178 Ind. Eng. Chem. Res.

1993,32, 178-193

A Modified UNIFAC Model. 2. Present Parameter Matrix and Results

for Different Thermodynamic Properties
Jurgen Gmehling,* Jiding Li,’ and M a r t i n Schiller
Lehrstuhl fur Technische Chemie (FB9),Universitdt Oldenburg, Postfach 2503, 0-2900 Oldenburg, F.R.G.

Several years ago a modified UNIFAC (Dortmund, FRG) method was proposed, which shows various
advantages when compared with the group contribution methods UNIFAC or ASOG; the latter are
used worldwide for the synthesis and design of rectification processes. These advantages were reached
by using a modified combinatorial part and by using a large data base to fit temperature-dependent
group interaction parameters simultaneously to vapor-liquid equilibrium (VLE),liquid-liquid
equilibrium (LLE),hE, and ymdata. The main advantages of the modified UNIFAC method are
a better description of the temperature dependence and the real behavior in the dilute region and
that it can be applied more reliably for systems involving molecules very different in size. T o increase
the range of its applicability, the temperaturedependent group interaction parameters of the modified
UNIFAC have been fitted for 45 main groups using phase equilibrium information (VLE,hE,ym,
LLE)stored in the Dortmund Data Bank. A comprehensive comparison with the results of other
group contribution methods confirms the high reliability of the modified UNIFAC (Dortmund)
method.

Introduction scription of the real behavior of these kinds of mixtures

The synthesis and design of separation processes re-
quires a reliable knowledge of the phase behavior cf the
system to be separated. For the description of multicom-
ponent non-electrolyte systems, gE-modelsor equations of
state can be applied using binary data alone. Experimental
data are however often missing. In such cases group
contribution methods such as ASOG (Derr and Deal, 1969;
Kojima and Tochigi, 1979)or UNIFAC (Fredenslund et
al., 1975,1977)can be successfully applied. These methods
are developed for the prediction of vapoAiquid equilibria
(VLE),so that the required group interaction parameters
were mainly fitted to experimental VLE data stored in the
Dortmund Data Bank (Gmehling, 1985,1991).The actual
parameters of these methods were published by Hansen
et al. (1991)and Tochigi et al. (1990). With the help of
these methods it is possible to obtain reliable results for
vapor-liquid equilibria, including azeotropic points.
However poor results are often obtained when these
methods are used for the prediction of the activity coef-
ficients at infinite dilution (7-1, heats of mixing (hE),or
systems with components very different in size. This is
not surprising because VLE data normally cover only the
concentration range 5-95 mol 9%. Furthermore, com-
pounds of similar size are usually considered, and with
VLE data from different authors no reliable information
about the temperature dependence (e.g., hE data) can be
derived.
But for design purposes (determination of the number
of theoretical stages), reliable information on the real
behavior in the very dilute region is particularly important.
For example, for positive deviation from Raoult’s law, the
greatest separation effort is required for the removal of the
last traces of the high boiling component at the top of the
column (smallest values for the difference cyl2 - 1).
Following the Gibbs-Helmholtz relation, a good de-
(e.g., the removal of solvents by physical absorption using
high boiling solvents).
Modified forms of the UNIFAC method by Weidlich
and Gmehling (1987)and Larsen et al. (1987)were pro-
posed in order to overcome the aforementioned weak-
nesses. Apart from a modified combinatorial part, these
methods introduce temperature-dependent group inter-
action parameters which were fitted to a data base (VLE,
hE) much larger than that for the original UNIFAC me-
thod. In the version developed in Dortmund by Weidlich
and Gmehling (1987),ymvalues were also used for fitting
the parameters. In a comprehensive comparison by
Gmehling et al. (1990),the great advantages of the mod-
ified forms of the UNIFAC method have already been
demonstrated; the Dortmund, FRG, version was superior
to the modified UNIFAC method developed in Lyngby,
Denmark, by Larsen et al. (1987),particularly because
more reliable ymresults were obtained.
Apart from more reliable results for industrial applica-
tions, a broad range of applicability is also important. The
existing parameter matrix for the modified UNIFAC
(Dortmund) method was therefore extended with the help
of the Dortmund Data Bank (DDB) and the integrated
fitting routines. The results were then checked with the
aid of a large data base and thoroughly compared with the
results of other group contribution methods.
The Modified UNIFAC Model
In the modified UNIFAC (Dortmund) model, as in the
original UNIFAC model, the activity coefficient is the s u m
of a combinatorial and a residual part:
In yi = In yci + In -yRi (1)
The combinatorial part was changed in an empirical way
to make it possible to deal with compounds very different
in size:

( ; (2))
scription of the hE-valuesallows the use of the parameters
across a larger temperature range (lower or higher tem-
peratures), e.g., to account for the real behavior during the In yci = 1 - V’i + In V: - 5qi 1 - - + In (2)
calculation of solid-liquid equilibria. The use of thermo-
dynamic mixture information from compounds very dif- The parameter V: can be calculated by using the relative
ferent in size (e.g., y”-values) will allow an improved de- van der Waals volumes Rk of the different groups.

+ Permanent address: Department of Chemical Engineering,

(3)
Tsinghua University, Peking, China.
o ~ ~ ~ - ~ ~ ~ ~ ~ ~ ~ 0~ 1993
z ~American
~ z - Chemical
o i ~ ~Society
~ o ~ . o o ~ o

All other parameters are calculated in the same way as for
the original UNIFAC model; i.e.
vi = -ri
(4)
Cxjrj
i
Fi = CYk(i)Rk (4a)
The residual part can be obtained by using the following
relations:
In yiR= Cuk(')(lnrk - In rk(i)) (6)
k
whereby the group area fraction 8, and group mole frac-
tion X, are given by the following equations:
Qmxm
e,,, = -
n
Qnxn
c V,%j
(9)
In comparison to the original UNIFAC method, only the
van der Waals properties were changed slightly, at the
same time temperature-dependent parameters were in-
troduced to permit a better description of the real behavior
(activity coefficients) as a function of temperature.
Data Base Used for Fitting the Group Interaction
Parameters
The generation of reliable group interaction parameters
requires the use of a large data base for fitting the required
parameters. The construction of a computerized data
compilation (DDB) was started at the University of
Dortmund as early as 1973. The intention was to use the
vast amount of published phase equilibrium information
for the development or improvement of group contribution
methods. At first, mainly VLE data were stored in com-
puter readable form together with the pure component
properties (e.g., Antoine constants, critical data, van der
Waals properties, structural information) required for
phase equilibrium calculations. Later, liquid-liquid
equilibrium data (LLE), heats of mixing (hE),gas solu-
bilities, excess heat capacities (cpE), activity coefficients
at infinite dilution (7-1, and azeotropic data were added.
These additions were partly carried out in collaboration
with the research groups of Prof. Aa. Fredenslund (Lyngby,
Denmark), Prof. A. G. Medina (Porto, Portugal), Prof. I.
Kikic and Prof. P. Alessi (Trieste, Italy), and Prof. H.
Knapp (Berlin, FRG). The present status of the DDB
(Gmehling, 1985,1991) is shown in Figure 1. To obtain
information about the real mixture behavior at low tem-
peratures, the construction of a data bank for solid-liquid
equilibria (SLE) is in progress. A great part of the data
(ca. 50%)has been published in an evaluated and unified
form in the different volumes of the DECHEMA Chem-
istry Data Series (Gmehling et al., 1977,1984; Tiegs et al.,
Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 179
Pure Component Properties
for appr. 3050 compounds
References for each type of data XYX
x*x = VLE, LLE HE.ACT GLE CPE AZD
appr 7700 references
Data on Mixtures
Number of Isotherms
or Isobars
Vapor-Liquid Equilibria ( V L E ) 14300
Liquid-Liquid Equilibria ( LLE ) 5600
Heats of Mixing ( HE )
Activity Coefficients at Infinite
8000
Dilution ( ACT ) 28500 values
Gas Solubilities ( GLE ) 5250
Excess Heat Capacities ( CPE ) 630
Azeotropic Data ( AZD ) 28000 values
Figure 1. Present status of the Dortmund Data Bank.
1986; Serrensen, 1979) and has been integrated in process
simulators by a large number of chemical and petrochem-
ical companies.
To complete the data base and to fill, at least partially,
the existing gaps in the data base, more than 100 hE-data
sets using isothermal flow calorimetry and ca. 1000 ym-
values using gas-liquid chromatography and ebulliometry
have been measured; in the case of the hE-data in partic-
ular, data at temperatures different from 25 OC where most
of the hE-data were obtained and data for compounds
containing new main groups (e.g., CCl,, ...) were measured.
Fitting Procedure
The temperature-dependent parameters for the modi-
fied UNIFAC (Dortmund) method were obtained, as far
as the required experimental data for the different ther-
modynamic properties were available in the DDB, by
fitting the parameters simultaneously to VLE, hE, and 7-
data. In a few cases LLE and cpE-datawere also used. The
parameter fitting procedure is shown in Figure 2. Using
the DDB, the selection of the desired pure component and
mixture data is quite simple. The procedure will be dis-
cussed for the arbitrary example of fitting alcohol-ester
parameters. With the decision as to what group pair (in
this example, alcohol-esters) should be fitted and what
additional groups are allowed (in this case, alkane groups),
a program (CODSNT) runs through the pure component
data file (STOFF) to find all the code numbers used in the
DDB for the different alcohols and esters with the help
of stored structural information. The selected code num-
bers are then stored in files (STL-files 1 and 2) and are
used to search the different binary data sets and to store
the appropriate mixture data in different files (VLE, ACT,
HE, CPE, LLE). Afterward the complete VLE data (x,
y, P, T ) or isothermal xy-data ( x , y, T given) are checked
for thermodynamic consistency using the programs
KONSlSRK and KONSSSRK, while for other incomplete
VLE data a flexible Legendre polynomial is used to fit the
data. The files are then checked for plausibility with the
help of other programs (XXXMOD). After a good dis-
tribution (compounds, temperature) of the systems has
been reached, the final data files are used to fit the pa-
rameters and Rk- and Qk-values, whereby the van der
Waah properties Rk and Qkof the different subgroups have
almost always been fitted using alkane systems, e.g., al-
cohol-alkanes, ester-alkanes, etc. The fitting procedure
involves the use of consistent VLE data (reliable Px-, Tx-,
180 Ind. Eng. Chem. Res., Vol. 32,No. 1, 1993
I I
Figure 2. Procedure used for fitting the required group interaction parameters of the modified UNIFAC (Dortmund) method.
and isothermal xy-data) together with other mixture in-
formation to minimize the following objective function:
J'(anm,bnm,Cnm8h,Qk) = CAVLE + CAY"+
CAhE+ CAcpE + CALLE = min (11)
In the case of VLE, depending on the data type (complete,
incomplete, etc.), it was necessary to define different
relative deviations which contribute to the objective
function. The contribution of the different types of data
to the objective function is given in Table I.
The following relations were used for calculating va-
por-liquid equilibria (yi, Ki, ...):
The real behavior of the vapor phase was taken into ac-
count by using the Soave-R.edlich-Kwong equation of state
(klZ= 0.0). In the case of carboxylic acids, chemical theory
was applied using the dimerization constants given in the
DECHEMA Chemistry Data Series (part 5 ) (Gmehling et
al., 1977).
During the fitting procedure (program NEMA), it is
possible to change the weighting factors for the different
types of binary data. For fitting the parameters the Sim-
plex-Nelder-Mead method by Nelder and Mead (1965)
is first used to obtain good initial values for the method
by Marquardt (1963). In all cases the fitting procedure
was started with constant group interaction parameters
(two parameters). When enough information about the
temperature dependence was available (hE, vLE(T),y"(T),
LLE(T)), linear temperature-dependent parameters were
fitted (four parameters) using the constant parameters as
initial values. In the case of very strong temperature de-
pendence, the number of fitted parameters was increased
to six (quadratic temperature dependence) when sufficient
information about the temperature dependence was
NEMA input
available (hE(T),cpE,besides VLE(T), 7"(T),LLE(T)). In
this case the linear temperature-dependent parameters
served as initial values for the fitting procedure. AU fitted
parameters were used subsequently for a thorough test of
the predicted results. Besides the deviation from the ex-
perimental data, the results were compared with other
group contribution methods. The comparison was sim-
plified by using programs which were able to check the
results not only for group combinations but also for the
whole DDB. The comparison was supported by helpful
printed tables and graphical representations. If unsatis-
factory results were obtained, the fitting procedure was
restarted with modified weighting factors. During the
fitting procedure data points or systems often had to be
excluded. For this job (fitting of group interaction pa-
rameters, comparison of the predicted results, etc.) the
DDB is the ideal tool, since all the required information
(mixture data, pure component properties such as Antoine
constants, critical data, structural information, etc.) for
checking the thermodynamic consistency or fitting the
required group interaction parameters can directly be
called from direct access files.
Since about 95% of the published hE-valueswere mea-
sured within the temperature range 10-50 OC, the fitted
temperature-dependent group interaction parameters can
lead to erroneous results when used outside the tempera-
ture range of the data base (in most cases 20-125 "C).
Apart from the comparison of the calculated results with
the experimental data, the reliability of the predicted
hE-valuesand activity coefficients at low (190 K)and high
temperatures (500 K) were checked using typical binary
systems for the group combination under consideration.
The reliability of the temperature extrapolation can be
judged from this information. For unreasonable results,
i.e., when very high positive or negative values for hEor
ym(near zero or very large) were obtained, the parameters
were, in most cases,fitted again. Most of these parameters
can now be used with confidence. For some group com-
binations (e.g. alkane-alcohols at low temperatures),
 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 181
Table I. Contribution of the Different Types of Data to the Table 11. Data Base Used for Fitting the Group Interaction
Objective Function Parameters
data type VLE hE 7-
thermodmamic information constant (a) Alcohol-Ester Systems
1 VLE (VLE) x,, Y1, p total no. of data seta 169 91
2 VLE (VLE) X , ? YIP T
total no. of data pointa 2926 1504 188
3 VLE (VLE) XI, p no. of consistent data seta 63
4 VLE (VLE) x,, T temperature range ("C) 25-193 25-75 20-150
5 VLE (VLE) x11 Y,
C-atoms alcohol 2-5 2-10 2-22: 2-4'
6 7- (ACT) Y -, C-atoms ester 3-9 3-6 4-26; 3-6'
7 hE (HE) x,, he (b) Ester-Carboxylic Acid Systems
8 cpE (CPE) X I , CPE
total no. of data seta 35 1
9 LLE (LLE) x ;, x ff, total no. of data points 463 13 52
VLE (data types 1, 2): no. of consistent data seta 6
2
temperature range ("C) 25-155 35 40-143
- Yik,calc
AVLE= 2nw k-1
E fIrl
(gm
7th
Ytk ) C-atoms ester
C-atoms carboxylic acid
3-13
2-12
3
2
4-18," 3-6'
2-18," 2-4'

