-Hexane 293.2 0 2.60 2.47
n-Hexane n-Propylamine 293.2 0 2.56 2.34
n-Butylamine n-Hexane 333.2 0.128 1.66 1.68
n-Hexane n-Butylamine 333.2 0.104 1.77 1.67
n -Hexylamine n-Hexane 333.2 0.123 1.55 1.49
n-Hexane n-Hexylamine 333.2 0.094 1.49 1.42

parameters are required to represent the interaction between
COOH and H 2 0 groups for the systems shown. Since data for
systems including formic acid are scarce, it is not certain
whether the formic acid-water prediction shown in Figure 1
is fortuitous. As more data become available, it may be ad-
vantageow to include formic acid as a special group in the
same manner as that for methanol.
Although no ternary (or higher) systems were included in
the data base, predicted multicomponent equilibria are in
good agreement with experiment. Table VI1 shows predictions
for the system chloroform-methanol-ethyl acetate. This
system is unusual, because it exhibits both large positive and
negative deviations from Raoult's law. Table VI11 shows
predicted and experimental activity coefficients for the system

454 Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977
Table VII. Experimental and Calculated Activity Coefficients a t 1 Atm for the System Chloroform(1)-Methanol(2)-
Ethyl Acetate(3) (Nagata, 1962)
Y1 Y2 Y3
x1 X2 Exptl UNIFAC Exptl UNIFAC Exptl UNIFAC
0.075 0.077 0.541 0.612 2.32 2.47 0.985 0.999
0.030 0.898 1.82 2.10 1.01 1.01 2.41 2.24
0.608 0.234 1.09 1.08 2.11 2.17 0.570 0.637
0.540 0.075 0.982 0.972 3.50 3.81 0.611 0.588
0.527 0.219 1.00 1.01 2.15 2.26 0.701 0.739
a The average absolute deviation between yl(exptl)and y,(calcd) is 0.011mole fraction.

Table VIII. Calculated Activity Coefficients for the System 1,2-Dichloroethane(l)-l-Propanol(2)-Toluene(3)-

Acetone(4) a t 700 mmHe (Ma et al.. 1969) Fitted with Binarv Data (Wilson Eauationk Predicted bv the UNIFAC Method
Exptl activity coefficients Calcd activity coefficients
x1 x2 13 Y1 Y2 Y3 Y4 Yl Y2 Y3 Y4

0.613 0.232 0.056 1.17 1.84 1.26 0.79 1.15 1.83 1.34 0.71 Wn
1.10 1.96 1.15 0.91 Ub
0.515 0.168 0.097 1.09 2.07 1.32 0.87 1.09 2.09 1.32 0.80 W
1.05 2.16 1.15 0.95 U
0.307 0.335 0.281 1.19 1.60 1.34 0.90 1.26 1.51 1.33 0.82 W
1.16 1.63 1.26 1.01 u
0.307 0.207 0.419 1.09 2.07 1.18 0.99 1.15 1.95 1.18 0.84 W
1.05 2.14 1.11 1.01 u
0.202 0.512 0.251 1.40 1.28 1.56 0.97 1.50 1.22 1.53 0.91 W
1.38 1.29 1.51 1.10 u
0.251 0.267 0.252 1.12 1.67 1.38 0.96 1.15 1.58 1.33 0.88 W
1.10 1.73 1.26 1.02 u
0.064 0.039 0.861 0.98 3.35 1.02 1.43 1.11 3.80 1.01 1.26 W
0.98 3.57 1.01 1.27 u
0.063 0.089 0.072 0.94 1.75 1.78 0.97 0.87 1.54 1.27 0.99 w
0.93 1.90 1.52 1.01 u
Mean Deviations between Experimental and Calculated Vapor-Phase Mole Fractions
Wilson UNIFAC method Raoult’s law
Component fitted predicted predicted
1 0.011 0.009 0.030 Mean deviation = 5,
=
2 0.010 0.006 0.087 ( 2 I):
k=l
h(expt1) - y,.k(calcd)
3 0.004 0.007 0.036 ilr = no. of data points
4 0.014 0.016 0.022
W = Wilson’s equation. U = UNIFAC method.

