I n d . Eng. Chem. Res.

1995,34, 1897-1909 1897

A Simplified SAFT Equation of State for Associating Compounds

and Mixtures
Yuan-Hao Fu and Stanley I. Sandler*
Center for Molecular and Engineering Thermodynamics, Department of Chemical Engineering,
University of Delaware, Newark, Delaware 19716

A simplified statistical associating fluid theory (SAFT)equation of state is developed for

associating and nonassociating compounds. The new equation of state has the same number of
adjustable parameters as the original SAFT equation, but is simpler. For pure compounds,
this equation of state can correlate the vapor pressure and liquid density with errors equal to
those of the original SAFT equation. Both self-associating and cross-associating binary mixtures
were used to test the simplified SAFT equation of state. With a single binary adjustable
parameter, the new equation results in better correlations of vapor-liquid equilibria than the
original SAFT equation for most mixtures. However, for some mixtures, both the original and
simplified SAFT equations of state fail to provide a satisfactory description. The optimized binary
parameter of the simplified SAFT equation of state is found to be linearly dependent on
temperature for each mixture. Consequently, the binary parameter computed from several data
sets can be used to accurately predict the vapor-liquid equilibrium at temperatures other than
those for which experimental data are available.

Introduction SAFT equation of state by using the single attraction

Strong attractive forces, such as hydrogen bonding,
affect the physical properties of associating compounds.
For example, the boiling and critical points of such
compounds are higher than those of similar size non-
associating compounds. Also associating compounds
may form highly nonideal mixtures. In the thermody-
namic modeling of associating compounds, the associa-
tion is typically considered to be a chemical reaction,
with the strength of association given by the value of
the chemical equilibrium constant. On the other hand,
in statistical thermodynamics, hydrogen bonding is
regarded as a short-ranged, directional, and strongly
attractive interaction between molecules. On the basis
of thermodynamic perturbation theory, Wertheim
(1984a,b, 1986a,b) developed a theory of associating
fluids. Wertheim’s association theory has been tested
against Monte Carlo simulation for associating hard
spheres (see, for example, Chapman et al. (1986),Joslin
et al. (1987), and Jackson et al. (1988)) and shown to
be quite good. Chapman et al. (1989) extended Wer-
theim’s theory to develop the statistical associating fluid
theory (SAFT) equation of state for associating fluids.
Huang and Radosz (1990) assumed the segment-
segment interaction to be described by the square-well
potential to improve the SAFT equation of state for real
compounds. This equation of state has been applied to
both pure nonassociating and associating components.
Huang and Radosz (1991) then extended the SAFT
equation to mixtures containing associating compounds.
In the SAFT equation of state of Huang and Radosz,
the residual Helmholtz energy for a pure component has
four contributions: the hard sphere, dispersion, chain,
and association terms. The hard sphere, chain, and
association terms were derived from statistical thermo-
dynamics. For the dispersion term, Huang and Radosz
used a double power series in temperature and density
which had been fit to argon physical property data by
Chen and Kreglewski (1977). Here we simplify the
term of Lee et al. (1985) for the square-well fluid to
replace the multiterm double series dispersion term,
while keeping the original hard sphere, chain, and
association terms. This results in a much simpler
equation of state.
The pure component parameters of this simplified
SAFT (SSAFT)equation of state are obtained by fitting
vapor pressure and liquid density data, and are found
to scale with molecular weight for the alkanes, as with
the original SAFT equation. We have applied the
SSAFT equation of state to calculate the vapor-liquid
equilibria of both self-associating and cross-associating
binary mixtures using one binary parameter, and the
correlations we obtain with the SSAFT equation of state
are compared with those of the SAFT equation.
Equation of State
A. Pure Components. In SAFT model, molecules
are considered t o be composed of equal-size, spherical
segments. Different molecules have different segment
diameters and numbers of segments. We develop the
equation of state by forming molecules from single hard
spheres using the procedure shown in Figure 1. Ini-
tially, the fluid is assumed to consist of equal-size single
hard spheres, and only hard sphere effects are consid-
ered. Next, the segment-segment attractive forces are
added to each sphere; the dispersion energy can be
described by any appropriate potential, such as the
square-well or Lennard-Jones potentials. Then chain
sites are added to each sphere and chain molecules are
formed by the bonding of chain sites. Finally, associa-
tion sites are added and the effect of association is
included. There is a free energy contribution for each
step in this procedure. Therefore, in the SAFT equation
of state, the residual Helmholtz energy per molecule for
a pure component has hard sphere, dispersion, chain,
and association contributions and is written as

* Author t o whom correspondence should be addressed.