>'
Solvent. Solute.
VLE (data types 3, 4):

AvLE=--C
1
nWk=l
nw (
g m
pk p+-:dc
VLE (data type 5):
Kik - K t k , d c
AVLE = -
(
nw
gvLE
2nwk=lI-1 K,k
7- (data type 6):
hE (data type 7):
cpE(data type 8):
LLE (data type 9):"
In the case of LLE, activity coefficienta at ca. four different tem-
peratures for every system were used in the fitting procedure. The
required activity coefficients in the coexisting phases were ob-
tained by fitting temperature-dependentNRTL or UNIQUAC pa-
rameters to the LLE data from different authors stored in the
Dortmund Data Bank using the program LLEOPT2 by Meyer and
Gmehling (1991).
however, it is dangerous to use the parameters in a tem-
perature range outside 20-125 "C. In the future the pa-
rameters marked by "+!", "-!", or "&!" will be revised, but,
first, hE-data in the temperature range 50-180 "C will be
measured for these systems using isothermal flow calori-
metry. This experimental work is in progress (Gmehling
and Meents, 1992).
In comparison to the original UNIF'AC method four new
main groups (cyclic hydrocarbons, cyclic ethers, chloro-
form, formic acid) were added to obtain more reliable
results for systems containing these components. Thus,
for example with the cyclic hydrocarbon group, hE-values
different from zero are obtained for systems containing
alkanes and cycloalkanes; with the cyclic ether group re-
sulta are improved for systems with compounds such as
dioxane, 1,4-tetrahydrofuran, dioxolane, etc. The same is
true for systems containing chloroform and formic acid.
Using the same main group for chloroform and the CC13
group, e.g., for l,l,l-trichloroethane, strong negative de-
viation from Raoult's law and large negative hE-valuesare
predicted (for example, for systems with acetone). But
because of the missing hydrogen bond, the system ace-
tone-l,l,l-trichlorothanebehaves very differently when
compared with the system acetone-chloroform. Thus in
contrast to the system acetone-chloroform, the system
acetone-l, 1,l-trichloroethane shows positive deviation
from Raoult's law and positive hE-values.
The group combinations which now have group inter-
action parameters are shown in Figure 3. In this figure
black squares characterize combinations for which, apart
from sufficient VLE data, enough hE- and 7"-data for
different compounds (e.g., different alcohols, different
esters) were also available across a large temperature range
for fitting the required group interaction parameters.
Shaded squares are used in the parameter matrix when
the data base was not fully satisfactory. However, even
in these cases at least the data base used to fit the original
UNIFAC parameters was applied. Examples for black and
shaded squares are given in Table I1 for the ester-alcohol
systems (black squares) and for the main group combi-
nation eaters with carboxylic acids (shaded squares). From
Table I1 it can be seen that for alcohol-ester mixtures more
than 4500 experimental data points were available within
the temperature range 20-193 "C and that at the same
time very different alcohols (ethanol4ocosanol) and eaters
(methyl acetate-bis(2-ethylhexyl) sebacate) were applied
to fit the parameters, whereby, with the use of 7"-data,
information about compounds very different in size is
included. For estel-carboxylic acids the data base is much
smaller.
The van der Waals properties of the different subgroups
together with the group assignments are given in Table III.
All the group interaction parameters obtained are listed
in Table IV. While in the first paper by Weidlich and
Gmehling (1987) parameters for only 15 group combina-
tions and 6 main groups were presented, the parameters
for 45 main groups and 530 group pairs are now available.
This means that the Rk-and Qpalues and group inter-
action parameters given in Tables I11 and IV allow the
prediction of the phase behavior of a large number of
non-electrolyte systems of interest for the chemical in-
dustry.
Rssults
A comprehensive comparison of the results of the dif-
ferent group contribution methods was carried out by
Schiller (1992) using all the information stored in the DDB.
Since the number of main groups and available group
182 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993