1,2-dichloroethane-l-propanol-toluene-acetone (Ma et al.,
1969). The authors give Wilson parameters based on the data,
and activity coefficients calculated from these parameters are
also shown. The UNIFAC method and the Wilson equation
(with the parameters of Ma et al.) give overall mean deviations
in vapor-phase mole fractions of 0.01;by contrast, using
Raoult’s law does not result in satisfactory predictions.
Systems Containing Branched Hydrocarbons and
O t h e r Isomers. Fredenslund e t al. (1975)considered the ef-
fect of isomerization to only a limited extent. Since then much
experience has been gained in this respect and, with the new
UNIFAC parameters, the phase behavior of systems con-
taining isomers may usually be predicted with good results.
Table V shows that secondary and primary alcohols are rep-
resented very well using the same set of parameters; similarly,
Figure 2 shows good agreement for predicted and calculated
activity coefficients for the 2,2,3-trimethylbutane-benzene
system. This favorable result is particularly gratifying because
no branched alkanes were included in the data base for de-
termining the methylene-aromatic hydrocarbon group in-
teraction parameters.
Liquid-Liquid Equilibria. The present set of UNIFAC
parameters is, where possible, based on vapor-liquid equi-
librium data only. For systems such as alkanes with water it
was necessary to include liquid-liquid equilibrium data in the
data base.
Although the parameters are almost exclusively based on
vapor-liquid equilibria, the present version of the UNIFAC
model can predict liquid phase-splitting as indicated in Figure
3. For design of a liquid-liquid extraction cascade, one needs
to know the relative distribution of the solute(s) between the
two liquid phases. Since the solute mole fractions are often
small, the relative error in the predicted mole fractions-and
hence in the solute distribution ratios-may be large. This
problem is encountered by all methods for calculating activity
coefficients and the UNIFAC model is no exception. There-
fore, UNIFAC is usually not suitable for accurate liquid-liquid
extraction calculations. However, UNIFAC often predicts
phase-splitting with sufficient accuracy for designing heter-
ogeneous-azeotropic-distillationcolumns.
Multicomponent Distillation Design Calculations
The multicomponent column-design procedure used here
is a modification of the successive approximation method
described by Naphtali and Sandholm (1971).The distillation
column configuration is shown in Figure 4.The general design
equations, which include material- and energy balances and
Murphree efficiencies coupled with vapor-liquid equilibrium