0888-5885/95/2634-1897$09.00f0 0 1995 American Chemical Society
1898 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995
I I L I
(e) (4
Figure 1. Procedure to form a molecule in the SAFT model. (a)
The proposed molecule. (b)Initially the fluid is a hard sphere fluid.
(c)Attractive forces are added. (d) Chain sites are added and chain
molecules appear. (e) Association sites are added and molecules
form association complexes through association sites.
Each compound is assumed to be a chain with m
segments. The hard sphere Helmholtz energy is given
by
a's = ma:
where a$ is the Helmholtz free energy for a hard
sphere in a hard sphere fluid at the same packing
fraction as in the chain fluid (see below). Since there
are m segments in a molecule, the total hard sphere
contribution of a molecule is mu:. The single hard
sphere contribution at;."t o the Helmholtz free energy is
calculated from the expression of Carnahan and Star-
ling (1969)
with
17 = hNA46)@,d3
where ea is the molar density of hard spheres and d is
the effective hard sphere diameter of a segment. The
molar density of hard spheres is equal to
e, = me
where e is the molar density of chain molecules.
Following Barker and Henderson (1967),the temper-
ature dependence of the effective hard sphere diameter
is given by
d = o[l - c exp(-3u0/kr)]
where CT is the temperature independent diameter of a
segment, c is a parameter which we take to be 0.333,
and uo is the temperature independent interaction
energy between segments. The value of c was obtained
by fitting ethane vapor pressure and liquid density data
using the simplified SAFT equation of state. It is more
convenient to use molar volume rather than the diam-
eter of a segment as an adjustable parameter. The
temperature independent segment molar volume in a
closed-packed arrangement, uoo, is
where z = 0.740 48.
The dispersion contribution t o the Helmholtz free
energy is
adisp = mad"sp
0 (8)
where a? is the dispersive Helmholtz energy of one
segment. Here and in the original SAFT equation the
attraction between segments is assumed to be the
square-well potential. In SAFT the equation of Chen
and Kreglewski (1977) was used for up,
which is a
double power series containing 24 coefficients
RT
where D,j. are the universal constants fit to thermody-
namic data of argon and u is the temperature dependent
square-well depth.
The equation we test here results from the replace-
ment of this dispersion term with the simpler equation
of Lee et al. (1985). The Helmholtz free energy for the
dispersion term derived by Lee et al. (1985) for the
(2) square-well fluid is
(10)
with
Y = ex&+) -1
where ZMis the maximum coordination number, which
was taken t o be equal to 36 in the simplified perturbed
(3) hard chain theory (SPHCT) of Kim et al. (19861, us is
the molar volume of a segment, u* = N*,d3/& is the
close-packed molar volume of a segment, and u is the
depth of the square-well potential. We assume that the
(4) square-well-potential depth depends on temperature as
given by Chen and Kreglewski (1977)
u = uo[l +( e / k ~ ) ~ (12)
We set elk = -10 K based on fitting the vapor pressure
(5) and liquid density of ethane.
The Helmholtz energy of chain formation achainis
estimated from Wertheim's association theory by setting
the association energy to infinity. In the SAFT equation
of state, the Helmholtz energy of chain formation is
given by
(6) achain 1 - (1/2)q
-= (1- m ) In (13)
RT (1 - VI3
 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995 1899
Finally, the association Helmholtz energy aassoc due to result of Mansoori et al. (1971)for hard sphere mixtures,
hydrogen bonding is also estimated from Wertheim’s the Helmholtz energy is
association theory, and is given by

,=T[(lnxA-E)+:M]
aassoc (14)
2
where XAis the fraction of association sites A that are
not bonded, and M is the number of association sites in
a compound. The summation is over association sites,
and XAis given by with

(15)
B

where Am is the association strength given by

Am = ghs(d)[exp(em/kT)- l l d 3 ~ m
Here P and K~ are the association energy and volume
for the interaction between association sites A and B,
and gh”(d)is the hard sphere radial distribution function
at contact given by
1 - (1/2)q
ghs(d)=
(1 - q)3
The simplified SAFT equation of state for pure fluids
where Q is the total molar density of molecules, xi is the
(16) mole fraction of compound i, mi is the number of
segments per molecule i, and d i is the temperature
dependent segment diameter.
Next we consider the attractive force between seg-
ments, again assuming that the attractive potential is
the square-well potential. Extending the equation
derived by Lee et al. (1985) for pure components to
mixtures, the dispersion term becomes
(17)
adisp
-- -mzM1n(
RT us
VS

+ (V*V
) (26)
obtained from the volume derivative of the Helmholtz
free energy is a sum of the compressibility factors from where us is the total molar volume of a segment which
each of the contributions above and is given by is equal to us = llQm, and ZM = 36. We choose the
P V = zhs+ Zdisp + rhain
z =- + zasBoc
+ 1 (18) following as our mixing rules for this equation
RT
with
and

i j
(20) (v*y> =

i j
(28)
with

In the SSAFT equation of state, there are three and

adjustable parameters for a nonassociating compound:
the temperature independent square-well depth uo, the
segment molar volume in a closed-packed arrangement
uoo, and the number of segments m in a compound. For
associating compounds, there are two additional
parameters: the association energy cABand association
volume P.
B. Mixtures. For mixtures, we use the same pro-
cedure t o develop the equation of state as for a pure
component. The total residual Helmholtz energy in the
SSAFT equation of state is again given by
(30)
where K i is taken as an adjustable parameter in binary
mixtures.
Next chain molecules in the system are formed by the
bonding of chain sites. The chain term for a mixture
derived by Chapman et al. (1990) is
-chain