Table 111. Rk-and Qk-Parametersand Group Assignment for the Modified UNIFAC (Dortmund) Method
main group subgroup no. Rk Qk
sample group assignment
1 'CHz" CH, 1 0.6325 1.0608 hexane 2 CH3,4 CHZ
CH; 2 0.6325 0.7081 octane 2 CH3,6 CHZ
CH 3 0.6325 0.3554 2-methylpropane 3 CH3,l CH
C 4 0.6325 O.oo00 neopentane 4 CHB, 1 C
2 'C=C" CHz=CH 5 1.2832 1.6016 1-hexene 1 CH3,3 CH2,l CHz=CH
CH=CH 6 1.2832 1.2489 2-hexene 2 CH3,2 CH2,l CH=CH
CHz=C 7 1.2832 1.2489 2-methyl-1-butene 2 CH3,l CH2,l C H 2 4
CH=C 8 1.2832 0.8962 2-methyl-2-butene 2 CH3,l CH=C
c=c 70 1.2832 0.4582 2,3-dimethyl-2-butene 4 CH3,l C=C
3 "ACH" ACH 9 0.3763 0.4321 naphthalene 8 ACH, 2 AC
AC 10 0.3763 0.2113 styrene 1 CHz=CH, 5 ACH, 1 AC
4 'ACCHz" ACCH3 11 0.9100 0.9490 toluene 5 ACH, 1 ACCH3
ACCHZ 12 0.9100 0.7962 ethylbenzene 1 CH3,5 ACH, 1 ACCHZ
ACCH 13 0.9100 0.3769 isopropylbenzene 2 CH3,5 ACH, 1 ACCH
5 'OH" OH (PI 14 1.2302 0.8927 1-propanol 2 CH3, 1 CH2, 1 OH (p)
OH (s) 81 1.0630 0.8663 2-propanol 2 CH3,l CH, 1 OH (9)
OH (t) 82 0.6895 0.8345 tert-butanol 3 CH3, 1 C, 1 OH (t)
6 'CH30H" CHBOH 15 0.8585 0.9938 methanol 1 CH30H
7 'H20" HZO 16 1.7334 2.4561 water 1 HzO
8 'ACOH" ACOH 17 1.0800 0.9750 phenol 5 ACH, 1 ACOH
9 'CHzCO" CH&O 18 1.7048 1.6700 2-butanone 1 CH3,l CH2,l CH3CO
CHzCO 19 1.7048 1.5542 2-pentanone 2 CH3,l CHp, 1 CHzCO
10 'CHO" CHO 20 0.7173 0.7710 propionic aldhyde 1 CH3,l CHZ, 1 CHO
11 "CCOO" CH3CO0 21 1.2700 1.6286 butyl acetate 1 CH3,3 CHZ, 1 CH3COO
CHZCOO 22 1.2700 1.4228 methyl propionate 2 CH3,l CHZCOO
12 "HCOO" HCOO 23 1.9000 1.8000 ethyl formate 1 CHR, 1 CH,. 1 HCOO
13 "CHzO" CH30 24 1.1434 1.6022 dimethyl ether 1 CH,, 1 CHjO
CHZO 25 1.1434 1.2495 diethyl ether 2 CH3,l CHP, 1 CHZO
CHO 26 1.1434 0.8968 diisopropyl ether 4 CH3,l CH, 1 CHO
14 'CNHz" CH3NHz 28 1.6607 1.6904 methylamine 1 CHBNHZ
CHzNH2 29 1.6607 1.3377 ethylamine 1 CH3,l CHzNHz
CHNHz 30 1.6607 0.9850 isopropylamine 2 CHe, 1 CHNH,
CNH, 85 1.6607 0.9850 tert-butylamine 3 CH,, 1 CNHz -
15 "CNH" CH3NH 31 1.3680 1.4332 dimethylamine 1 CHB, 1 CH3NH
CHzNH 32 1.3680 1.0805 diethylamine 2 CH3,l CH2,l CHzNH
CHNH 33 1.3680 0.7278 diisopropylamine 4 CH3,l CH, 1 CHNH
16 "(C)3N" CH3N 34 1.0746 1.1760 trimethylamine 2 CH3,l CH3N
CHzN 35 1.0746 0.8240 triethylamine 3 CH3,2 CH2,l CHZN
17 'ACNHZ" ACNHZ 36 1.1849 0.8067 aniline 5 ACH, 1 ACNHz
18 'Pyridine" C5H5N 37 2.5000 2.1477 pyridine 1 C5HSN
C5H4N 38 2.8882 2.2496 2-methylpyridine 1 CH3,l C5H4N
C5H3N 39 3.2211 2.5000 2,3-dimethylpyridine 2 CH3,l C5H3N
19 "CCN" CH3CN 40 1.5575 1.5193 acetonitrile 1 CH3CN
CHzCN 41 1.5575 1.1666 propionitrile 1 CH3,l CHZCN
20 'COOH" COOH 42 0.8000 0.9215 acetic acid 1 CH3,l COOH
21 "CCl" CHzCl 44 0.9919 1.3654 1-chlorobutane 1 CH3, 2 CHz, 1 CH,Cl
CHCl 45 0.9919 1.0127 2-chloropropane 2 CH3, 1 CHCl
CCl 46 0.9919 0.6600 tert-butyl chloride 3 CH3, 1 CCl
22 "CClZ" CHzClz 47 1.8000 2.5000 dichloromethane 1 CHzClz
CHClz 48 1.8000 2.1473 1,l-dichloroethane 1 CH3, 1 CHClz
CClZ 49 1.8000 1.7946 2,2-dichloropropane 2 CH3, 1 CC12
23 'CCl," CCl, 51 2.6500 2.3778 l,l,l-trichloroethane 1 CH,. 1 CCL
24 'CCl," CCl, 52 2.6180 3.1836 tetrachloromethane 1 cci4'
25 "ACCl" ACCl 53 0.5365 0.3177 chlorobenzene 5 ACH, 1 ACCl
26 "CN02" CH3N02 54 2.6440 2.5000 nitromethane 1 CH,NO,
CHzNOz 55 2.5000 2.3040 1-nitropropane 1 CH,, 1 6Hz, 1 CHZNOz
CHNOz 56 2.8870 2.2410 2-nitropropane 2 CH3,l CHNOz
27 'ACNOZ" ACNOz 57 0.4656 0.3589 nitrobenzene 5 ACH, 1 ACNO,
28 "CSZ" CSZ 58 1.2400 1.0680 carbon disulfide 1cs2
29 'CH3SH" CHBSH 59 1.2890 1.7620 methanethiol 1CHSH
CHZSH 60 1.5350 1.3160 ethanethiol 1 CH,, 1 CHzSH
30 'furfural" furfural 61 1.2990 1.2890 furfural 1 furfural
31 'DOH" DOH 62 2.0880 2.4000 1,2-ethanediol 1 DOH
32 'I" I 63 1.0760 0.9169 ethyl iodide 1 CH3,l CHZ, 1 I
33 "Br" Br 64 1.2090 1.4000 ethyl bromide 1 CH3, 1 CH,, 1 Br
34 'C=C" CH=C 65 0.9214 1.3000 1-hexyne 1 CH3,3 CH2,l C H 4
CEC 66 1.3030 1.1320 2-hexyne 2 CH3,2 CHZ, 1 C 4
35 'DMSO" DMSO 67 3.6000 2.6920 dimethyl sulfoxide 1 DMSO
36 'ACRY" acrylonitrile 68 1.oooO 0.9200 acrylonitrile 1 acrylonitrile
37 'ClCC" Cl(C=C) 69 0.5229 0.7391 trichloroethylene 1 CH=C, 3 Cl(C=C)
38 'ACF" ACF 71 0.8814 0.7269 hexafluorobenzene 6 ACF
39 'DMF" DMF 72 2 . m 2.0930 NJ-dimethylformamide 1 DMF
HCON(CH2)z 73 2.3810 1.5220 NJ-diethylformamide 2 CH3, 1 HCON(CHz)z
40 'CFZ" CF3 74 1.2840 1.2660 l,l,l-trifluoroethane 1 CH3, 1 CF3
CFZ 75 1.2840 1.0980 perfluorohexane 2 CF,. 4 CFo
CF 76 0.8215 0.5135 perfluoromethylcyclohexane 1 CF,; 5 CF;, 1 CF
 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 183

Table I11 (Continued)

main group subgroup no. sample group assignment
Rk Qk
41 'COO" coo 77 1.6000 0.9000 methyl acrylate 1 CHq, 1 CH,=CH, 1 COO
42 'c-CH," c-CHZ 78 0.7136 0.8635 cyclohexane 6 c-CH,
C-CH 79 0.3479 0.1071 methylcyclohexane 1 CHS, 5 c-CH~,1 C-CH
c-c 80 0.3470 O.oo00 1,l-dimethylcyclohexane 2 CH3, 5 c-CH,, 1 c-C
43 'C-CHZO" C-CHZOCH~ 27 1.7023 1.8784 tetrahydrofuran 2 c-CH~,1 c-CH~OCH~
c-CHzO[WIi z 83 1.4046 1.4000 1,3-dioxane 1 c-CH~,2 ~-CH20[CH2]1/2
C-[CH21120[C~211/2 84 1.0413 1.0116 1,3,5-trioxane 3 c-[CH211 20[CHZ11/2
44 'HCOOH" HCOOd 43 0.8000 1.2742 formic acid 1 HCOOd
45 "CHC13" CHCl, 50 2.4500 2.8912 chloroform 1 CHCI,

Figure 3. Present status of the modified UNIFAC (Dortmund) parameter matrix.

interaction parameters is very different for the group
contribution methods studied (ASOG by Tochigi et al.
(1990), UNIFAC by Hansen et al. (1991), modified UNI-
FAC (Dortmund) (thiswork), modified UNIFAC (Lyngby)
by Larsen et al. (1987)), there is also a difference in the
total number of systems which can be predicted by the
different methods. With the original and the modified
UNIFAC (Dortmund) method, more systems can be pre-
dicted than with the ASOG or modified UNIFAC (Lyngby)
method. The results for binary systems are summarized
in Tables V-VIII. In these tables the results are given
for compounds with a limited number of different main
groups; furthermore the comparison was limited to the
number of systems which could be calculated with the
modified UNIFAC (Lyngby) method proposed. Since
more systems can be predicted with the original UNIFAC
and the modified UNIFAC (Dortmund) methods, the ta-
bles also contain deviations for all the systems which could
be predicted with these latter methods. Tables V and VI
provide the results for VLE (P< 5000 mmHg, cpvi/cpSi =
1). While in Table V the results are shown only for the
data seta which passed two thermodynamic consistency
tests (Gmehling et al., 1977), in Table VI the deviations
in vapor-phase mole fraction, temperature, and pressure
are given for all binary data sets (P< 5000 mmHg, p v i / &
= 1). From these results it is concluded that modified
UNIFAC (Dortmund) gives the best results. When com-
pared with the original UNIFAC method, which today is
used in most of the commercial process simulators for
VLE, a clear improvement can be recognized. An im-
provement in Ay = 0.5 mol % (36%), AT = 0.3 K (33%),
and hp of ca. 6 mmHg (45%) is obtained. Also when
comparison is made with the modified UNIFAC (Lyngby)
method, better results are predicted for all the mentioned
quantities. That the absolute deviations presented in
Table VI are much larger than those in Table V is due to
the fact that all data were considered and all experimental
errors are included in the deviations calculated.
Table VI1 shows the deviation between experimental
and predicted heats of mixing data. Besides the results
for 4900 data sets for the UNIFAC method and the mod-
ified UNIFAC (Dortmund) method, the deviations are also
given for all predictable data sets. It can be seen that
improved results are obtained for the modified UNIFAC
184 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993

Table IV. Modified UNIFAC (Dortmund) Group Interaction Parameters"

n m on, (K) brim c,, (K-7 amn(K) bmn c, (K-9
1 2 189.66 -0,2723 0.0 -95.418 0.6171 X lo-' 0.0
1 3 114.20 0.9330 X lo-' 0.0 16.070 -0.2998 0.0
1 4 7.3390 -0.4538 0.0 47.200 0.3575 0.0
1 5 -! 2777.0 -4.6740 0.1551 X 1606.0 -4.7460 0.9181 x 10-3
1 6 -! 2409.4 -3.0099 0.0 82.593 -0.4857 0.0
1 7 1391.3 -3.6156 0.1144 X low2 -17.253 0.8389 0.9021 X
1 8 1381.0 -0.9977 0.0 1987.0 -4.6150 0.0
1 9 433.60 0.1473 0.0 199.00 -0.8709 0.0
1 10 875.85 0.0 0.0 256.21 0.0 0.0
1 11 98.656 1.9294 -0.3133 X lo-* 632.22 -3.3912 0.3928 x
1 12 508.40 -0.6215 0.0 238.50 -0,5358 0.0
1 13 233.10 -0.3155 0.0 -9.6540 -0,3242X 10-1 0.0
1 14 -164.04 4.9683 -0.1025 X 10-1 326.04 -2.6348 0.3358 X
1 15 350.58 0.6673 X 10-I 0.0 207.26 -1.0916 0.0
1 16 -175.70 1.8570 0.0 205.65 -1.4436 0.0
1 17 +! 958.74 -0.1484 0.0 2257.3 -5.6676 0.0
1 18 -9.2805 1.9682 -0.1405 X 258.57 -2.1156 0.1574 X
1 19 593.07 0.7335 0.0 293.81 -1.3979 0.0
1 20 1182.2 -3.2647 0.9198 X 2017.7 -9.0933 0.1024 X 10-1
1 21 401.00 -0.7277 0.0 -65.685 0.7409 X 10-1 0.0
1 22 -233.66 1.2561 0.0 311.55 -1.1856 0.0
1 23 -653.74 4.5311 -0.8735 X 1302.6 -8.4270 0.1442 X 10-1
1 24 267.51 -1.7109 0.3388 X lo-' -148.07 1.0927 -0.2416 X lo-*
1 25 -1385.0 15.890 -0.4831 X lo-' 3264.0 -20.840 0.3317 X 10-1
1 26 2345.0 -13.200 0.2156 X 10-1 -396.50 3.0920 -0.6266 X
1 27 2383.0 -2.693 0.0 1744.0 -4.0820 0.0
1 28 24.330 1.5210 0.0 72.120 -1.1260 0.0
1 29 465.90 -0.8557 0.0 -59.900 -0.8313 X 0.0
1 30 577.70 0.9384 0.0 210.50 -1.0810 0.0
1 31 -! 897.70 0.0 0.0 28.170 0.0 0.0
1 32 559.90 -0,3564 0.0 166.00 -0,7116 0.0
1 33 527.70 -0.4990 0.0 -62.080 -0.3658 0.0
1 34 477.50 -0.6581 0.0 -22.040 -0,1018 0.0
1 35 -547.50 3.4570 0.0 477.10 -2.1750 0.0
1 36 *! 1662.0 0.0 0.0 -291.90 0.0 0.0
1 37 +! 334.50 0.9102 X 0.0 3.2020 -0.6894 0.0
1 38 468.50 -1.0420 0.0 -160.30 -0.1080 x 10-1 0.0
1 39 406.20 0.6525 0.0 151.00 -0.9023 0.0
1 40 342.00 -1.6790 0.0 -484.30 2.4670 0.0
1 41 1312.0 -3.6430 0.0 -314.60 1.2870 0.0
1 42 +! -680.95 4.0194 -0.6878 X lov2 1020.8 -6.0746 0.1015 X 10-1
1 43 79.507 0.7089 -0,2098 X 186.71 -1.3546 0.2402 x
1 44 -! 1935.7 0.0 0.0 -21.230 0.0 0.0
1 45 164.25 -0.2683 0.0 -44.069 0.2778 X lo-' 0.0
2 3 174.10 -0.5886 0.0 -157.20 0.6166 0.0
2 4 117.30 -0.8552 0.0 -113.10 1.1720 0.0
2 5 2649.0 -6.5080 0.4822 X 1566.0 -5.8090 0.5197 X
2 6 -628.07 1o.ooo -0.1497 X lo-' -96.297 0.6304 -0.1800 x
2 7 -! 778.30 0.1482 0.0 -1301.0 4.0720 0.0
2 8 1207.0 -1.9550 0.0 191.60 0.4936 0.0
2 9 179.80 0.6991 0.0 91.811 -0.7171 0.0
2 10 476.25 0.0 0.0 202.49 0.0 0.0
2 11 980.74 -2.4224 0.0 -582.82 1.6732 0.0
2 12 309.80 0.0 0.0 -28.630 0.0 0.0
2 13 -! 733.30 -2.5090 0.0 -844.30 2.9450 0.0
2 14 *! 1857.0 -8.6530 0.1088 X 10-1 498.80 -5.1480 0.1039 X 10-1
2 15 t! 224.80 0.0 0.0 -124.32 0.0 0.0
2 16 *! 165.30 0.0 0.0 -131.50 0.0 0.0
2 17 2800.0 -10.720 0.1339 X 10-1 3982.0 -19.720 0.2783 X lo-'
2 18 *! 13.502 0.0 0.0 -13.317 0.0 0.0
2 19 634.85 0.0 0.0 -181.93 0.0 0.0
2 20 *! -2026.1 8.1549 0.0 -347.50 1.2160 0.0
2 21 498.90 -1.4870 0.0 -359.60 1.2380 0.0
2 22 -44.958 0.0 0.0 55.881 0.0 0.0
2 23 &! -204.51 0.0 0.0 255.41 0.0 0.0
2 24 616.62 -2.1164 0.0 -663.45 2.3281 0.0
2 25 -56.690 9.8050 0.0 215.50 -1.5190 0.0
2 26 417.60 0.8726 X 10-1 0.0 452.20 -1.9970 0.0
2 28 a! 46.060 1.5450 0.0 70.880 -1.0900 0.0
2 30 470.40 0.0 0.0 -146.10 0.0 0.0
2 33 -19.820 0.5941 0.0 160.40 -0.5148 0.0
2 34 -44.760 0.0 0.0 180.60 0.0 0.0
2 35 -174.60 1.9600 0.0 154.00 -1.3030 0.0
2 36 179.70 0.0 0.0 -113.80 0.0 0.0
2 37 967.90 -0.3862 X 10-1 0.0 -300.60 -0.9576 X 10-1 0.0
2 38 141.10 -0.3025 0.0 -139.50 0.9076 0.0
2 39 388.40 0.0 0.0 -152.20 0.0 0.0
 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 185