Ind. Eng. Chem., Process Des. Dev., Vol. 16,No. 4, 1977 455
 - UNIFAC
0 OBSERVED
XI
Figure 2. Activity coefficients for the 2,2,3-trimethylbutane(l)-
benzene(2) system at 1 atm (Harrisonand Berg, 1946). This binary
system was not included in the data base.
- UNIFAC
X1
A T = 0.0175
Figure 3. Experimental and calculated vapor phase mole fractions
and phase-splitin the system n-heptane(l)-acetonitrile(2) (Werner
and Schuberth, 1966).
relationships, are given in Appendix B. A simplified set of
design equations, based on the assumption of constant molal
overflow, is also given.
The calculation scheme is shown schematically in Figure
5. Input to the calculations is as follows.
(1) Identification of Components to Be Separated.
Antoine constants, giving the pure-component vapor pres-
sures, and enthalpies of vaporization must be known for each
component. The latter are not needed for the simplified ver-
sion.
(2) Parameters for Determination of Thermodynamic
Properties. If all the necessary UNIFAC group-interaction
parameters are available, the activity coefficient of every
component i, infinitely dilute in component j for all possible
i-j pairs in the multicomponent system, is calculated using
the UNIFAC method. As explained in Appendix A, these
calculations are carried out a t two temperatures T I and T2,
typically the saturation temperatures of the least and most
volatile components. The activity coefficients a t infinite
dilution form the basis for estimating the UNIQUAC pa-
rameters for the molecular energy interactions. The linearized
temperature dependence, eq 8A, is used rather than the ex-
ponential form, eq 7A. The calculated infinite-dilution activity
coefficients a t the temperatures T I and T2 enable the deter-
mination of Aji (0) and A;i(I).The linear temperature depen-
456 Ind. Eng. Chern., Process Des. Dev., Vol. 16,No. 4, 1977
Distillate
r-bondense-
w Reflux
-
Feed
Fn f n , i
1 2 1
Figure 4. Distillation column configuration.
dence is introduced to save computer time. This introduces
no significant error.
Second virial coefficients are used to calculate vapor-phase
fugacity coefficients. We use the method of Hayden and
O’Connell(l975, see Appendix C) to estimate the virial coef-
ficients for all possible binary interactions a t temperatures
T I and Tz and interpolate the virial coefficients linearly in the
temperature.
(3) Specification of Separation Problem. The user must
specify the number of actual stages, stage efficiencies, feed-
and sidestream locations, feed compositions, flow rates, and
thermal states, total distillate flow rate, sidestream phase
conditions and flow rates, reflux ratio, and column pres-
sure.
Above it was stated that UNIFAC is used to obtain UNI-
QUAC parameters. Using UNIQUAC parameters rather than
UNIFAC parameters directly is based on the following. (1)
The UNIQUAC method, which uses only molecular compo-
sitions, is faster than the UNIFAC method, which uses both
molecular and group compositions. (2) Tests for systems
where experimental data are available show that activity
coefficients calculated from the UNIQUAC model and esti-
mated limiting activity coefficients are, on the average, as
accurate as those calculated directly using the UNIFAC
method. (3) If experimental information is available for some
of the constituent binaries, UNIQUAC parameters based on
these data may be incorporated directly into the calcula-
tions.
The column calculations can now proceed. The scheme
outlined in Figure 5 is that of the simplified version of the
program (constant molal overflow). The procedure for the full
version is analogous.
The total molar flow rates for each stage are calculated
based on the separation problem specification. (In the case
of the full version, they can only be estimated a t this point).
As an initial estimate, a linear temperature profile is assumed,
and the phase compositions on each stage are equated to the
nearest feed composition. This gives the zeroth estimate of
the independent variables l,,,, u,,,,, and T,, and hence the
zeroth values of the test functions. The Newton-Raphson
 Define mixture to be separated:
Antoine constants Ai Bi Ci
Group counts vk‘i)
Temperature range T1 to T2
*
Calculate activity coefficients at infinite dilution, y?,
at T1 ard Ti using UNIFAC. This also gives ri, q i , and1Ei
to UlilQLlAC eqcation. This gives A ! ? ’ and A!:):
J 1
T.. I A(?’ + A!f).T
J l J1 J1
~
Specify separation problem: No. of stages, feed stages,
r e f l L x ratio, feed compositions and no. of moles per hour,
amount of b o t t o m s product, sidestreams, and column pressure
Calc-late total liquid and vapor molar fiow rates on each
stage: Lr and V,. Estimate initial temperature- and
car.cer,trat
ior. profiles
.Calculate for each stage n and each component i , using
J.I~I.Q C A C , t h e equilibrium ratio at the last estimated tem-
peratdye and concentration i K . . Determine the deriva-
t h e ; o r Zn,: ~ i T hrescect to.!f;uid phase component molar
f l o w rates and temperature
1
Solve tne ccrrpor.ent naterial balances for each stage with
‘he new values o f t i l e stripping factors C
n,i ‘JnKn,i‘Ln
I -
Are new
the previously
estimated
values?
Yes, within
suecified limits
Print resulting distillate and bottoms compositions and
column temperature- and concentration profiles
Figure 5. Procedure for distillation column calculations (simplified
version).
iteration method, utilizing simultaneous convergence of all
independent variables, is now used to obtain the true values
of l,,,, u,,,~,and T,,. Simultaneous convergence is more efficient
than a sequential convergence method when the volatilities
of the components depend both on temperature and compo-
sitions.
Convergence is normally attained within 4-9 iterations. The
computer time per iteration is proportional to the number of
stages. In the simplified version (constant molal overflow),
four components and 20 stages typically require 0.4 s per it-
eration on an IBM 370/165 computer using a Fortran G or
Watfiv compiler. About 50%of this time is used for algebraic
manipulations, and 50%is used for evaluating activity coef-
ficients. The full Naphtali-Sandholm procedure requires the
same number of iterations and typically 2.0 s per iteration for
the above example.
Similar calculations, where the Wilson equation is used
instead of the UNIQUAC equation, require slightly less
computer time. The parameters in the Wilson equation (or
any other two-parameter expression for activity coefficients)
may be calculated from the UNIFAC parameters in the same
manner as that used to determine UNIQUAC parameters.
Results of Distillation Calculations (Simplified Ver-
sion). Distillation-column design calculations assuming
constant molal overflow and ideal vapor phase were carried
out for three different systems: cyclohexane(1)-ethanol(2)
-l-propanol(3)-toluene(4); 1,2-dichloroethane(l)-l-propa-
nol(2)-toluene(3)-acetone(4); and methylcyclohexane(1)-
toluene(2)-phenol(3). The first system was chosen because
it exhibits large deviations from ideality and is thus an ex-
--- RAOULT S LAW
m \
.c \
0 4 . a
0
I 0.3 . P
-I
b 3 5 7 9 11 13 15 17 19 d
Bottom S t a g e Number TOP
Figure 6. Liquid-phase concentration profiles for 1-propanol and
toluene with cyclohexane and ethanol in a simple distillation col-
umn.
ample of systems where estimation of activity coefficients is
I absolutely essential; the second system was chosen because
of the availability of extensive experimental multicomponent
vapor-liquid equilibrium data (Table VIII); the third system
is an example of extractive distillation.
For the first two systems, feed is introduced on stage 10,
there are 20 stages, and there are no sidestreams. The column
configuration for the extractive-distillation example is given
in Figure 7.
The System Cyclohexane( 1)-Ethanol(2)-1-Propa-
nol(3)-Toluene(4). Hydrocarbon-alcohol systems are known
to deviate greatly from ideality; minimum-boiling azeotropes
are found in many cases. In this system, no fewer than four
binary azeotropes exist. Predictions of equilibrium ratios in
the ternary system of components 2,3, and 4, using the UN-
IFAC method, indicate that no ternary azeotropes exist in this
system.
For this system we choose as feed composition x 1 = 0.1, x p
= 0.4,x 3 = 0.4, x 4 = 0.1. The reflux ratio is 2.25, and 60 mol
out of 100 mol in the feed are specified as distillate. The main
results of the column calculations are shown in Table IX. The
toluene-ethanol azeotrope has a marked effect on the results.
Although toluene is the heaviest-boiling component, i t goes
into the distillate almost quantitatively. The relative content
of toluene and ethanol in the distillate corresponds closely to
that of the azeotrope. It boils a t 77”C, 20°C lower than the
normal boiling point of 1-propanol, which forms 99% of the
bottoms product. A similar calculation, where the UNIQUAC
model is replaced by the Wilson equation gives essentially the
same results. Raoult’s law, on the other hand, gives completely
erroneous results. The calculated propanol and toluene con-
centration profiles are shown in Figure 6.
Computations performed with the full version of the column
design procedure indicate that the assumptions of constant
molal overflow and ideal vapor phase are justified in this
case.
The System 1,2-Dichloroethane( 1)-1-Propanol(2)-
Toluene(3)-Acetone(4). Predicted activity coefficients using
the UNIFAC method are given in Table VIII, which also
shows experimental activity coefficients.
Essential results of the column calculations are given in
Table IX together with those based on Raoult’s law and those
using the Wilson equation instead of the UNIQUAC equa-
tion.
Ind. Eng. Chem., Process Des. Dev., Vol. 16,No. 4,1977 457
 c d=:2.21- mles/h I I