= ahs
ares + adisp + achain
+ aassoc (23)
In the hard sphere term the segments are not bonded where giihs((dii) is the pair correlation function a t contact
to form chains, but are single hard spheres; therefore, in a mixture of hard spheres. As derived by Mansoori
the mixture is a hard sphere mixture. Based on the et al. (19711,guh”(d,j.)is given by
1900 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995
Table 1. Parameters for the SSAFT Equation of State
compound uolk (K) uoo (mL) m @lk (K) 1 0 0 0 ~ ~
ethane 90.529 16.236 2.022
propane 92.571 16.507 2.735
butane 102.823 19.263 2.962
pentane 101.564 18.574 3.708
hexane 99.724 17.657 4.548
For segments of the same diameter, this equation heptane 98.650 16.981 5.380
becomes benzene 129.471 17.807 3.206
acetone 111.463 11.962 3.794
chloroform 118.961 14.547 3.429
tetrachloromethane 132.828 20.933 2.970
acetic acid 118.088 16.236 2.282 5810.5 28.840
propanoic acid 111.788 16.500 3.017 5240.2 19.998
(33) butanoic acid 109.916 15.753 4.000 4584.6 26.399
methanol 89.135 14.000 1.989 2710.4 119.107
Finally, the effect of association is considered. The ethanol 93.131 16.000 2.540 2802.7 56.634
association term for a mixture given by Chapman et al. propanol 104.651 16.000 3.316 2511.7 41.420
(1990) is butanol 103.80 16.000 4.006 2458.6 49.971
water 188.231 6.560 2.000 825.9 119.930

pressure and liquid density are shown in Table 2.

For small n-alkanes, we find that the number of
segments m increases linearly with molecular weight.
where Mi is the total number of association sites in From a least squares analysis, we find that the equation
compound i, and X4 is the mole fraction of sites Ai which relating the two is
are not bonded and is given by
M +
= 0.047Mw 0.511 (42)
Similarly, we find that

where ej is the molar density of compound j equal to ~j muoo= 0.835Mw 8.206 + (43)
= qe, and AkBj is the association strength between site
A, and Bj given by and
AA.B. - 1](d,)3~AiBj(36)
= gp(d,)[exp(cACBJ/kT) mu'lk = 4.912Mw 30.318 + (44)
where €AB, and K ~ are ~ Jthe association energy and These correlations are plotted in Figure 2. With these
volume for an interaction between site Ai and Bj. correlations it is possible to estimate the values of the
The final form of the SSAFT equation of state for parameters of larger n-alkane compounds for use in the
mixtures is SSAFT equation of state.
For associating compounds, we have to specify the
z= Z h s + Zdisp + Zchain
+ zassoc
+1 (37) number of association sites and the site-site interac-
tions for each compound. Table 3 lists the types of
with association that may occur. On the basis of spectro-
scopic data, acids usually associate to form dimers.
Therefore, we assume that acids contain only one
association site. We also assume that alcohols contain
two association sites: one at the hydrogen atom (site
53523
( 1 - 5313
] (38)
A) and the other at the unbonded electron pair on
oxygen (site B). However, site A can only form a
hydrogen bond with site B. Water has four association
sites: two at the unbonded electron pairs and two at
the hydrogen atoms. Only the unbonded electron pair
(39) will form a hydrogen bond with a hydrogen atom. Some
experimental results (Wei et al., 1991)suggest that only
three sites of water form hydrogen bonds. We chose the
two hydrogen atoms and the one unbonded electron pair
as the association sites since steric hindrance of the two
association sites on an oxygen atom may not allow the
formation of two hydrogen bonds.
Table 1 also lists the values of the parameters uo, m,
ea, and K~ for the associating compounds obtained by
fitting vapor pressures and liquid densities of the
Results compounds studied. Except for small compounds, the
segment volume uoo was fixed at 16 for simplicity. The
A. Pure Components. The parameters uo,uoo, and errors in the correlation for the vapor pressures and
m of the SSAFT equation of state for pure nonassoci- liquid densities are shown in Table 2, which also lists
ating components were obtained by simultaneously errors after parameter optimization for the original
fitting vapor pressures and liquid densities, and these SAFT equation of state. It should be noted that since
are listed in Table 1. The correlation errors in the vapor the parameters reported by Huang and Radosz were
 Ind. Eng. Chem. Res., Vol. 34,No. 5 , 1995 1901
Table 2. Errors in Vapor Pressure and Liquid Densities for Pure Components Resulting from Correlations with the
SSAFT and SAFT Equations of State
SSAFT SAFT
data
compound temp range (K) error % pressure error % density error % pressure error % density sources
ethane 150-305.5 0.53 2.30 2.02 4.77 1
propane 189.5-367.18 1.13 1.56 2.00 2.05 1
butane 213.15-323.15 0.27 0.83 0.84 1.51 1
pentane 233.15-463.15 1.47 0.97 1.90 2.72 1
hexane 243.15-503.15 2.06 0.89 2.05 3.31 1
heptane 273.15-533.15 2.14 1.02 1.78 3.35 1
benzene 300-540 0.90 1.08 1.40 2.10 1
acetone 223.15-493.15 2.41 2.77 2.78 1.67 2
chloroform 213.15-343.15 1.40 1.23 0.87 1.50 2
tetrachloromethane 273.15-543.15 1.13 1.20 1.50 2.51 3
acetic acid 273.15-573.15 2.87 0.96 2.35 1.34 3
propanoic acid 293.15-603.15 0.42 1.13 3.26 1.38 3
butanoic acid 303.15-623.15 0.51 0.93 2.83 1.24 3
methanol 253.15-493.15 1.65 1.05 1.10 0.85 2
ethanol 250-510 1.28 1.46 0.34 1.17 3
propanol 260-530 0.22 1.52 0.70 1.53 3
butanol 270-550 0.21 1.23 0.30 2.63 3
water 283-613 2.22 3.30 1.30 3.20 1
av error over all compds 1.27 1.41 1.63 2.16
av error for nonassociating compds 1.34 1.385 1.71 2.55
av error for associating compds 1.17 1.45 1.52 1.67
a (1) Vargaftik, N. B. Table on the Thermophysical Properties of Liquids and Gases; John Wiley & Sons: New York, 1975. (2)
Thermodynamic Tables for mn-Hydrocarbons; Thermodynamic Research Center, Texas A&M University: College Station, TX. (3) Daubert,
T. E. Data Comuilation Tables of Prouerties of Pure Comuounds; Design Institute for Physical Property Data, American Institute of
Chemical Engineers: New York, ‘1985:

obtained using a different optimization procedure than Table 3. Types of Association

we did, and that the temperature ranges of their compound formula association type
correlations are different than used here, to be fair in acid cAA# 0 and KAA t 0
our comparisons we also redetermined the parameters 17-- -H-o \
c
for the SAFT equation of state. We see that, in general, ‘0-H- - -01:
the SSAFT equation is slightly more accurate than the
original equation, though the difference is not large.
In Table 1,we see that for the SSAFT equation the
segment interaction energies u0/k are close to 100 K for
both nonassociating and associating compounds, except site A
for water. This suggests that the dispersion term is
correctly accounting for only the weak attraction forces,
and explains why the segment interaction energies of ne M ‘H
associating and nonassociating compounds have similar site A
values. However, the segment interaction energy of
water is larger than that of other compounds, which does the original SAFT equation. The reason may be
may be due to the high polarity of water. Table 1 also that the correlation of the data with the original SAFT
shows that the association energies em/k for acids and equation of state results in less association for acids
alcohols decrease as molecular weight increases. Fi- than with the SSAFT equation. Figures 3 and 4 are
nally, the association energy for an acid is approxi- examples of phase diagrams calculated using both the
mately twice as large as for an alcohol, which is simplified and original SAFT equations of state.
reasonable since an association site of an acid involves Cross-association occurs in associating compound-
two hydrogen bonds, while alcohol association sites associating compound mixtures. The cross-association
involve only a single hydrogen bond. parameters cannot be estimated from pure component
B. Mixtures. Since we are interested in associating information. Therefore, we have had to make assump-
mixtures, we have computed the phase diagrams only tions about the type of association and values of the
for such mixtures. The SSAFT equation of state pa- cross-association parameters. Table 5 lists the types of
rameters of the compounds were obtained from the pure association assumed for different cross-associating mix-
component properties as discussed in the previous tures. Explanations of the assumptions made and the
section. For self-associating mixtures, there is only one results obtained are given below.
additional adjustable parameter kv, and this binary For acid-acid mixtures, acids 1 and 2 each have
parameter was obtained by fitting binary mixture single association sites, A1 and Az, respectively. In these
vapor-liquid equilibrium data. The calculated results mixtures, cross-association occurs, and the cross-as-
for the SSAFT equation of state are listed in Table 4 sociation energy and volume are assumed to be given
and compared with those of the SAFT equation of state. by
For alcohol-alkane mixtures, both the simplified and
original SAFT equations of state represent the phase
diagrams quite well. For acids, the SSAFT equation of
€AiAz = -4 (454
state produces small errors in pressure, as does the and
SAFT equation of state. However, the SSAFT results
in smaller errors in the vapor phase mole fractions than
1902 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995

6 300
0 experiment

m 4,

3,

2,
40 60 100 1: 0.00 0.20 0.40 0.60 0.80 1

molecular weight
mole fraction of Benzene
Figure 3. Binary mixture of acetic acid and benzene at 50 "C.
The points are the experimental data, the solid line is the result
of the original SAFT equation, and the dashed line is results for
the SSAFT equation proposed here.

cn
2
100

100
20 40 60 80
molecular weight
100 120
Q

100
I-,: :,
..... , , 1
0.00 0.20 0.40 0.60 0.80 1.00
90
mole fraction of propanol
80 Figure 4. Binary mixture of propanol and heptane at 60 "C.
Legend as in Figure 3.
70 Therefore acid-acid mixtures also have only a single
m VI adjustable parameter per binary in the dispersion term.
60
The results for acid-acid mixtures are given in Table
6, and Figure 5 is an example of a vapor-liquid phase
diagram for one such mixture. The SSAFT equation of
50 state can represent this phase diagram very well, while
the SAFT equation results in larger errors in the vapor
40 phase mole fractions.
For alcohol-alcohol mixtures, we assume that each
alcohol has two association sites A1 and B1 on alcohol
30 1, and sites A2 and B2 on alcohol 2, and that AlB2 and
20 40 60 80 100 120 AzBl cross associations can occur. The cross-association
molecular weight parameters are assumed to be given by