Table IV (Continued)
n m 4nm (K) bnm cnm W-') 4mn (W bmn Cmn W-')
2 41 -339.80 1.2970 0.0 698.50 -2.1590 0.0
2 42 -78.190 0.1327 0.0 182.40 -0.3030 0.0
2 43 *! -322.10 -0.2037 0.4517 X 1182.6 -5.oooo 0.3745 X
2 45 389.28 0.0 0.0 -174.41 0.0 0.0
3 4 139.20 -0.6500 0.0 -45.330 0.4223 0.0
3 5 3972.0 -13.160 0.1208 x 10-1 3049.0 -12.770 0.1435 X 10-1
3 6 1604.3 -2.0299 0.0 13.733 -0.1177 0.0
3 7 792.00 -1.7260 0.0 332.30 1.1580 0.0
3 8 1356.0 -2.1180 0.0 2340.0 -5.0430 0.0
3 9 146.20 -1.2370 0.4237 X -57.530 1.2120 -0.3715 X
3 10 -365.50 1.8740 0.0 1011.0 -2.1670 0.0
3 11 -274.54 0.9149 0.0 622.73 -1.7605 0.0
3 12 170.50 -0.2393 X lo-' 0.0 108.30 -0.2620 0.0
3 13 -87.080 -0.1859 0.0 179.00 0.5615 X lo-' 0.0
3 14 2036.0 -8.7290 0.8138 X -121.00 -1.9010 0.6999 X lo-*
3 15 139.67 0.3769 X 10-1 0.0 105.63 -0.6067 0.0
3 16 -71.400 0.7078 0.0 16.290 -0.6022 0.0
3 17 1044.7 -1.7112 0.0 154.39 1.2458 0.0
3 18 1047.0 -5.5620 0.8771 X -590.00 2.9160 -0.4935 x 10-2
3 19 -17.440 0.9437 0.0 111.80 -0.5959 0.0
3 20 69.561 1.8881 0.0 613.32 -1.5950 0.0
3 21 73.046 -0.2132 0.0 -58.972 0.1046 0.0
3 22 133.66 -0.4614 0.0 -142.20 0.3966 0.0
3 23 66.214 -0.6363 0.0 -78.116 0.6998 0.0
3 24 269.0 -1.7760 0.2645 X -305.50 2.1200 -0.3239 X
3 25 595.20 3.3090 -0.2844 x 10-1 1885.0 -10.980 0.1661 X lo-'
3 26 134.10 -0.8156 0.1450 X lo-' -330.00 3.0660 -0.5376 X
3 27 746.90 0.0 0.0 36.450 0.0 0.0
3 28 3736.0 -25.000 0.4593 X lo-' 574.60 -3.7020 0.3682 X
3 29 A! 59.230 0.0 0.0 -41.770 0.0 0.0
3 30 331.60 0.3778 0.0 0.4086 -0.4601 0.0
3 31 345.50 0.0 0.0 -14.060 0.0 0.0
3 32 *! -82.280 0.5677 0.0 298.90 -0.8374 0.0
3 33 -248.20 1.2140 0.0 187.50 -0.9020 0.0
3 35 347.60 -1.4300 0.0 -345.60 1.5450 0.0
3 37 602.10 -7.7980 0.1966 X 10-1 1887.0 -8.7070 0.7813 X
3 38 808.00 -5.3310 0.6077 X loe2 -1367.0 7.8830 -0.7754 x 10-2
3 39 15.570 0.8460 0.0 -4.2990 -0.4298 0.0
3 41 -126.20 0.3860 0.0 670.80 -1.8070 0.0
3 42 33.344 -0.4849 0.0 84.418 0.4046 0.0
3 43 -26.852 -0.4421 0.0 47.230 0.6404 0.0
3 44 +! -1172.0 10.106 -0.1428 X lo-' -1141.6 8.6562 -0.1544 X lo-'
3 45 380.02 -0.2333 0.0 -201.52 -0.6877 X lo-' 0.0
4 5 -! 3989.0 -14.090 0.1530 X lo-' 2673.0 -5.7650 -0.3320 X
4 6 436.21 1.9094 0.0 145.54 -0.4880 0.0
4 7 1050.2 -1.9939 0.0 24.144 1.6504 0.0
4 8 1375.0 -1.7020 0.0 1825.0 -3.7430 0.0
4 9 1001.0 -1.8710 0.2390 x 10-3 -146.60 0.2419 0.1133 X
4 10 683.60 -1.0200 0.8690 x 10-3 1963.0 2.6560 -0,1355X 10-1
4 11 -242.50 2.7200 -0.3449 x 10-2 1624.0 -9.4090 0.1338 X lo-'
4 12 *! 78.940 0.0 0.0 732.00 0.0 0.0
4 13 -595.10 2.9780 0.0 375.00 -1.5700 0.0
4 14 2977.0 -19.160 0.3333 X lo-' -45.440 5.1410 -0.1420 X 10-1
4 15 *! 1250.0 0.0 0.0 -316.22 0.0 0.0
4 16 -2631.0 13.560 -0.7036 X 978.30 -6.4810 0.7088 X
4 17 4000.0 -16.680 0.2112 x 10-1 3969.0 8.4970 -0.5945 x 10-2
4 18 -189.30 1.8600 0.0 214.20 -1.2790 0.0
4 19 208.10 1.3330 0.0 170.10 -0.8218 0.0
4 20 1352.5 0.0 0.0 29.747 0.0 0.0
4 21 -46.994 0.3044 0.0 113.07 -0.5957 0.0
4 22 213.85 0.2000 0.0 -75.010 -0.4268 0.0
4 23 192.52 -0.2536 0.0 -38.939 -0,1938 0.0
4 24 -106.20 0.6081 0.0 107.80 -0.6785 0.0
4 25 -113.60 19.720 0.0 -69.230 -0.7359 0.0
4 26 1358.0 -9.9680 0.2093 X lo-' 1014.0 -4.7020 0.4381 X
4 27 -2345.0 12.290 0.0 1567.0 -2.6780 0.0
4 28 2586.0 -9.5ooo 0.8819 X -1494.0 7.6790 -0.1225 X lo-'
4 30 157.90 1.4080 0.0 181.20 -1.0810 0.0
4 31 323.60 -0.2739 0.0 694.80 -0.8527 0.0
4 32 69.000 0.4317 0.0 448.80 -0.9919 0.0
4 33 277.00 -0.5955 0.0 -156.70 0.1221 0.0
4 35 88.930 0.2236 0.0 178.60 -0,7113 0.0
4 37 234.20 -0,2311 0.0 -115.90 -0.2925 X 10-I 0.0
4 38 -172.20 0.2257 0.0 -13.150 0.1763 X 0.0
4 39 403.30 -0.3234 0.0 -45.150 -0.5665 X 0.0
4 41 2303.0 -6.3460 0.0 -736.80 3.3320 0.0
4 42 147.38 -0.4889 0.0 -62.534 0.1798 0.0
186 Ind. Eng. Chem. Res., Vol. 32, No.1, 1993