?12=76.74
1
=o
-
Feed stage 12
moleslh
2
;o
21
stages ZC'4P:TER TIYE:
x -1.0 p = l atn 5 . 4 s e c a n t-le 191: ? 7 0 / 1 C 5

ST3RA3E SEQLIRE

.%e+ stage 7
_.c
Fy23.26 mles/h
xl=0.5
x 2--0 ' 5
x,=o

cb =W.:f no:espb

T h e f r a m e d nunoe?s a r e c a l c u l i t e 3 FeiUltS S t a s e YU7ber

Figure 7. Column configuration and liquid phase concentration profiles for extractive distillation of methylcyclohexane(1)and toluene(2) with
phenol(3).

Table IX. Component Flow Rates of Distillate and Bottoms. Comparison of Calculations Based on UNIFAC. Raoult's
Law and Wilson's Equation. Simplified Version; 20 Stages; Feed Stage: 10; Pressure: 1 atm; No Sidestreams
UNIQUAC Raoult's law WilsonC
Feed," Distillate," Distillate, Bottoms, Distillate, Bottoms, Distillate, Bottoms,
mol of mol Refluxa molof mol of mol of mol of mol of mol of
comp. i total ratio comp. i comp. i comp. i comp. i comp. i comp. i
Cyclohexane(l)-Ethanol(2)-l-Propanol(3)-Toluene(4)
(1): 10 60 (1):10.0
2.25 (1): 0.0 (1): 9.7 (1): 0.3 (1):10.0 (1): 0.0
(2):40 (2):39.7 (2): 0.3 (2):39.9 (2): 0.1 (2):39.9 (2): 0.1
(3):40 (3): 0.3 (3):39.7 (3):10.3 (3):29.7 (3): 0.7 (3):39.3
(4):10 (4): 9.9 (4): 0.1 (4): 0.1 (4): 9.9 (4): 9.3 (4): 0.7
1,2-Dichloroethane(l)-l-Propanol(
2)-Toluene(3)-Acetone(4)
(1):45 50 4 (1): 34.2 (1): 10.8 (1):42.3 (1): 2.7 (1): 35.5 (I): 9.5
(2):45 (2):10.8 (2):34.2 (2): 2.6 (2):42.4 (2): 9.6 (2):35.3
(3): 5 (3): 0.0 (3): 5.0 (3): 0.0 (3): 5.0 (3): 0.0 (3): 5.0
(4): 5 (4): 5.0 (4): 0.0 (4): 5.0 (4): 0.0 (4): 4.9 (4): 0.1
a Specified by user. Parameters estimated with UNIFAC method. c Parameters fitted with binary data.