Figure 2. Correlation of the segment number m, mu0/k,and muoa

in the SSAFT equation with molecular weight for n-alkanes. The
points are the optimum values found from correlating data, and
the lines are the result of a least squares fit.
 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995 1903
Table 4. Errors in Total Pressure and Vapor Phase Mole Fraction for Self-AssociatingMixtures
SSAFT SAFT
mixture kij error P (mmHg) error y kii error P ( " H E ) error Y data sourcea
+
benzene acetic acid at 45 "C 0.038 1.54 0.0163 0.040 3.20 0.0231 1
+
benzene acetic acid at 50 "C 0.028 1.95 0.0102 0.031 4.46 0.0166 1
+
acetic acid tetrachloromethane at 35 'C 0.042 2.03 0.0073 0.035 1.36 0.0360 2
+
heptane propanoic acid at 25 "C 0.040 0.40 0.0166 0.015 0.55 0.0349 3
+
heptane propanoic acid at 45 "C 0.040 0.36 0.0094 0.016 1.77 0.0311 3
+
heptane propanoic acid at 50 "C 0.030 1.52 0.0122 0.010 0.95 0.0402 1
+
benzene propanoic acid at 40 "C 0.002 2.05 0.0662 0.005 2.02 0.1220 1
+
propanoic acid tetrachloromethane a t 30 "C 0.011 8.17 0.0041 0.017 14.75 0.0022 2
+
hexane ethanol at 25 "C 0.023 2.12 0.0092 0.020 2.35 0.0098 1
hexane+ ethanol at 40 "C 0.028 1.92 0.0070 0.024 1.47 0.0065 1
+
ethanol heptane at 40 "C 0.028 2.15 0.0182 0.023 2.25 0.0148 1
+
hexane propanol a t 50 "C 0.016 3.04 0.0106 0.013 2.89 0.0086 1
+
propanol heptane at 60 "C 0.020 2.71 0.0119 0.018 2.70 0.0103 1
av error over all mixtures 2.30 0.0153 3.13 0.0273
a (1)DECHEMA Chemistry Data Series: Vapor-Liquid Equilibrium Data Collection; DECHEMA: Frankfurt, 1977. (2) Tamir, A.;
Dragoescu, C.; Apelblat, A.; Wisniak, J. Fluid Phase Equilib. 1983,10,9-42. (3) Lark, B. S.; Banipal, T. S.; Singh, S. J. Chem. Eng. Data
1985,30,286-288.
Table 5. Type - Mixtures
~- of Association and Cross-AssociationParameters for Cross-Associating

mixture component 1 component 2 association type cross-association parameters

0
acid-acid
,."
\
0-H
] site Al site A~ 1r H-o,

0
C;,
€AIAI #

alcohol-alcohol site B1 site B2

C-ti C-ti
\H \H
site AI site A2
acid-alcohol
CI/"
\
0-H
} site A1
site B2
C-ti
\H
site A2
water -acid site C1 H-0
H-ti
site B ~ \ ~ site A2 [ )
site A,
water-alcohol
H-0
..
site C1 site B2
C-ti
site B ~ \ ~ \H
site Al site A2

Table 6. Binary Interaction Parameters and Errors in Total Pressure and Vapor Phase Mole Fractions for
Cross-AssociationMixtures
~~

SSAFT SAJ?T
mixture kij error P (mmHg) error y kij error P (mmHg) error y data sourcea
+
acetic acid propanoic acid at 30 "C 0.013 0.10 0.0134 0.014 0.24 0.0820 1
+
acetic acid propanoic acid at 40 "C 0.013 0.09 0.0084 0.021 0.19 0.0774 1
+
ethanol propanol a t 70 "C 0.027 3.72 0.0128 0.025 2.35 0.0096 1
+
ethanol propanol at 40 "C 0.005 0.78 0.0066 0.004 0.12 0.0051 1
+
ethanol butanol a t 70 "C 0.011 4.18 0.0054 0.010 1.21 0.0051 1
+
ethanol acetic acid a t 35 "C -0.070 1.08 0.0249 -0.023 1.16 0.0110 1
+
butanol acetic acid at 35 "C -0.055 0.39 0.0112 -0.046 0.43 0.0213 1
+
ethanol water at 50 "C -0.180 3.59 0.0066 -0.120 3.56 0.0080 1
+
water propanoic acid at 60 "C -0.147 3.34 0.0273 -0.085 5.77 0.0278 1
+
water acetic acid a t 40 "C -0.179 2.09 0.0290 -0.134 2.74 0.0376 1
+
acetone chloroform a t 25 "C 0.001 3.87 0.0120 0.001 3.86 0.0125 1
acetone + chloroform at 40 "C -0.001 3.27 0.0082 0.000 3.41 0.0084 1
acetone + chloroform at 50 "C -0.006 6.02 0.0129 -0.003 5.89 0.0122 1
av error overall data sets 2.50 0.0137 2.38 0.0244
a (1)DECHEMA Chemistry Data Series: Vapor-Liquid Equilibrium Data Collection; DECHEMA: Frankfurt, 1977.
Therefore, again, there is only one adjustable binary mixture. Both the SAFT and SSAFT equations of state
parameter for alcohol-alcohol mixtures. Table 6 lists produce small errors in the pressure and vapor phase
the correlated results for the simplified and original mole fractions, and the difference between the two
SAFT equations of state. Figure 6 shows the correlated versions of SAFT is small. However, because of its
phase diagram for one system, the ethanol-butanol relative simplicity and fewer terms in the dispersion
1904 Ind. Eng. Chem. Res., Vol. 34,No. 5 , 1995