Table IV (Continued)
n m (K)
a,, brim cn, (K-9 a, (K) bmn c,, (K-9
4 43 -26.486 -0,2952 0.0 199.48 0.3370X 10-I 0.0
4 44 +! -514.79 4.9372 0.0 291.65 -1.2039 0.0
4 45 297.73 -0.2420 0.0 -248.30 0.2547 0.0
5 6 346.31 -2.4583 0.2929X -1218.2 9.7928 -0.1616X 10-I
5 7 -801.90 3.8240 -0.7514X 1460.0 -8.6730 0.1641X 10-I
5 8 83.910 -1.2620 0.0 465.40 -1.8410 0.0
5 9 -250.00 2.8570 -0,6022X 653.30 -1.4120 0.9540X
5 10 -! -281.40 2.3790 -0,6668X 1590.0 -24.570 0.6212X lo-'
5 11 973.80 -5.6330 0.7690X 310.40 1.5380 -0.4885 X
5 12 235.90 -0.5874 0.0 839.60 -1.2150 0.0
5 13 1102.0 -7.1760 0.9698X 1631.0 -7.3620 0.1176 X lo-'
5 14 -! -923.70 2.4680 0.0 -75.630 -0,1511 0.0
5 15 -! -355.10 0.5800 0.0 -660.20 1.7430 0.0
5 16 104.60 -5.0140 0.8854X lo-* 1876.0 11.500 0.9Ooox 10-1
5 17 -1114.0 5.9160 -0.7126X 1325.0 -6.2630 0.7584x
5 18 -! 3979.0 -19.790 0.2691X lo-' -1496.0 9.3530 -0.1410X 10-I
5 19 123.50 0.8503 -0.2478X -46.000 4.4150 -0.8780X
5 20 -! -1295.0 4.3634 0.0 1525.8 -4.9155 0.0
5 21 238.10 -0.7077 0.0 2177.0 -4.3630 0.0
5 22 -126.00 0.1322 0.0 2389.0 -4.5090 0.0
5 23 1314.8 0.0 0.0 963.37 0.0 0.0
5 24 925.60 -2.0270 0.0 3139.0 -5.9640 0.0
5 25 1862.0 32.070 -0.9397x 10-2 3664.0 34.130 0.2987X
5 26 741.80 -2.0980 0.0 1091.0 -1.2740 0.0
5 27 2100.0 0.0 0.0 316.60 0.0 0.0
5 30 738.40 -1.7710 0.0 616.50 -0.1457 0.0
5 31 499.80 -2.4100 0.0 -468.80 2.4210 0.0
5 32 838.80 0.0 0.0 774.7 0.0 0.0
5 33 699.70 -1.7670 0.0 1439.0 -1.6730 0.0
5 34 -148.90 1.0340 0.0 1255.0 -2.5380 0.0
5 35 190.40 -1.2000 0.0 -452.30 1.9560 0.0
5 36 1117.0 -2.1960 0.0 1072.0 -1.2480 0.0
5 37 439.40 0.0 0.0 959.30 0.0 0.0
5 38 h! 848.60 0.0 0.0 1253.0 0.0 0.0
5 39 1036.0 -2.9950 0.0 -366.40 1.1290 0.0
5 41 403.80 -0.9346 0.0 703.40 -1.3830 0.0
5 42 3856.0 -17.970 0.2083X loF1 3246.0 -4.9370 -0.1143X
5 43 401.89 -0,4363 -0,2004X -238.36 5.oooo -0.8186X
5 45 -32.643 -0.1043X lo-' 0.0 2985.8 -6.2270 0.0
6 7 108.20 -0.9224 0.0 -774.50 3.8720 0.0
6 8 f! -867.00 -1.2580 0.2998X lo-' 265.50 -2.9050 0.2283X
6 9 86.439 -0,4651 0.0 394.78 -0.3605 0.0
6 10 f! -392.50 2.2560 0.0 -158.40 -0,6469 0.0
6 11 299.23 -1.2702 0.0 294.76 0.3745 0.0
6 12 220.70 -0.6402 0.0 444.70 -0.6819X 10-1 0.0
6 13 -87.480 -0,5522 0.0 475.20 0.1198 0.0
6 14 -! -495.25 1.0807 0.0 -467.95 0.6574 0.0
6 15 -! -1508.5 4.4917 0.0 -278.09 -0.3989 0.0
6 16 -! -1039.0 5.6030 -0.6551 X 39.330 -3.3540 0.6714X
6 17 -2012.0 13.460 -0.2004x 10-1 251.20 -1.2740 0.2214X
6 18 3153.0 -13.320 0.1190x 10-1 1556.0 -14.970 0.3041X 10-I
6 19 97.973 -0.2867 0.0 615.01 -0.9444 0.0
6 20 -733.07 2.3351 0.0 1075.5 -3.4339 0.0
6 21 -16.521 -0.2814 0.0 1831.2 -2.9694 0.0
6 22 -85.926 -0.2637 0.0 1904.4 -2.7981 0.0
6 23 -139.58 0.0 0.0 893.38 0.0 0.0
6 24 -40.130 -0.6709X 10-I 0.0 2150.0 -2.8130 0.0
6 25 3000.0 -11.810 0.0 2955.0 -6.3830 0.0
6 26 374.20 -2.2120 0.2688X 1079.0 -1.7660 0.1238X
6 28 +! -332.40 4.4190 -0,7797x 10-2 2645.0 -9.1720 0.1177X lo-'
6 29 +! 75.710 -0,3753 0.0 1334.0 -1.8630 0.0
6 30 -369.80 2.2030 0.0 662.00 -1.9030 0.0
6 31 33.190 -0.2074 0.0 -3.4280 0.4830 0.0
6 32 180.50 0.3161 0.0 1965.0 -3.8580 0.0
6 33 f! 28.950 -0,3303 0.0 648.80 0.8050 0.0
6 35 f! -185.90 0.3906x lo-' 0.0 145.00 -0.6343 0.0
6 36 164.00 0.0 0.0 135.90 0.0 0.0
6 37 -43.880 0.0 0.0 2421.0 0.0 0.0
6 38 -99.580 0.0 0.0 1235.0 0.0 0.0
6 39 101.20 -1.0780 0.0 -269.70 1.7320 0.0
6 41 308.70 -1.1750 0.0 678.10 -1.3350 0.0
6 42 68.972 -0.4200 0.0 2540.7 -3.5236 0.0
6 43 -308.7 1.7454 -0.3350X 952.24 -3.3287 0.5360X lo-*
6 45 -242.60 0.2956 -0.9006x 10-4 4519.3 -19.456 0.2598x lo-'
7 8 -2686.0 19.440 -0.2702X 10.' 148.40 -2.7570 0.2329X
7 9 190.50 -3.6690 0.8838X 770.60 -0.5873 -0.3252X
7 10 -! -1545.0 6.5120 0.0 512.60 -2.1450 0.0
 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 187

7 -675.50 3.6090 0.0 322.30 -1.3050 0.0

7 13 -197.50 0.1766 0.0 140.70 0.5679 X 10-I 0.0
7 14 -! 798.50 -5.8690 0.1032 X lo-' -980.60 3.6710 -0.5908 X
7 15 -! 1524.0 -2.5310 0.0 -851.00 1.0340 0.0
7 16 -! 274.50 -0,5905 0.2205 X -446.00 -0.7738 0.2634 X
7 17 158.40 0.5246 0.0 -131.00 -0.7957 0.0
7 18 -! 732.20 -0.6607 0.2019 X -619.30 1.9300 -0.3386 X lo-*
7 19 -634.10 3.5900 0.00 509.60 -1.9160 0.0
7 20 -1795.2 12.708 -0.1546 X lo-' 624.97 -4.6878 0.5237 X
7 21 86.690 1.5920 0.0 313.30 -0,5041 0.0
7 22 134.10 0.9495 0.0 748.20 -1.3190 0.0
7 24 +! 1008.0 -1.7950 0.0 1282.0 -2.8150 0.0
7 25 -1895.0 9.3030 0.0 591.60 -3.0800 0.0
7 26 -595.70 2.6340 0.0 882.60 -2.6060 0.0
7 30 -123.80 3.8470 0.0 501.40 -1.9390 0.0
7 31 372.50 -0.9091 0.0 -368.80 0.7775 0.0
7 33 822.20 0.0 0.0 -17.990 0.0 0.0
7 35 -! 117.00 -0,6110 0.0 -370.80 0.1043 0.0
7 36 419.80 2.4360 0.0 276.90 -0.9948 0.0
7 39 -! -494.20 2.8260 0.0 -121.80 -0.6029 0.0
7 41 676.00 -0.9909 0.0 808.40 -2.9290 0.0
7 42 274.37 -0.5861 -0.3001 x 10-3 1632.9 -2.8719 0.3455 X
7 43 54.962 -2.5850 0.8218 X 843.09 -2.6350 0.7040 X
7 44 -! -804.28 2.8280 0.0 594.45 -2.2535 0.0
7 45 509.30 -0.2900 0.0 -523.80 3.1580 0.0
8 9 -! -145.20 -0.7380 0.0 -666.80 1.9180 0.0
8 11 -! -212.90 0.0 0.0 -224.40 0.0 0.0
8 13 -329.30 0.0 0.0 -80.580 0.0 0.0
8 17 -! 542.00 -6.7920 0.1655 X lo-' -131.10 -0.9399 0.4690 x 10-3
8 18 -! -1231.0 4.9730 -0.6327 X lo-' 608.20 -6.2610 0.9693 X
8 20 401.88 0.0 0.0 281.08 0.0 0.0
8 24 2356.0 -3.3470 0.0 2157.0 -3.7180 0.0
8 25 555.50 0.0 0.0 1554.0 0.0 0.0
8 31 -! -309.00 0.0 0.0 191.70 0.0 0.0
8 42 -749.40 6.5890 -0.1101 x 10-1 1826.0 -1.0350 -0.2210 x 10-2
9 10 197.60 0.0 0.0 -93.080 0.0 0.0
9 11 -16.486 -0.2792 0.0 33.415 0.2191 0.0
9 12 -83.570 0.0 0.0 101.30 0.0 0.0
9 13 3645.0 -26.910 0.4757 X lo-' 695.80 -0.9619 -0,2462 X
9 15 -47.970 0.0 0.0 119.50 0.0 0.0
9 16 -389.60 0.1944 0.1863 X 2831.0 -13.010 0.1558 X 10-1
9 17 1732.0 -9.896 0.141 X lo-' 1460.0 -13.730 0.2917 X lo-'
9 18 513.30 -1.0360 0.0 -258.00 0.5070 0.0
9 19 -191.00 0.6835 0.0 79.080 -0,3808 0.0
9 20 -109.51 0.9689 0.0 178.22 -0.9168 0.0
9 21 -99.976 0.0 0.0 55.270 0.0 0.0
9 22 -! -18.695 -0.5261 0.0 -218.94 1.0749 0.0
9 23 810.17 -3.2209 0.2144 X -48.641 -0.7950 0.3713 X
9 24 -808.60 4.5640 -0.7230 X lo-' 913.90 -3.3060 0.4963 X
9 25 1297.0 -1.3650 -0.2253 X lo-' 1375.0 2.4990 0.6309 X lo-*
9 26 -35.890 -0.1009 0.0 -32.600 0.8470 X lo-' 0.0
9 27 -169.60 2.9860 0.0 -328.10 0.3045 0.0
9 28 419.90 0.9772 X lo-' 0.0 315.30 -0.5617 0.0
9 29 f! 2.7140 0.0 0.0 64.410 0.0 0.0
9 30 -! -986.00 3.8470 0.0 277.00 -1.3570 0.0
9 31 *! 478.50 -1.1480 0.0 -72.580 0.4909 0.0
9 32 A! 346.60 -0.7017 0.0 -182.00 0.7905 0.0
9 33 -717.76 2.9431 0.0 319.69 -1.4362 0.0
9 34 -62.430 -0.8977 0.0 -481.20 9.6040 0.0
9 35 -76.870 0.5372 0.0 38.060 -0.5189 0.0
9 37 64.010 -1.0770 0.0 -153.40 3.1430 0.0
9 39 80.792 -3.7020 0.1159 X lo-' 1955.5 -1o.Ooo 0.1139 X 10-1
9 41 64.210 0.0 0.0 -148.30 0.0 0.0
9 42 156.53 -0.7135 0.0 498.92 -0,4400 x 10-1 0.0
9 43 -62.857 0.2898 0.0 80.038 -0.1012 0.0
9 45 -! -497.98 0.7972 0.2982 X 945.14 -3.8168 0.4535 X
10 11 -208.40 0.0 0.0 389.70 0.0 0.0
10 12 -160.70 0.0 0.0 226.60 0.0 0.0
10 13 209.00 -0.6241 0.0 235.70 0.1314 0.0
10 20 435.64 0.0 0.0 -188.00 0.0 0.0
10 21 a! 985.70 -2.9860 0.0 -888.30 3.4260 0.0
10 22 f! -111.50 0.0 0.0 473.30 0.0 0.0
10 29 f! -373.70 0.0 0.0 -397.50 0.0 0.0
10 30 *! -742.70 0.0 0.0 -214.80 0.0 0.0
10 32 f! 114.30 0.0 0.0 293.50 0.0 0.0
10 37 +! -43.560 0.0 0.0 945.60 0.0 0.0
10 39 a! 2371.0 0.0 0.0 -225.30 0.0 0.0
188 Ind. Eng. Chem. Res., Vol. 32, No.1, 1993