Table X. Component Flow Rates of Distillate and to-stage solution of a n extractive-distillation process for the
Bottoms. Comparison of Calculations Based on UNIFAC above two components using phenol as a solvent. Using UN-
and Raoult's Law. Full Version." Ethanol( 1)- IFAC coupled with the simplified version of the distillation
I-Propanol(2)'-Water(3)-Acetic Acid(4) program, we obtain the same results as those presented by
Mol in Mol in bottoms Smith. The process and resulting concentration profiles are
Component distillate product Method shown in Figure 7.The solution of this problem required seven
iterations and 3.4 s on the IBM 370/165 computer.
1 24.8 0.2
2 14.3 10.7 Raoult's Results of Distillation Calculations (Full Version). If
3 10.4 14.5 law excess enthalpy effects cannot be neglected, if stage efficien-
4 0.4 24.6 cies are to be included, or if the vapor phase is strongly noni-
deal, it is necessary to use the full Naphtali-Sandholm pro-
1 22.4 2.6 Full cedure. (Slight vapor phase nonidealities can be included in
2 9.2 Naphtali-
15.7 the simplified version by inserting the vapor-phase fugacity
3 18.4 Sandholm
6.6
4 0.0 25.0 with coefficient in the stripping factor (see Appendix B,eq 7B)and
UNIFAC subsequently neglecting derivatives of the test functions with
UReflux ratio: 2.0;distillate: 50 molh; number of stages: 15;feed respect to vapor-phase composition). Systems containing
stage: number 7;feed: (1):25 mol/h; (2):25 mol/h; (3):25 mol/h; organic acids are examples of systems where the full Naph-
(4):25 mol/h. tali-Sandholm procedure must be used. Liquid-phase noni-
dealities are, as before, accounted for via the UNIFAC cor-
relation, and vapor-phase nonidealities, including organic-acid
In the example given here, the feed contains mainly com- dimerization, are determined as explained in Appendix C. The
ponents 1 and 2, and the reflux ratio is 4. Separation between results shown in Tables X and X I are for the case of a simple
these two components is poor due t o the 1,2-dichloroethane- distillation column with one feed stream at stage 7 , no side-
1-propanol azeotrope (boiling point 68 "C) going into the streams, and 15 stages. Figure 8 shows results for a more
distillate. complex column.
The UNIQUAC results agree well with those using the The System Ethanol(l)-l-Propano1(2)-Water(3)-
Wilson equation. However, Raoult's law predicts a different Acetic Acid(4). For a n even feed of 25 mol/h of each com-
(and erroneous) distribution ratio for components 1and 2. ponent to a column as specified in Table X, one might expect
The System Methylcyclohexane( l)-Toluene(2)-Phe- a split between 1-propanol and water, such that most of the
nol(3). Methylcyclohexane and toluene are difficult t o sepa- 1-propanol goes into the distillate, most of the water into the
rate by simple distillation. Smith (1963) presents a stage- bottoms product, Raoult's law gives this result. However, as

458 Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977
Table XI.Component Flow Rates of Distillate and
Bottoms. Comparison of Calculations Based on UNIFAC
and Raoult’s Law. Full Version.n Benzene( 1)-1-
Propanol(2)-Toluene(3)-Acetic Acid(4)
I\I
Compo-
nent Distillate Bottom Method
I 1 24.95 0.05 Raoult’s
2 9.77 0.23 law 1 stages 1
3
4
5.39
9.89
4.61
45.11
lf7i = 1
yi = 1
Constant
1 n n , =O.7
I Sidestream (Saturated
stage 9 ,
Liquij:

I1 1 25.00 0.00
2 9.43 0.57 molal flow
3 10.00 0.00 (oi =1
4 5.57 49.43 yi from UNIFAC
F,:5L mcles/h
I11 1 25.00 0.00 Constant
2 6.95 3.05 molal flow
3 9.99 0.01 Pi f 1
4 8.06 46.94 yi from UNIFAC
IV 1 25.00 0.00 Full
2 6.96 3.04 Naphtali-
3 9.99 0.01 Sandholm
4 8.05 46.95 Pi f 1
yi from UNIFAC X i 4 ’ J T E F , TI:.iE: 17.4 s e c on t h e IBK :70/155
Reflux ratio: 2.0; distillate: 50 mol/h; number of stages: 15;
feed stage: number 7; feed: (1): 25 mol/h; (2): 10 mol/h; (3): 10 STORAGE R E Q U I R E M E N T : e 8 K Bytes.
mol/h; (4): 55 mol/h.
-he framed n u n t e r s a r e c a l c d i a t e d results.
Figure 8. Distillation results for the system ethanol(1)-1-propa-
the UNIFAC correlation correctly predicts, water has a much nol(2)-water(3)-aceticacid(4).
higher activity in acetic acid than 1-propanol has, and hence
most of the 1-propanol goes into the bottoms product. In these
calculations, we have neglected the effect of the relatively slow Omissions in the group-parameter table clearly indicate
esterification of the alcohols with acetic acid. where new experimental data are needed. As new and better
Figure 8 shows a summary of results for a complex column, phase-equilibrium data become available, the UNIFAC
where Murphree stage efficiencies of 0.7 were included. This method, appropriately revised, will increase its accuracy of
required five iterations and 17.4 s computer time on the IBM predictions and, more important, increase its range of appli-
370/165 computer. cability. However, even a t this incomplete state of develop-
The System Benzene(l)-l-Propano1(2)-Toluene(3)- ment, it is evident that UNIFAC may be useful in at least some
Acetic Acid (4).Table XI shows results for the case of an of those commonly encountered industrial situations where
uneven feed: 25 mol/h benzene, 10 mol/h each of 1-propanol required data are lacking and where, for commercial reasons,
and toluene, and 55 mol/h of acetic acid. These results show a reasonable design is needed quickly. In chemical engineering
the effects of successively including corrections for liquid- process design there is always a need for good data, seasoned
phase nonideality (II), vapor-phase nonideality (III), and judgment, and sound experience. UNIFAC is no substitute
excess enthalpy effects (IV). I t is essential to include correc- for these requirements but it can contribute toward meeting
tions for both liquid and vapor-phase nonideality, whereas the their demands.
inclusion of enthalpy balances has only limited effect on the A description and print-out of the UNIFAC programs for
calculations. For most of the systems we have studied, the estimating activity coefficients and the computer programs
inclusion of enthalpy balances has little effect on the product which interface UNIFAC with distillation-column design is
compositions. They may, however, be of much importance in given by Fredenslund et al. (1977).
the determination of internal column flow rates.
Acknowledgment
Conclusions The authors thank Mr. Vagn Hansen for carrying out the
This work has indicated that UNIFAC provides a powerful “full version” of the Naphtali-Sandholm column calculations,
tool for the chemical design engineer. As outlined and illus- Mr. Thomas Anderson for his assistance in reducing to prac-
trated here, it is possible to construct a completely comput- tice the correlation indicated in Appendix C, the National
erized procedure for process design of a multicomponent Science Foundation and Statens teknisk-videnskabelige
distillation column, including estimation of phase equilibria. Forskningsraad for partial financial support, and Professor
The UNIFAC method for calculating activity coefficients Ulfert Onken (University of Dortmund) for his active interest
interfaces easily with iteration techniques for distillation- in this work.
column computations.
While the engineering utility of UNIFAC has been dem- Appendix A
onstrated, its utility inevitably rests on the quantity and T h e UNIQUAC a n d UNIFAC Models. Equations giving
quality of UNIFAC group-interaction parameters. These, in the activity coefficients as functions of composition and
turn, depend on the quantity and quality of experimental temperature are here stated very briefly, both according to the
phase-equilibrium data. The essence of UNIFAC is that it molecular UNIQUAC model (Abrams and Prausnitz, 1975)
interprets and correlates such data to enable predictions of and according to the group-contribution method, the UNI-
phase equilibria in previously studied mixtures under new FAC model (Fredenslund et al., 1975). Both models have a
conditions and in mixtures that have not been studied a t all combinatorial contribution to the activity coefficients, es-
experimentally. sentially due to differences in size and shape of the molecules,

Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977 459
and a residual contribution, essentially due to energetic in- group-composition variable, e k , is now the group fraction of
teractions group k in pure fluid i.
In yi = In y i c + In y i R
(1A)
111. Enthalpy of Mixing. One may obtain enthalpies of
mixing from the UNIQUAC and UNIFAC models. From
combinatorial residual classical thermodynamics, it follows that
I. Combinatorial Part. The combinatorial contribution
is the same in the two models

t
li = - (ri
2
- q i ) - (ri - 1); t = 10 Substituting eq l A , 2A, and 6A into eq 13A we obtain

