Pergamon

Chemical Envineering Science, Vol. 5L No, 20, pp. 3579--3588, 1997

1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PI I : S0009-2509(97)00143-7 0009-2509/97 $17.00 + 0.00
Critical points with the Wong-Sandler
mixing rule II. Calculations with a
modified Peng-Robinson equation of state
M a r c e l o C a s t i e r *t a n d S t a n l e y I. S a n d i e r ~,~
* Escola de Quimica, Universidade Federal do Rio de Janeiro, Rio de Janeiro-RJ-21949-900,
Brazil; ~Center for Molecular and Engineering Thermodynamics, Depart ment of Chemical
Engineering, University of Delaware, Newark, DE 19716-3119, U.S.A.
(Received 18 November 1996; in revised form 26 March 1997; accepted 11 April 1997)
Abst ract --Thi s is the second of two papers in which critical point calculations in binary systems
were performed utilizing cubic equations of state (EOS) combined with excess energy models
using the Wong-Sandl er mixing rule. In the first paper, a qualitative study of critical phase
diagrams calculated using the simple van der Waals EOS combined with the NRTL model was
made. In this paper, the Stryjek and Vera version of the Peng-Robi nson EOS was also
combined with the NRTL model and the resulting model was used in the comput at i on of the
critical loci of real systems. The binary interaction parameters of the model were estimated by
correlating vapor-l i qui d equilibrium (VLE) dat a and, for some systems, successful predictions
of the critical loci were obtained even when VLE dat a far from the critical point were used. To
estimate parameters in systems for which the equation of state model may incorrectly predict
a false liquid-liquid split, we used a penalty function approach based on the results of global
stability tests. While the model studied here has been able to quantitatively predict the critical
behavior of some non-ideal systems, involving compounds such as water, acetone and alkanols,
only qualitatively correct behavior could be predicted for some highly asymmetric and non-
ideal mixtures, such as water + n-dodecane. 1997 Elsevier Science Ltd
K e y w o r d s : Critical phenomena; phase diagrams; mixing rules; equations of state; local com-
position; excess free energy.
INTRODUCTION
Although critical point calculations utilizing cubic
equations of state (EOS) are routinely needed in
several applications, few papers have investigated the
effect on such calculations of mixing rules that com-
bine cubic EOS with excess free-energy models.
Therefore, as pointed out by Sadus (1994), despite the
large interest they have caused in the literature, these
mixing rules have not yet been extensively tested for
the prediction of critical points, and little seems to be
known about their ability in modeling this type of
phenomena. In one of the few papers that deal with
this subject, Kolfir and Kojima (1996) predicted and
correlated several types critical phase diagrams using
the PSRK EOS (Hol derbaum and Gmehling, 1991),
which combines the Mathias and Copeman (1983)
tOn leave at Department of Chemical Engineering, Uni-
versity of Delaware, Newark, DE, U.S.A.
~Corresponding author.
version of the SRK EOS and the UNI FAC model
(Fredenslund e t al., 1977) using the MHV1 mixing
rule (Michelsen, 1990). In anot her study, Knudsen
e t al. (1994) modeled complex systems t hat exhibit
critical type VI behavior using the MHV2 mixing-rule
and a quadratic mole fraction dependence for the
b-parameter to combine the Soave-Redl i ch-Kwong
EOS (Soave, 1972) with the UNI QUAC and
UNI FAC models (using temperature-dependent
parameters). However, there was no attempt to deter-
mine critical states for these systems.
This is the second of two papers whose objective
was to study the effect of one of these mixing rules, the
Wong-Sandl er (1992) mixing rule, on critical point
calculations. In the first paper (Castier and Sandler,
1997), the van der Waals EOS and the NRTL model
were used in a systematic study of the types of critical
phase diagrams t hat are generated within certain
ranges of the model parameters. Since there we were
more interested in the qualitative aspects of the phase
diagrams, no attempt was made to compare the
results with experimental data.
3579
3580 M. Castier and
In this paper, the objective is to compare the predic-
tions of this EOS model with experimental critical
dat a of binary mixtures. Since only a very crude
representation of pure component properties can be
expected from the van der Waals EOS, an EOS suit-
able for engineering calculations, the Stryjek and Vera
(1986), PRSV EOS, version of the Peng- Robi nson
(1976) EOS, was combined with the modified form
(Huron and Vidal, 1979) of the NRTL model (Renon
and Prausnitz, 1968) and used in our calculations. In
order t o comprehensively search for the critical states
of mixtures exhibiting complex behavior, including
the possibility of multiple critical points at any speci-
fied composition, the Hicks and Young (1977) algo-
rithm was used. The model parameters were estimated
from vapor-l i qui d equilibrium (VLE) data, only some
of which at high pressure, but no experimental critical
information was directly used in the fitting procedure,
except to guide the choice of parameters in systems
that could be equally well represented by several sets
of parameters. Apart from that, the calculations
represent predictions rather than correlations of the
critical curves.
The critical points were calculated as described
earlier (Castier and Sandler, 1997) using a modified
version of the Hicks and Young (1977) algorithm to
determine possible multiple critical points at any
given composition and refining the solutions with the
Hei demann and Khalil (1980) procedure. Onl y critical
points t hat passed the local and global stability tests
are reported here. However, it should be mentioned
t hat the global stability test was only implemented to
"verify the possibility of additional fluid phases; the
possibility of forming solid phases was not tested in
our implementation.