Table IV (Continued)
n m a,, (K) bnm c,,,, (K-9 a, (K) bmn cmn (K-')

10 42 *! 856.5 -1.9Ooo 0.0 1129.0 -0.4978 0.0

11 12 -! 342.40 0.0 0.0 -251.70 0.0 0.0
11 13 195.30 -9.75 0.4051 X 10-1 824.20 -6.m 0.8271 X lo-*
11 15 3168.0 -24.070 0.4303 X 10-' 3329.0 -13.780 0.1193 X lo-'
11 16 +! 152.80 -1.0990 0.0 160.80 0.8719 0.0
11 17 -! -1355.0 7.6830 -0.1012 x 10-1 3499.0 -22.960 0.3543 X lo-'
11 19 -193.23 0.4301 0.0 139.55 -0.4367 0.0
11 20 62.031 1.0567 0.0 59.594 -0.7120 0.0
11 21 -49.339 0.0 0.0 48.852 0.0 0.0
11 22 *! 168.17 -1.0536 0.0 -461.35 1.8569 0.0
11 24 -5.7100 -0.2724 0.0 223.40 0.1237 0.0
11 25 -! 3351.0 -14.540 0.0 -788.60 1.6930 0.0
11 26 9.2220 -0,3292 0.0 -50.360 0.2448 X lo-' 0.0
11 28 A! 861.10 -1.6930 0.0 280.00 -0.9491 0.0
11 30 80.690 0.0 0.0 -136.30 0.0 0.0
11 31 -72.070 0.0 0.0 69.250 0.0 0.0
11 32 *! 82.960 0.0 0.0 11.620 0.0 0.0
11 33 -386.30 1.8920 0.0 248.30 -1.1980 0.0
11 35 *! 296.80 -1.2640 0.0 -337.10 0.8843 0.0
11 36 -! -92.120 0.9031 0.0 503.50 -1.7920 0.0
11 37 -! -201.40 0.5487 0.0 -320.00 1.0520 0.0
11 39 231.00 0.0 0.0 -173.50 0.0 0.0
11 41 -! -338.80 1.8370 0.0 3.9240 -1.1740 0.0
11 42 296.88 -1.1816 0.0 323.18 0.3626 0.0
11 43 -28.231 0.0 0.0 36.948 0.0 0.0
11 44 -! 745.40 0.0 0.0 -447.04 0.0 0.0
11 45 &! -579.11 0.9455 0.0 966.35 -2.1861 0.0
12 18 167.50 0.0 0.0 -14.230 0.0 0.0
12 19 *! 92.210 0.0 0.0 -33.640 0.0 0.0
12 24 *! -142.20 0.5720 0.0 465.80 -0.7730 0.0
12 25 *! 1894.0 0.0 0.0 18.790 0.0 0.0
12 29 h! 161.80 0.0 0.0 13.970 0.0 0.0
12 37 *! 745.40 -0.6220 0.0 -479.10 0.8031 0.0
12 39 -! 580.30 0.0 0.0 -285.50 0.0 0.0
12 42 i! 245.10 -0.8394 0.0 475.90 -0).1080 0.0
12 44 -! 489.15 0.0 0.0 -441.01 0.0 0.0
12 45 -! 260.64 -1.2868 0.0 -597.09 2.5295 0.0
13 18 957.80 -5.7730 0.1074 X lo-' 460.30 -5.6870 0.9776 x lo-*
13 19 1987.0 -8.0220 0.1065 X lo-' -588.80 1.4810 -0.2636 x
13 20 521.48 0.0 0.0 -310.82 0.0 0.0
13 21 -208.60 -0.2571 0.2418 X 872.00 -2.9390 0.1269 X
13 22 *! 492.90 -6.4750 0.1806 x lo-' 215.30 -2.4820 0.2745 x
13 23 -607.35 2.3467 0.0 97.128 -0.6439 0.0
13 24 -425.40 0.9514 0.0 641.20 -1.4860 0.0
13 25 974.00 -1.3680 -0,1983 X lo-' 381.10 -5.6820 0.1675 X lo-'
13 26 &! -305.10 0.7063 0.0 319.60 -1.3680 0.0
13 28 ! 35.020 1.7020 0.0 198.50 -1.4340 0.0
13 29 *! 102.60 0.0 0.0 -210.10 0.0 0.0
13 30 513.70 0.0 0.0 -299.60 0.0 0.0
13 32 +! -104.80 0.0 0.0 464.00 0.0 0.0
13 37 -! -422.70 2.2300 0.0 -326.40 0.2400 0.0
13 38 &! 155.70 -1.5780 0.0 -528.80 2.8220 0.0
13 42 251.40 -1.0210 0.0 -86.600 0.9724 0.0
13 43 -124.33 -0.294 0.0 561.14 -0.7058 0.0
13 44 -! -454.92 0.0 0.0 310.75 0.0 0.0
13 45 -! -515.93 0.3835 0.0 1368.0 -2.6254 0.0
14 15 +! 1517.0 -12.720 0.2557 X 10-' -1074.0 9.oooO -0,1795 X lo-'
14 16 -472.40 -0.2051 0.1058 X lo-' 836.60 -5.2080 0.4801 X
14 19 -4 12.38 -0.4909 0.6255 X 2412.2 -10.495 0.9741 X
14 24 t! -65.760 -0.3148 0.0 333.90 -0,1415 0.0
14 25 *! 2553.0 -11.900 0.0 3873.0 -9.315 0.0
14 29 -205.10 0.0 0.0 244.40 0.0 0.0
14 39 &! 162.14 0.0 0.0 -112.76 0.0 0.0
14 42 444.60 -3.1420 0.2975 X -526.10 7.6850 -0.1110 x 10"
14 43 *! -143.07 0.0 0.0 182.58 0.0 0.0
15 16 402.60 -1.6140 0.0 -639.90 2.5610 0.0
15 19 242.20 0.0 0.0 -131.90 0.0 0.0
15 24 -3.2800 0.0 0.0 43.830 0.0 0.0
15 25 &! 3888.0 -16.260 0.0 -868.80 2.9480 0.0
15 38 &! -330.20 0.0 0.0 904.10 0.0 0.0
15 42 +! 154.50 -0.9466 0.0 528.30 -0.3991 0.0
15 43 -186.98 0.0 0.0 295.07 0.0 0.0
16 22 f! -473.00 0.8883 0.0 406.80 -1.5240 0.0
16 24 k! 215.90 -1.3990 0.0 -825.90 3.1500 0.0
16 25 -! 1622.0 -4.8120 -0.1856 X lo-' -94.870 -9.6120 0.3722 x lo-'
16 38 &! -7.5320 -0.8077 0.0 35.160 0.9723 X lo-' 0.0
16 39 965.00 0.0 0.0 -311.90 0.0 0.0
 Ind. Eng. Chem. Res., Vol. 32,No. 1, 1993 189

16 45 *! 420.24 0.2632 0.0 -1035.8 3.0786 0.0

17 18 -! 1489.0 -13.480 0.2990 x 10-1 245.80 -0.1692 -0.6990 X
17 19 -! 393.90 -4.703 0.9003 X 2987.0 -9.3360 0.7147 X
17 21 a! 582.10 -2.3300 0.3770 X -338.0 3.3720 -0.3676 x
17 24 3986.0 -16.150 0.1635 X 10-1 2626.0 -10.590 0.1466 X 10-l
17 27 3770.0 1.6860 0.0 1.6550 -1.1640 0.0
17 31 -! 1268.0 -3.0420 0.0 -818.80 3.2290 0.0
17 39 -! -391.90 0.0 0.0 650.70 0.0 0.0
17 42 1186.0 -2.2810 -0.1336 X lo-* 1851.0 -4.4760 0.5577 x
18 19 81.520 0.0 0.0 31.100 0.0 0.0
18 20 -! -502.21 1.0583 0.0 -504.25 0.4034 0.0
18 22 *! -63.540 -0,4358 0.0 -92.490 0.2791 0.0
18 33 i! -623.80 2.5670 0.0 243.20 -1.4720 0.0
18 37 50.527 -0.7980 0.0 -110.08 2.1903 0.0
18 38 196.00 -1.1780 0.0 -474.50 2.1540 0.0
18 42 173.70 -1.7780 0.1480 X 32.270 2.6840 -0.3948 X
18 43 i! -95.689 -0.1720 0.0 173.18 -0.3557 x 10-1 0.0
18 45 -! -29.855 -0.7479 0.0 -422.66 1.8153 0.0
19 21 176.50 -1.2370 0.0 -368.70 1.9920 0.0
19 22 -78.960 0.0 0.0 14.760 0.0 0.0
19 24 65.820 -0.6265 0.0 357.60 0.7676 0.0
19 25 1283.0 3.3610 -0.2978 X 10-1 2331.0 -9.2380 0.1158 X lo-'
19 26 117.53 -0.4469 0.0 -128.21 0.5035 0.0
19 28 i! 468.80 0.0 0.0 434.80 0.0 0.0
19 29 i! -18.800 -0.3652 0.0 41.540 0.6460 0.0
19 31 *! 506.60 -1.2630 0.0 11.720 0.7004 0.0
19 33 *! -211.20 0.0 0.0 362.60 0.0 0.0
19 34 i! 11.650 -1.2290 0.0 -1428.0 7.6980 0.0
19 36 i! 267.10 0.0 0.0 -144.70 0.0 0.0
19 37 61.960 -0.4161 0.0 -19.100 1.1950 0.0
19 39 *! 396.60 -1.8290 0.0 -663.00 2.6910 0.0
19 41 -75.670 0.0 0.0 26.800 0.0 0.0
19 42 -128.30 0.8538 -0.2378 X 2402.0 -10.300 0.1521 X 10-1
19 43 -28.653 -0.4815 0.0 56.754 0.8978 0.0
19 45 -! 237.42 -1.2928 0.0 -642.44 2.8574 0.0
20 21 27.618 0.0 0.0 702.40 0.0 0.0
20 22 94.606 0.0 0.0 425.97 0.0 0.0
20 24 701.95 -1.7576 0.0 213.34 2.1861 0.0
20 25 i! -1398.7 0.0 0.0 1Ooo.o 0.0 0.0
20 32 146.06 0.0 0.0 780.71 0.0 0.0
20 33 -18.328 0.0 0.0 753.21 0.0 0.0
20 37 *! -447.95 1.5141 0.0 283.64 1.5491 0.0
20 39 -421.21 0.0 0.0 93.773 0.0 0.0
20 42 *! 1169.3 -3.0737 0.0 582.81 1.4976 0.0
20 43 720.45 -1.5187 0.0 -140.77 0.3090 0.0
20 44 -! -65.631 0.0 0.0 -14.016 0.0 0.0
20 45 508.72 -1.4005 0.0 -386.93 2.3961 0.0
21 22 70.790 0.0 0.0 -66.210 0.0 0.0
21 23 592.40 -4.2459 0.6905 X 603.29 -3.9770 0.6248 X
21 24 16.340 0.7287 X lo-' 0.0 95.050 -0.2348 0.0
21 25 *! 3985.0 -15.700 0.0 15.620 -1.0990 0.0
21 26 24.440 -0.4713 0.0 142.10 -0.1530 0.0
21 27 +! 1248.0 -2.0400 0.0 1295.0 -4.2240 0.0
21 28 i! 295.90 0.0 0.0 -137.70 0.0 0.0
21 30 -! 666.00 0.0 0.0 -390.60 0.0 0.0
21 33 128.80 -0,2077 0.0 -92.680 -0.1307 x 10-l 0.0
21 37 280.00 0.0 0.0 -207.30 0.0 0.0
21 42 -65.685 0.7409 X lo-' 0.0 401.00 -0.7277 0.0
21 43 -! -325.77 2.0412 0.0 70.075 -1.1490 0.0
21 44 530.30 0.0 0.0 17.052 0.0 0.0
21 45 207.12 -0.4396 0.0 -175.29 0.3275 0.0
22 23 187.43 -3.4460 0.6718 X 1468.9 -5.oooo 0.3701 X
22 24 46.290 -0.2115 0.0 46.030 0.5388 x lo-' 0.0
22 25 -! 3353.0 -14.200 0.0 368.60 -1.7480 0.0
22 26 *! 822.40 -2.0500 0.0 -423.10 0.8154 0.0
22 30 -! -174.60 0.0 0.0 106.30 0.0 0.0
22 32 i! 132.70 -0.1183 0.0 -23.810 -0.9204 X lo-' 0.0
22 33 i! -139.60 1.0220 0.0 96.400 -0,7760 0.0
22 35 i! -178.30 0.7426 0.0 -39.450 -0.8556 0.0
22 37 160.70 0.0 0.0 -135.90 0.0 0.0
22 42 -! 34.133 -0.3925 0.0 193.77 0.3179 x 10-l 0.0
22 43 108.83 -0.8606 0.0 -358.57 1.3307 0.0
22 45 7.3664 0.4046 0.0 -1.6641 -0.3783 0.0
23 24 t! -323.17 1.1973 0.0 350.92 -1.3456 0.0
23 33 -! 599.82 0.0 0.0 -364.76 0.0 0.0
23 37 i! 325.81 0.0 0.0 -199.87 0.0 0.0
24 25 -131.80 9.8020 -0.3582 X lo-' 972.10 -6.8200 0.9219 X lo-*
190 Ind. Eng.Chem. Res., Vol. 32, No. 1, 1993