Pure-component parameters ri and qi are, respectively,

measures of molecular van der Waals volumes and molecular The parameter T,, is given by eq 8A.
surface areas. They are calculated as the sum of the group- Equation 14A provides only a crude estimate when, as done
volume and group-area parameters, R k and Qk here, parameters (U,, - U,,) and (ulL- u,,) are determined
from vapor-liquid equilibrium data and are assumed to be
r; = Uk (i)Rk; qi = Uk (’)& (44
independent of temperature.
k k
where V k ( I ) , always an integer, is the number of groups of type Appendix B
h in molecule i. Group parameters R k and Qk are obtained
from van der Waals group volumes and surface areas, vk and Equations for Multicomponent Distillation Design. The
Ah, given by Bondi (1968) distillation column configuration is shown in Figure 4. Dis-
tillation columns with up to 50 (actual) stages, up to ten
Rk = Vk/15.17; Qk = Akl(2.5 X lo9) (5A) components, a partial condenser, and any number of feed- and
sidestreams may be considered. In our “operating column
11. Residual Part. A. UNIQUAC Equation. analysis” (King, 1971, p 520), the user must specify: (a) the
number of actual stages, (b) stage efficiencies, (c) feed- and
(6.4) sidestream locations, (d) feed compositions, flow rates, and
thermal states, (e) distillate flow rate, (f) sidestream phase
conditions and flow rates, (g) reflux ratio, and (h) column
(7-4) pressure. The nomenclature for an arbitrary stage n ,which
includes the possibility of feed- and sidestreams, is given
where u,, is a characteristic energy for the j-i interaction. For below.
a small temperature range, the effect of temperature on T,, can
be approximated by a linear form
T,, = A,, (O) + A,, ( l ) * T (8.4)
where A,,(O) and A,, ( l )are coefficients related to (u,, - u,,).
B. UNIFAC Method (Group-Contribution).

In y,R = Uk(’)[lnr k - In r k “ ) ] (9.4)

k
all groups
I’k is the group residual activity coefficient, and r k (I)is the
residual activity coefficient of group k in a reference solution
containing only molecules of type i.

E Um(i)X, Ln vfl- 1
8, = ’- Q m X m (1W
EQ,X,’ x m = CC U k ( i ) x i hn ln,i un- I ,i Hn- 1
n i k
Subscript n: flow from stage n , n = 1 , 2 , . . . , N ; subscript i:
X , is the fraction of group m in the mixture. component i, i = 1 , 2 , . . . M ; H = vapor phase enthalpy; h =
liquid phase enthalpy; H I = feed enthalpy; V = total vapor
Qnm = exp[-(a,,/T)I *( 12A)
flow; u = component vapor flow; L = total liquid flow; 1 =
Parameter anm characterizes the interaction between groups component liquid flow; F = total feed; f = component feed;
n and m. For each group-group interaction, there are two SL= liquid sidestream; Sv = vapor sidestream.
parameters: anm # amn. No ternary (or higher) parameters General Relations w i t h Enthalpy Balances. For stage
are needed to describe multicomponent equilibria. n one obtains the following set of dependent relationships
Equations 10A-12A also hold for In rk ( i ) , except that the (test functions F k ( f l , i ) which
) must be satisfied.

480 Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4, 1977
 Component Balances. (Total: N X M relations) The assumption of equality of heats of vaporization and zero
excess enthalpy is tantamount to the assumption of “constant
molal overflow”. I t is not necessary to assume ideal vapor
phase a t this point. However, in the solution of eq 9B it is
convenient to assume that {,i does not depend upon the vapor
~,,i - ~,-1,j - In+l,j - fn,j =0 (1B) phase composition.
Newton-Raphson Iteration. Solving eq 4B or 9B means
Enthalpy Balances. (Total: N relations)
finding the set of values of the independent variables, x , which
makes the set of test functions become equal to zero
F(x) = 0
H , - Hn-l - hn+l- Hf,, = 0 (2B) In Newton-Raphson iterations, a new set of values of the test
functions, FcneW),are generated from a previous estimate in
Equilibrium Conditions with Murphree Stage Ef- the following fashion
ficiencies, v,,,. (Total: N X M relations).
F(new)(x(new))
= F(old)(X(old))
F.?(n,i)= vn,iKn,lVnL,i/Ln - on,,
+ (1 - vn,i)un-1,iVn/Vn-1 = 0 (3B)

This equation is used to estimate x(new). When (x(new) - x(Old))

The above relationships comprise a vector of test functions
+
which contains N X (2M 1) elements, and which may be
solved for equally many unknowns
is sufficiently small, the correct set of values of x has been
found, and the iteration stops.
The variations between subsequent iterations are limited
as follows: (1) negative component molar flow rates are
equated to zero; (2) component flow rates exceeding L, are
equated to L,; (3) the maximum change in component molar
flow rates is O.25Ln, and (4)the maximum change in the
temperature a t each stage, T,, is 10K. The limits of 0.2515,
and 10K are chosen arbitrarily.