40
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15

- 1 -" 1
0.00 0.15 o.;o O.$S 1.b 0.00 0.10 0.zo o.ko oko 1 10

mole fractlon of butanol

mole fraction of acetlc acid
Figure 7. Binary mixture of butanol and acetic acid at 35 "C.
Figure 5. Binary mixture of acetic acid and propanoic acid at 40 Legend as in Figure 3.
"C. Legend as in Figure 3.
rameter in the dispersion term in the equation of state
600
0 txpwimcnt I for acid-alcohol mixtures. The errors for the simplified
and original SAFT equations of state are given in Table
500
0 experiment 6, and Figure 7 is the phase diagram for butanol-acetic
acid mixture. The SSAFT equation can more accurately
correlate the vapor-liquid equilibrium data for this
400 mixture than the original SAFT equation, especially in
the high butanol concentration region.
In water-alcohol mixtures, water has three associa-
300 tion sites and an alcohol has two, but only the unbonded
electron pair can form a hydrogen bond with a hydrogen
atom. In this case, for simplicity, all the cross-associa-
200 tion energy and volume parameters are taken to be
equal and are estimated as follows

100

and
0
0.00 0.25 0.50 0.75 1.00

mole fraction of ethanol
Figure 6. Binary mixture of ethanol and butanol at 70 "C. Legend
as in Figure 3.
term, SSAFT equation of state is easier to use for these
calculations.
For acid-alcohol mixtures, the acid is assumed to
have one association site A1 and the alcohol to have two
association sites A2 and Bz,and that site A1 can cross-
associate with both sites A2 and B2. In the mixture, the
chain length of association is shorter than for a pure
alcohol, since if an alcohol and acid associate, the chain
terminates. The cross-association parameters are as-
sumed to be
and
Consequently, we again have only one adjustable pa-
We use only the one adjustable parameter kq in the
dispersion term for the water-alcohol mixture. Figure
8 is the vapor-liquid equilibrium phase diagram of the
water-ethanol mixture correlated using the original
and simplified SAFT equations of state. Both equations
of state represent the phase diagram well, though the
SSAFT equation of state better describes the mixture
in the azeotropic region.
For water-acid mixtures, we assume that all three
sites of water can associate with an acid, and that the
values of the cross-association parameters are
and
KA~Az= K B ~ A z= KC1A2 = (KAIC1 + KA2-4z)/2 (49b)
Figure 9 shows the comparison of the correlated vapor-
liquid equilibrium results from the original and simpli-
fied SAFT equations of state for the water-propanoic
acid mixture. A better correlation results from the
 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995 1905
60
0 eaperiment

0 experiment

A
m A
I m
E I
E E
Y E
W

E!
3
t
f
u) UJ
UJ u)
E! t
a P

"" 1 1 I I
35 Q I 1 I

0.00 0.25 0.50 0.75 1.b 0.00 0.25 0.50 0.75 1

mole fraction of ethanol mole fraction of water

Figure 8. Binary mixture of water and ethanol at 50 "C. Legend Figure 10. Binary mixture of water and acetic acid a t 40 "C. The
as in Figure 3. value of parameter for simplified SAFT with one parameter is
-0.179. The values of parameters for simplified with two param-
200 eters are -0.179 in dispersion term and 0.09 in association term.
0 experiment
700
0 experiment' 0 experiment

- SAFT 0 experiment
A
UJ ...... ssm ...rtnn-':1 - SAFT
r 600
E ..._. SSAFT
E
W

100
2
3 500
En
u)

E!
P 50

400

- 1
0.00 0.;5 0.io 0.k 1 3
300

mole fractlon of water

Figure 9. Binary mixture of water and propanoic acid at 60 "C.
Legend as in Figure 3.
200
SSAFT equation of state in the azeotropic region than
from the SAFT equation. Figure 10 shows the cor-
related results for both the simplified and original SAFT
equations of state for the water-acetic acid mixture. In io0
this case, neither of the equations of state can describe E 1 0.15 0.iO 0.b 1.00
this phase diagram satisfactorily. Further, in an at-
tempt to improve the correlation of the water-acetic mole fraction of acetone
acid mixture, we added an second binary parameter in Figure 11. Binary mixture of acetone and chloroform at 50 "C.
Legend as in Figure 3.
the cross-association energy. The correlated results
with two binary parameters are also shown in Figure hydrogen bond; however, a hydrogen bond can form by
10; the improvement is small. cross-association. In this case the association param-
Finally, we consider a mixture containing compounds eters in either of the SAFT equations cannot be obtained
that cannot form a hydrogen bond by themselves, but from only the physical properties of pure compounds.
can only cross-associate with other compounds. For Consequently, we fit one set of isothermal binary
example, acetone has unbonded electron pairs on its mixture vapor-liquid equilibrium data to obtain the
oxygen atom but does not have a proton donor. In binary parameter kjj and the two cross-association
contrast, chloroform is a proton donor but not an parameters. Since the association parameters are tem-
electron donor. Neither acetone nor chloroform can self perature independent by assumption in the model, after
1906 Ind. Eng. Chem. Res., Vol. 34, No. 5 , 1995