Table IV (Continued)
n m anm (K) brim c,, (K-9 ,a, (K) bmn Cmn (K-')
24 26 f ! 441.50 -0.5353 0.0 -65.740 0.9670 X lo-' 0.0
24 27 f ! 3286.0 0.0 0.0 167.50 0.0 0.0
24 28 9.3620 1.0330 0.0 52.010 -0.9095 0.0
24 30 -! 750.20 0.8165 0.0 100.50 -0,8269 0.0
24 32 i! 49.510 0.6829 0.0 186.40 -0.7294 0.0
24 33 203.20 -1.3280 0.0 -1360.0 7.4020 0.0
24 35 f ! 325.20 0.4405 0.0 -60.890 -0.6321 0.0
24 36 f ! 902.00 0.0 0.0 -194.90 0.0 0.0
24 37 220.60 0.3756 0.0 -134.40 -0,3226 0.0
24 38 197.40 -0.4858 0.0 -98.980 -0.2128 X lo-' 0.0
24 39 i! 512.70 0.2702 X 10-1 0.0 -168.40 -0.1230 0.0
24 42 -37.183 -0.4783 X lo-' 0.0 60.780 0.2426 X lo-' 0.0
24 43 190.45 0.1272 X 10" 0.0 -131.87 -0,1420 X lo-' 0.0
24 45 22.779 0.4214 X 10-1 0.0 14.947 -0.1109 0.0
25 26 3986.0 25.000 0.0 3638.0 -14.250 0.0
25 27 518.50 0.0 0.0 -1713.0 0.0 0.0
25 33 -69.880 0.0 0.0 981.50 0.0 0.0
25 42 1352.0 -3.7970 0.0 2838.0 -12.980 0.0
25 43 f ! 96.855 -1.2993 0.0 2991.9 -9.3959 0.0
25 45 -! -27.161 0.6110 0.0 4235.3 -16.954 0.0
26 27 -! 85.600 0.0 0.0 986.00 0.0 0.0
26 28 f ! 68.870 3.2170 0.0 655.70 -2.2030 0.0
26 32 f ! 643.80 -0.7376 0.0 17.810 -0.2245 0.0
26 33 -! 9.2580 -0.1079 0.0 121.40 0.5397 X 10-1 0.0
26 34 -70.240 0.0 0.0 132.20 0.0 0.0
26 37 159.00 0.0 0.0 108.40 0.0 0.0
26 39 i! 606.90 0.0 0.0 -340.90 0.0 0.0
26 42 115.60 -0.5435 0.0 531.00 -0.2908 0.0
26 43 53.750 0.0 0.0 -47.089 0.0 0.0
27 42 i! 1804.0 0.6361 0.0 2500.0 -3.8140 0.0
28 32 i! 212.40 -0.3692 0.0 200.60 -0.2280 0.0
28 37 -93.310 -0.1286 0.0 319.40 0.3419 X lo-' 0.0
28 42 f ! 29.450 -0.9194 0.0 92.400 1.1910 0.0
28 43 *! 166.56 -1.0407 0.0 1.0902 1.5927 0.0
28 45 89.744 -1.0122 0.0 40.987 1.1526 0.0
29 35 i! 467.10 0.0 0.0 -360.00 0.0 0.0
29 39 356.60 0.0 0.0 -247.60 0.0 0.0
29 42 f ! -255.30 0.3653 0.0 685.30 -1.0480 0.0
30 37 -! -277.60 0.0 0.0 1168.0 0.0 0.0
30 42 96.590 -0.7691 0.0 846.70 0.2545 0.0
30 44 f ! 778.78 0.0 0.0 -384.29 0.0 0.0
31 35 a! -228.40 0.0 0.0 -47.810 0.0 0.0
31 39 f ! 373.80 0.0 0.0 -231.60 0.0 0.0
32 33 f ! -536.20 1.9950 0.0 558.00 -1.9240 0.0
32 45 i! -47.772 -0.9201 X 0.0 92.429 0.1744 0.0
33 35 i! -83.700 0.1436 0.0 -116.70 -0.6775 X lo-' 0.0
33 41 f ! -378.10 2.5600 0.0 13.780 -0.9360 0.0
33 42 f ! -146.20 0.2411 0.0 498.10 -0.7754 0.0
33 43 f ! -186.40 0.0 0.0 265.42 0.0 0.0
34 39 -! 1025.0 0.0 0.0 -416.50 0.0 0.0
35 39 i! -2 13-80 0.0 0.0 203.40 0.0 0.0
35 45 -! -322.46 -0.2083 x 10-l 0.0 67.069 0.2396 0.0
36 37 -74.880 0.0 0.0 1004.0 0.0 0.0
37 41 -! -211.10 0.0 0.0 516.50 0.0 0.0
37 42 1026.0 -7.4690 0.1114 X lo-' -1189.0 8.8650 -0.1285 X lo-'
37 43 f ! 321.62 -4.9963 0.1387 X 10-I 713.90 -2.7759 0.9172 X
37 45 185.82 0.0 0.0 -139.00 0.0 0.0
38 40 i! -57.380 0.0 0.0 110.40 0.0 0.0
38 42 96.190 -0.4476 0.0 32.470 -0.7141 X 10-1 0.0
38 43 f ! -22.572 0.0 0.0 -7.5600 0.0 0.0
39 42 141.20 -0.8783 0.0 666.50 -0.1555 0.0
39 43 53.871 -0.6775 0.0 -54.260 1.0612 0.0
39 44 -! -310.13 0.0 0.0 -367.48 0.0 0.0
40 42 i! 108.50 0.0 0.0 -69.940 0.0 0.0
41 42 610.10 5.9600 0.0 835.20 -2.6780 0.0
42 43 242.49 -0.3832 X 10-l 0.0 20.834 4.3472 0.0
42 45 i! 183.79 -0.1518 0.0 -61.922 -0.5944 x 10-1 0.0
43 45 f ! -523.96 0.4945 0.0 1414.0 -2.8776 0.0
"The use of these modified UNIFAC interaction parameters (+!) at high temperatures, (-!) at low temperatures, (f!)at high and low
temperatures can lead to erroneous results.
methods. While for the original UNIFAC method an ab- limited temperature range) a more reliable description of
solute deviation of 324.6 J/mol and a relative deviation the temperature dependence of the activity coefficients,
of 77.2% are obtained, with the present parameters a much and thus a more reliable prediction of the temperature
better estimation of hE-data (102.9 J/mol, 28.5% relative dependence of azeotropic points and LLE. This should
deviation) is possible; this should provide (at least for a allow the prediction of the appearance of lower or upper
 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 191

=I =I =1

Figure 4. Experimental and predicted results for cyclic ether-alkane systems. VLE: (A) tetrahydrofuran (1)-n-hexane (2) at 760 mmHg;
(B) 1,3-dioxolane (1)-n-heptane (2) at 70 OC; (C) 1,4-dioxane (1)-n-heptane (2) at 80 "C. hE: (D)tetrahydrofuran.(l)-n-hexane (2) at 30 OC;
(E) 1,3-dioxolane(1)-n-heptane (2) at 25 OC; (F) 1,Cdioxane (1)-n-heptane at 25 "C. Lines and symbols: (-) modified UNIFAC (Dortmund)
resulta;
(a-) original UNIFAC results; (0,w ( ) experimental values.