(t}
The Jacobi matrix, (&Flax),is here very large, often of the
order 200 X 200. The evaluation is greatly facilitated by the
x= fact that the conditions on stage n only is influenced directly
+
by the conditions on stages n 1and n - 1. As a result, the
Jacobian becomes block-tridiagonal in structure, which per-
mits rapid solution by block elimination.
where the vector 1 contains all the elements l,,,, v all elements The derivatives of test functions with respect to tempera-
and T all elements T,. ture are found analytically, those with respect to component
Once all I,,,, u ~ ,and
~ , Tn’sare known, the product compo- flow rates numerically.
sitions and product flow rates and the concentration- and
temperature profiles in the column follow readily.
Simplified Version (Constant Molal Overflow). If one Appendix C. Determination of Pure-Component
assumes Properties and Vapor-Phase Nonideality
Pure-Component Reference Fugacity. The UNIFAC
q n I = 1, Pn,i = 1, and AHnM= 0, all n and i, and correlation applies to vapor-liquid equilibria a t normal
s l w = S 2 w .. . . = u M v a P
pressures. The pure-component reference fugacity is calcu-
eq 1B and 3B may be combined as follows lated from eq 3 in the text.
Antoine constants are used to calculate P,”,and values for
pis are obtained from the correlation by Hayden and O’Con-
ne11 (197~4,which includes components deviating strongly
from ideality due to chemical interactions.
Vapor-Phase Nonideality. A t normal pressures, vapor-
phase fugacity coefficients of pure components and compo-
nents in a mixture may be calculated from second virial
coefficients, B,,

where P,,,s is the pure-component vapor pressure of compo-

nent i on stage n .
One other set of independent relations is in this case given
by the mass balance on each stage
F5(n)= Ln - ln,1 - ln,2 - . . . - l n ,=
~ 0 (8B) M is the number of components in the system.
Equations 6B and 8B comprise N X ( M + I ) relations In Hayden and O’Connell’s generalized correlation for
predicting second virial coefficients, the overall second virial
coefficient is considered as a sum of contributions form free
pairs of molecules, metastable pairs, physically bound pairs.
and chemically bound pairs
containing equally many independent variables

(10B)
and equations are presented for each contribution. For asso-

Ind. Eng. Chem., Process Des. Dev., Vol. 16, No. 4 , 1977 461
ciating components such as carboxylic acids, the dimerization
equilibrium constant, K p , is obtained from
K = - B b o u n d -k Bmetastable -k Bchern.
P (4C)
RT
The Hayden-O'Connell generalized correlation for Bi; is ap-
plicable to most systems where the UNIFAC method is
presently used. Input to the correlation consists of: (a) pure-
component information: critical temperature and pressure,
Thompson's mean radius of gyration, dipole moment, and an
association factor, which depends only upon the type of as-
sociating group (hydroxyl, amine, carboxylic acid, etc.); (b)
mixture information: solvation factor; (c) the system tem-
perature. Hayden and O'Connell give the input parameters,
including association and solvation factors, for a large number
of systems.
For systems containing carboxylic acids, we have chosen to
neglect Bfreeand use the values of K p given by Tamir and
Wisniak (1975) and Prausnitz (1969, p 138) to represent the
vapor-phase nonideality.
Nomenclature
anm = UNIFAC binary interaction parameter (related to
qnrn 1 UNIFAC", Elsevier, Amsterdam, 1977.
A;; = UNIQUAC parameter, see eq 8A
Bi - second virial coefficient for i-j interaction
fid pure-component reference fugacity of component i
=
fn,i molar feed rate of component i on stage n
F, = molar feed rate on stage n
H, = enthalpy of vapor from stage n
h, = enthalpy of liquid from stage n
AHM = enthalpy of mixing
M v a p = enthalpy of vaporization
K,,i = equilibrium ratio of component i on stage n
1,,i = liquid molar flow rate of component i from stage n
1, = pure-component constant defined in eq 3A
L , = total liquid molar flow rate from stage n
Pis = pure-component vapor pressure of component i
qi = pure-component area parameter of component i
Qk = group area parameter for group k
ri = pure-component volume parameter of component i
R k = group volume parameter of group k
R = gas constant
SnV = vapor-phase sidestream from stage n
S , L = liquid-phase sidestream from stage n
T = temperature
u,; = UNIQUAC binary interaction parameter (related to
~ , and
i A .i)
V , = totai vapor molar flow rate from stage n
462 Ind. Eng. Chem.. Process Des. Dev., Vol. 16, No. 4, 1977
un,i = vapor-phase molar flow rate of component i from stage
n
u; = molar liquid volume of component i
xi = liquid-phase mole fraction of component i
Xk = group fraction of group k
yi = vapor-phase mole fraction of component i
z = lattice coordination number, here equal to 10
Greek Letters
y I = activity coefficient of component i
rk = activity coefficient of group k
rk( i ) = activity coefficient of group k in pure component i
pi = fugacity coefficient of component i
@i = segment fraction of component i
U k (i) = number of groups of kind k in molecular species i
0; = area fraction of component i
(3k = area fraction of group k
T,> = UNIQUAC parameter, see eq 7A
qnrn= UNIFAC parameter defined in eq 12A
= stripping factor of component i on stage n
L i t e r a t u r e Cited
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Receiced for reuieu: November 5. 1976
Accepted April 8, 1977