Table 7. Binary Interaction Parameters and Errors in Pressure and Vapor Mole Fractions for High Pressure Mixtures
SSAFT SAFT
mixture temp ("C) k, error % pressure error y kij error 5% pressure error y data sourcea
propane + methanol 39.95 0.056 4.92 0.0066 0.036 5.25 0.0080 1
69.95 0.063 2.33 0.0126 0.042 2.64 0.0185 1
99.95 0.067 1.45 0.0159 0.043 1.66 0.0257 1
pentane + methanol 100 0.070 1.90 0.0273 0.053 2.27 0.0173 2
125 0.071 1.46 0.0283 0.052 2.46 0.0171 2
150 0.078 1.99 0.0258 0.050 3.71 0.0140 2
methanol + benzene 25 0.017 0.46 0.0064 0.011 0.51 0.0060 3
100 0.020 2.50 0.0107 0.012 2.09 0.0095 4
120 0.012 2.76 0.0130 0.007 2.25 0.0112 4
140 0.005 4.47 0.0226 -0.003 3.81 0.0205 4
160 -0.004 4.63 0.0234 -0.012 3.87 0.0181 4
180 -0.010 4.76 0.0202 -0.012 3.67 0.0152 4
200 -0.025 4.68 0.0158 -0.020 3.38 0.0107 4
220 -0.017 2.73 0.0156 -0.015 1.83 0.0130 4
butane + ethanol 25 0.032 1.75 0.027 2.29 5
50.6 0.034 0.35 0.031 1.31 5
72.5 0.037 1.20 0.034 2.84 5
pentane + ethanol 100 0.032 0.34 0.0039 0.028 0.50 0.0034 6
125 0.035 0.92 0.0109 0.034 0.86 0.0112 6
150 0.035 0.56 0.0080 0.031 1.30 0.0064 6
methanol +water 25 -0.235 3.96 0.0131 -0.137 0.76 0.0036 3
100 -0.202 2.08 0.0148 -0.108 1.57 0.0087 7
150 -0.184 0.70 0.0181 -0.080 0.83 0.0130 7
200 -0.166 0.38 0.0177 -0.070 1.06 0.0116 7
250 -0.147 0.73 0.0440 -0.057 2.30 0.0296 7
ethanol + water 25 -0.202 1.57 0.0177 -0.135 0.38 0.0028 3
150 -0.141 1.25 0.0091 -0.087 1.15 0.0051 8
200 -0.121 1.06 0.0110 -0.077 1.06 0.0040 8
250 -0.100 0.86 0.0186 -0.066 3.15 0.0079 8
275 -0.081 1.35 0.0402 -0.066 4.84 0.0188 8
300 -0.069 1.25 0.0507 -0.067 5.39 0.0178 8
325 -0.056 2.08 0.0702 -0.083 7.76 0.0239 8
2-propanol + water 25 -0.162 1.11 0.0097 -0.126 2.03 0.0125 3
150 -0.096 1.13 0.0136 -0.076 1.49 0.0153 8
200 -0.075 1.85 0.0117 -0.068 2.94 0.0106 8
250 -0.051 2.69 0.0190 -0.059 4.31 0.0097 8
275 -0.028 2.31 0.0280 -0.046 4.36 0.0113 8
methanol + ethanol 25 0.021 0.28 0.0035 0.005 0.19 0.0033 3
100 0.034 0.57 0.0054 0.008 0.42 0.0029 9
120 0.025 0.30 0.0058 0.003 0.27 0.0024 9
140 0.023 0.17 0.0052 0.002 0.14 0.0019 9
160 0.019 0.32 0.0060 0.002 0.25 0.0025 9
all data 1.77 0.0180 2.27 0.0114
a (1)Galivet-Solastiouk, F.; Laugier, S.; Richon, D. Fluid Phase Equilib. 1986,28, 73-85. (2) Wilsak, R. A,; Campbell, S. W.; Thodos,
G. Fluid Phase Equilib. 1987, 33, 157-171. (3) DECHEMA Chemistry Data Series: Vapor-Liquid Equilibrium Datu Collection;
DECHEMA: Frankfwrt, 1977. (4) Butcher, K. I.; Medani, M. S. J. Appl. Chem. 1986,18,100-107. (5) Holderbaum, T.; Utzig, A.; Gmehling,
J. Fluid Phase Equilib. 1991, 63, 219-226. (6) Campbell, S. W.; Wilsak, R. A.; Thodos, G. J. Chem. Thermodyn. 1987,19, 449-460. (7)
Griswold, J.; Wong, S. Y. Chem. Eng. Prog. Symp. Ser. 1952,48(3), 18-34. (8) Barr-David, F.; Dodge, B. F. J . Chem. Eng. Data 1959,4,
107-121. (9) Butcher, K. L.; Robinson, W. I. J . Appl. Chem. 1966, 16, 289.

determining the cross-association parameters, we then
correlate vapor-liquid equilibrium data for the same
mixture at other temperatures with only the one binary
parameter ki. Figure 11 shows the correlations ob-
tained by using the original and simplified SAFT
equations of state and the experimental data a t three
temperatures. We see that both equations of state can
+
accurately describe the acetone chloroform mixture.
C. High Pressure Vapor-Liquid Equilibrium.
To test the utility of the SSAFT equation of state for
high pressure vapor-liquid equilibria, we consider nine
self-associating and cross-associating binary mixtures
for which data are available over a large temperature
and pressure range. We use the same association types
and mixing rules as we did for low pressure mixtures.
Therefore, there is only one adjustable binary parameter
kg in the equation of state.
Table 7 lists the results of correlations with both the
SAFT and SSAFT equations of state; the average
percentage errors in pressure are found to be smaller
than 5 % and the average errors of vapor phase mole
fractions are small except a t very high temperature.
Figures 12a and 13a are examples of the correlations
of both equations of state compared with the experi-
mental data. Both the original and simplified SAFT
equations of state lead to good correlations of the
experimental high pressure vapor-liquid equilibrium
data for mixtures containing alcohols, though the errors
become larger in the near-critical regions.
Inspection of the optimized parameters in Table 7 for
the SAFT and SSAFT equations shows that the binary
parameter ku is temperature dependent. We find that
for water-alcohol mixtures, the binary parameter k i in
the SSAFT equation depends linearly on temperature
as follows:
k,=A+BT (50)
as shown in Figure 14a. Using the least squares
 10000
a b 250T