Table V. Deviations between Experimental and Predicted Table VIII. Deviations between Experimental and
Binary VLE Data (1730 Consistent Isothermal or Isobaric Predicted Activity Coefficients at Infinite Dilution (10000
Data Sets) Data Points (Coefficients with a n Asterisk Determined
with 9900 Data Points))
AP
group contribution method Ay A T (K) (mmHg) AY-'nl AY-reI*
contribution
~ O U D method A V (%) AT-* (%)
ASOG 0.0137 1.03 12.51
UNIFAC 0.0135 0.93 12.53 ASOG 1.30 26.69 1.56 26.69
(2141 data seta) 0.0141 1.06 12.56 UNIFAC 1.42 26.03 1.85 25.82
modified UNIFAC (Dortmund) 0.0087 0.62 6.89 (approximately 14000 data 2.09 28.15
(2130 data seta) 0.0088 0.68 6.55 points)
modified UNIFAC (Lyngby) 0.0117 0.80 11.95 modified UNIFAC 0.82 13.92 0.99 13.35
(Dortmund)
(approximately 13600 data 1.06 15.56
Table VI. Deviations between All Experimental and points)
Predicted Binary VLE Data (Approximately 7000 modified UNIFAC (Lyngby) 1.53 21.72 1.68 21.15
Iaothermal or Isobaric Data Sets)
< 100
7- without water
AP
group contribution method Ay A T (K) (mmHg) selection of selective solvents for extractive distillation,
ASOG 0.0219 1.63 14.56 extraction, or absorption. It can again be seen that with
UNIFAC 0.0213 1.58 14.75 the parameters for the modified UNIFAC method pres-
(approximately 9OOO data sets) 0.0224 1.74 15.00 ented in this paper much better results (approximatelya
modified UNIFAC (Dortmund) 0.0167 1.39 9.36 factor of 2 better) are obtained in comparison with the
(approximately 9OOO data seta) 0.0172 1.46 9.28
modified UNIFAC (Lyngby) 0.0195 1.50 13.43 results given by the other group contribution methods.
The resulta for ternary systems are presented in Tables
Table VII. Deviations between Experimental and Predicted IX and X. For VLE no consistency test was performed.
Binary Heats of Mixing Data (4900 Ieothermal Data Sets) Therefore all data seta (P < 50oO mmgHg, (pVi/& = 1) were
contribution method
~ O U D AhE (J/mol) A h E d (%) used for the comparison. This means that the experi-
mental error has a considerable influence on the calculated
ASOG 550.7 202.8
UNIFAC 324.6 77.2 deviations. Also,a large number of systems show a large
(6061 data seta) 335.0 88.8 miscibility gap. Both factors lead to a similar error, as
modified UNIFAC (Dortmund) 102.9 28.5 obtained for the case where all binary VLE data sets
(5990 data seta) 103.8 30.0 (Table VI) were used for the comparison. Apart from the
modified UNIFAC (Lyngby) 152.8 47.5 deviations in y, T,and P or hE. Tables IX and X contain
uErel I(hEerpt - hEcd/hEexpt,maxI X 100 (%). the number of data sets for which the examined group
contribution method provided the lowest (+) and the
critical solution temperatures. largest deviations (-1. It can be concluded from the de-
The results for activity coefficients at infinite dilution viations and the number of data sets with a plus or minus
are listed in Table VIII. Since the values published by sign that the best results are again obtained using the
different authors are contradictory especially for strongly method presented in this paper. Because of the problems
non-ideal systems (e.g., wateralkanes, water with higher mentioned, the improvements obtained for VLE are not
esters, etc.), Table VI11 contains deviations only for binary large, but prediction of hE-data shows considerable im-
systems with 7'-values < 100 or for all water-free systems. provement (by a factor of 2-3). Figure 4 shows resulte for
All '7 measured by liquid-liquid chromatography are VLE and hE in the form of y-x- or h%-diagrams for
excluded because the results are often very poor. As different cyclic ethers with alkanes. These systems usually
mentioned before, reliable values for 7' are of special caused great problems for the original UNIFAC method,
importance for the design of separation processes and the because for the cyclic ethers the same main group as for
192 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993

Table IX. Deviationr between Experimental and Predicted Ternary VLE Data (Approximately 660 Isothermal or Isobaric
Data Sets)
(516 data seta) (357 data seta) (187 data seta)
group contribution method AY - + AT (K) - +
AP(mmHg) + -
ASOG 0.0194 106 156 1.24 86 86 20.64 26 73
UNIFAC 0.0203 65 191 1.28 88 128 24.39 40 59
modified UNIFAC (Dortmund) 0.0172 202 74 1.09 106 60 15.43 68 20
modified UNIFAC (Lyngby) 0.0181 143 95 1.15 77 83 18.02 53 35

Table X. Deviations between Experimental and Predicted sures and not to different activities.
bE-Data for Ternary Syrtemr (144 Isothermal Data Sets) During this research work we attempted to improve the
AhE &Ele? situation somewhat for the different alcohols (primary,
POUP contribution method
(J/mol) (%) + - secondary, tertiary) by introducing different Rk- and
ASOG 532.1 82.7 4 93 Qk-vduesfor different alcohol group. These systems show
UNIFAC 312.5 34.9 12 46 a very different LLE behavior with water. While there are
modified UNIFAC (Dortmund) 106.7 13.3 82 2 miscibility gaps for 1-butanol, isobutanol, and 2-butanol,
modified UNIFAC (Lyngby) 154.8 23.5 46 3 no miscibility gap is observed for tert-butanol. This means
&'rei - hEule)/hEerpt,mluI x 100 (%).
I(hEexpt
that the deviation from Raoult's law decreases on going
from 1-butanol via isobutanol and 2-butanol to tert-bu-
aliphatic ethers was used. A great improvement of the tanol. The use of different main groups for the primary,
results is obtained using a special main group, as in this secondary, and tertiary alcohols would be very helpful for
work. As shown in Figure 4, all azeotropic points are describing the observed behavior. This would however
predicted with the desired accuracy. Furthermore, in involve a great increase in the number of required group
agreement with the experimental findings, no miscibility interaction parameters, and the present limited data base
gap is predicted for the system dioxolanen-heptane and does not allow a fit of the required parameters for three
much better agreement between experimental and pre- alcohol main groups with all the other main groups given
dicted is obtained for heats of mixing. in Table IV. Thus only different Rk- and €&-valueswere
introduced to improve this situation. In Table XI the
Problems activity coefficients at infinite dilution for the different
In the previous section the results for VLE, hE,and 7" butanols in water are given in the temperature range
of different group contribution methods were compared. 25-100 OC. For the m&ied UNIFAC method presented
It is concluded that the modified UNIFAC method pres- here, it can be seen that the highest 7"-values are obtained
ented in this paper provides the best predictions for these for 1-butanol and isobutanol, while the valuea for 2-butanol
properties. Further results for VLE, LLE, hE, T", azeo- are smaller. The smallest value is obtained for tert-bu-
tropic data, and solid-liquid equilibria are given (Schiller, tanol. At the same time a maximum of the 7"-values is
1992; Schiller et al., 1992). The user should apply the predicted in the temperature range given. This is in
method only in the temperature range for which experi- agreement with the experimental hE-values. For all bu-
mental data were available. An extrapolation may be tanol-water systems a miscibility gap is however still
dangerous, especially because the greatest part of the predicted using the parameters presented in Table IV.
hE-data, which following the Gibbs-Helmholtz relation
provides the most important information about the tem- Conclusion
perature dependence, were measured only in the tem- The modified UNIFAC method presented here allows
perature range 25-50 OC. Furthermore the reader should better predictions of the real behavior of non-electrolyte
remember that there are still weaknesses connected with systems than do other group contribution methods. This
the solution of groups concept when only a very limited was made possible by using a modifed combinatorial part,
number of adjustable parameters is fitted. For example additional main groups, and temperature-dependent pa-
it is very difficult with a limited number of parameters to rameters in the UNIFAC model which were fitted to all
account for isomeric effects. Of course new main groups the suitable phase equilibrium information stored in the
can be included, which would improve the results, but even Dortmund Data Bank. At the same time the large pa-
when the DDB is applied, the data base is still too small rameter set guarantees a large range of applicability. These
to account for isomeric effects, e.g., the behavior of isomeric advantages should allow a more reliable synthesis and
hydrocarbons, alcohols, etc., or substitution effects (e.g., design of separation processes, selection of solvents for
ortho, meta, or para substitution) in the case of the dif- extractive distillation or extraction, calculation of chemical
ferent benzene derivates. Fortunately, the different VLE equilibria, etc. When new experimental phase equilibrium
behavior of isomers is often due to different vapor prss- data and especially hE-data at temperatures very different
Table XI. Activity Coefficientr at Infinite Dilution for Different Butanol-Water Systems
modified modified modified modified
UNIFAC UNIFAC UNIFAC UNIFAC
temp ("C) ASOG UNIFAC (Dortmund) (Lyngby) ASOG UNIFAC (Dortmund) (Lyngby)
I-Butanol in Water Isobutanol in Water
25 45.7 54.1 41.9 30.2 30.8 54.2 41.9 30.0
50 46.5 47.9 43.0 40.5 31.7 48.0 43.0 40.2
75 47.4 43.1 42.2 48.2 32.7 43.2 42.2 47.8
100 49.0 39.4 40.0 53.1 34.1 39.4 40.0 52.7
2-Butanol in Water tert-Butanol in Water
25 30.8 54.2 36.2 30.0 17.1 51.0 27.2 35.2
50 31.7 48.0 36.9 40.2 18.0 45.0 27.6 47.6
75 32.7 43.2 36.0 47.8 18.8 40.3 26.7 56.9
100 34.1 39.4 33.9 52.7 19.9 36.6 25.0 62.6

from 25 OC are available, some of the group interaction
parameters should be revised and the existing modified
UNIFAC parameter matrix should be extended. This
would require the fitting of the group interaction param-
eters as well as the regular update of the Dortmund Data
Bank and the measurement of required missing data. This
kind of work is impossible without financial support from
industry or government.
Acknowledgment
The authors thank "Arbeitsgemeinschaft Industrieller
Forschungavereinigungen (AIF)" for the financial support
received for the development of the modified UNIFAC
method and B. Meents and R. B6lts for technical assis-
tance.
Nomenclature
a, = UNIFAC group interaction parameter between groups
n and m (K)
b,, = UNIFAC group interaction parameter between groups
nandm
c,, = UNIFAC group interaction parameter between groups
n and m (K-l)
cpE = excess heat capacity [J/(mol K)]
p i= standard fugacity of component i (kPa)
F = objective function
Fi= auriliaryproperty for component i (surface fraction/mole
fraction)
gi= weighting factor for the different types of data
hE = molar excess enthalpy [J/moll
Ki= K-factor for component i
nw = number of data pointa in a data set
qi = relative van der Waals surface area of component i
Qk= relative van der Waals surface area of subgroup k
ri = relative van der Waals volume of component i
Rk = relative van der Waals volume of subgroup k
T = absolute temperature (K)
Vi = auriliary property for component i (volume fraction/mole
fraction)
V i= empirically modified Vi-value
xi = mole fraction of component i in the liquid phase
X, = group mole fraction of group m in the liquid phase
yi = mole fraction of component i in the vapor phase
Greek Symbols
q2= separation factor
rk = group activity coefficient of group k in the mixture
= group activity coefficient of group k in the pure sub-
stance
7 ; = activity coefficient of component i
ymi= activity coefficient of component i at infinite dilution
8, = surface fraction of group m in the liquid phase
Y k ( j ) = number of structural groups of type k in molecule i
(pvi = fugacity coefficient for component i in the vapor phase
di= saturation fugacity coefficient for component i
9,, = UNIFAC group interaction parameter between groups
nandm
Indexes
calc = calculated quantity
C = combinatorial part
expt = experimental quantity
E = excess quantity
Ind. Eng. Chem. Res., Vol. 32, No. 1,1993 193
i = component i
R = residual part
= at infinite dilution
Supplementary Material Available: The parameters
can be obtained on a diskette, at cost, from the authors.
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Received for review May 19, 1992
Revised manuscript received September 16, 1992
Accepted September 30,1992