10000

A
m
I
E
E
Y

1000 lo00
E
¶
v)
v)
En

25'C

100 100

experimen
Q experimenl
- SAFT - SAFT
-.e- SSAFT ._..S S A R
10 I I I 10 I I 1
I M 0.25 0.50 0.75 1.00

mole fraction of methanol

Figure 12. Binary mixture of methanol and water several temperatures. (a) Correlations using the SAFT and SSAFT equations of state
compared to experimental data (points). (b) Predictions using the SAFT and SSAFT equations of state.
Table 8. Coefficients for the Equation k" = A + BT ("C) state can correlate the vapor pressure and liquid density
mixture A x lo2 B x 104 for both nonassociating and associating compounds very
+
propane methanol 4.9176 1.8333 well. The errors in vapor pressure and liquid density
+
pentane methanol 5.3000 1.6000 calculated using the simplified SAFT equation of state
+
methanol benzene 2.8662 -2.1305 are generally similar to, or slightly smaller than, those
+
butane ethanol 2.9174 1.0451 from the original SAFT equation of state.
+
pentane ethanol 2.6500 0.6000
methanol water+ -24.292 3.8705 For self-associating mixtures, with only a single
+
ethanol water -21.427 4.7928 adjustable parameter, both the SAFT and the simplified
+
2-propanol water -17.531 5.1618 SAFT equations of state produce small errors in pres-
+
methanol ethanol 2.2052 0.0
sure and vapor phase mole fractions for mixtures
containing alcohols, though the simplified SAFT equa-
method, we obtained the parameters A and B for each tion better correlates the vapor-liquid equilibrium of
system given in Table 8. In Figures 12b and 13b, we
show the vapor-liquid equilibrium coexistence curves mixtures containing an organic acid. For cross-as-
for the methanol-water and the ethanol-water mix- sociating mixtures, the type of cross-association and the
tures, respectively, obtained using values of KG from the cross-association parameters have to be specified. Both
above equation. For these mixtures, the calculations models have only one adjustable parameter; the simpli-
using the SSAFT equation of state are in good agree- fied SAFT equation of state usually leads to better
ment with the experimental data. In contrast the correlated results than the original SAFT equation, and
values of the binary parameter K,j. obtained by correla- is simpler and easier to use because it contains many
tion of these systems with the original SAFT equation fewer terms. However, for some mixtures, such as the
are not such simple functions of temperature, as shown water-acetic acid mixture, neither equation of state
in Figure 14b, and consequently the predictions in correlates the data very well with only one adjustable
Figures 12b and 13b with the SAFT equation are not binary parameter.
quite as accurate as those with the SSAFT equation.
High pressure binary vapor-liquid equilibrium data
were also used to test the simplified SAFT equation of
Conclusions state. With one adjustable binary parameter, the
A simpler SAFT equation of state has been developed. simplified SAFT equation of state can be used t o
For pure compounds, this simplified SAFT equation of accurately correlate such data for binary mixtures. Also
1908 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995

100000
a b looooo

200'C

lOOOo+ 150'C 1m-r 150'C

1000 j 15'C

100
1 0
'23'C

experime
100

0 experiment
0 expcrime 0 cxpcrimcnt
- SAFT
._..SSAFT 10
10 1 1 I
0.00 0.25 0.50 0.75 1.00

mole fraction of ethanol mole

fraction of ethanol
Figure 13. Binary mixture of ethanol and water at several temperatures. (a)Correlations using the SAFT and SSAFT equations of state
compared to experimental data (points). (b) Predictions using the SAFT and SSAFT equations of state.

a b
0.000 - /. I

-0.050 -

-0.100-
--
Y

-0.150-

-0.200 -

-0.250 X
0.00 100.00 200.00 300.00
I
400.00
-0.250 I I I i
l.00

Figure 14. Binary parameter k" vs temperature for water-alcohol mixtures. The points are correlated results, and the lines are calculated
by linear least squares method. (a) SSAFT equation of state. (b)SAFT equation of state.
it is found that a linear relation exists between the and temperature which allows this model to be used for
binary interaction parameter in the SSAFT equation extrapolation and prediction.

Acknowledgment
This research was supported, in part, by Contract No.
DE-FG02-85ER13436 from the U.S. Department of
Energy and Grant No. CTS-91123434 from the U.S.
National Science Foundation, both to the University of
Delaware. We also wish to thank Dr. Hasan Orbey for
his advice and comments on this work.
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Received for review September 23, 1994
Accepted February 2, 1995 @
IE9405605
@ Abstract published in Advance A C S Abstracts, April 1,
1995.