T H E R M O D Y N A M I C M O D E L
The Peng- Robi nson EOS (PR EOS) (1976) is
R T a
P
v - b v 2 + 2bv - b 2
with the a and b parameters given by
0.477235R 2 T~
all - - - - ~PR, i
Pc,
0 . 0 7 7 7 9 6 RT~,
bi =
Pc,
with
~eR,, = [1 + x,(l - x/~R,)] 2
where the reduced temperature is
TR, = T / T c ,
In the PRSV EOS, Ki is given by
xi = ~o, + xl,(1 + x/~R,)(0.7 - T~, )
where
Xo, = 0.378893 + 1.4897153oi - 0.1713848o~
+ 0.019655409~
(1)
S. I. Sandier
and xl, is a characteristic parameter of each compon-
ent. Values of the critical properties, acentric factor
and characteristic parameter ~q, were taken from
Stryjek and Vera (1986).
In the Wong- Sandl er mixing rule, the mol ar excess
Helmholtz free-energy calculated from the EOS at
infinite pressure (a~ Es) is equated to the same prop-
erty comput ed from an excess free-energy model (a~)
such as NRTL, i.e.:
a E, Eos E
= a ~ . ( 8 )
Wong and Sandler showed that the a and b para-
meters are then given by
R T Qw s Dw s
a = R T D~ s b (9)
1 - D w s
Qw~
b - - - (10)
1 - D w ~
where
a~ (11)
Ows=~+ ~ xia.
i= 1 R T b i
Qws = x i x j b -
~=1 j =l ij" (12)
The paramet er c depends upon the equation of state
and, for the PRSV EOS, it is given by
c =- - ~-
The following combi ni ng rule has been used:
b - ~ ij 2 (1 - ki j ). (14)
Expressions for the fugacity coefficient and its deriva-
tives with respect to composition at const ant temper-
ature and total volume required in the critical point
calculations were determined using Ma t h e ma t i c a
(Wolfram, 1991) and can be obtained from the
authors on request.
( 2 ) P A R A M E T E R E S T I M A T I O N
The binary interaction parameters of the model
(3) employed in the critical point calculations were either
obtained from the literature (Orbey and Sandier,
1995) or determined using a modified version of the
(4) parameter-fitting program originally developed by
them. The following objective function was used:
nt,
(5) f - - ~ fP~ - P~I + P (15)
j = l
where P~ and Pf , respectively, denote the calculated
(6) and measured values of pressure at experimental
point j, and p is a penalty parameter t hat is added to
prevent the model from predicting liquid-liquid equi-
librium when no experimental evidence supports its
existence. Examples of systems in which this may
(7) occur include propane + methanol and hexane +
Critical points with the Wong-Sandler mixing rule--II
et hanol , as observed by Or bey and Sandi er (1995) and
Englezos et al. (t989), respectively.
The i mpl ement at i on of the cri t eri on pr oposed by
Englezos et al. (1989) tests for l ocal st abi l i t y at the
experi ment al points. However, it is t heoret i cal l y pre-
ferable to test for gl obal st abi l i t y and for this reason
we used the following expressi on for the penal t y term:
nun,
p = - t/ ~" dk (16)
k=t
where nuns is t he number of gl obal l y unst abl e poi nt s
with respect to the f or mat i on of an addi t i onal liquid
phase and dk is the mi ni mum nondi mensi onal ' dis-
t ance' in the t angent pl ane cri t eri on (Michelsen, 1982)
at a poi nt k t hat is unstable. This ' di st ance' is negative
for unst abl e poi nt s and is given by
n,
d = min ~ w~(ln(w~qS~) - ln(xiq~/)) (17)
i = 1
where q~ denot es fugacity coefficients, the dot indicates
pr oper t i es at t ri al composi t i ons, and the mi ni mi zat i on
is carri ed out havi ng as vari abl es the i ndependent
mol e fractions of the t ri al phase. I n t he case of bi nar y
systems, as t hose st udi ed in this paper, the cal cul at i on
of this ' di st ance' reduces to a uni di mensi onal mi ni mi z-
at i on probl em. In eq. (16), we also used a scaling
factor t/ with an ar bi t r ar i l y large numeri cal value
(10 s bar) to penalize unst abl e poi nt s even if close to
the st abi l i t y limit.
In this paper, P - T - x or P - T - x - y dat a were used t o
est i mat e four model par amet er s in bi nar y systems: the
bi nar y par amet er k~2 in eq. (14) and the three par a-
meters in the modi fi ed NRTL model: ~, g~2/R and
021/R.
RESULTS
Cri t i cal loci were cal cul at ed for some highly non-
ideal mixtures such as n-al kane + 1-al kanol systems,
n-pent ane + acetone, car bon di oxi de + water, wat er
+ n-dodecane and met hane + n-hexane. Tabl e 1
presents t he par amet er s used for t he critical poi nt
cal cul at i ons of each system st udi ed here, t hough the
specifics of the par amet er est i mat i on for each system
are discussed separat el y. Int erest i ngl y, t he est i mat ed
values of the ~ par amet er range from 0.4 to 0.6 for
most of the systems studied, but are as high as 0.9 in
3581
the met hane- et hanol system as det ermi ned by Or bey
and Sandi er (1995).
Even t hough hi gh-pressure VLE dat a were used in
the par amet er est i mat i on for some of the systems
present ed in this paper, no critical dat a were directly
used. However, we observed t hat for some of the
systems, several sets of par amet er s yi el ded a similar
correl at i on of the VLE dat a, but resulted in not i ceabl y
different behavi or when used to predi ct the critical
loci. For such systems, as ment i oned in the text, the
critical dat a provi ded gui dance as to which par amet er
set t o use; apar t from t hat , the report ed critical behav-
i or represents predi ct i ons rat her t han correl at i ons.
n-Alkane + 1-alkanol systems
Binary systems cont ai ni ng an n-al kane and a 1-
al kanol can devi at e significantly from ideal behavi or
and therefore represent a severe test of t her modyn-
amic models. For the met hane + et hanol mixture,
Fig. 1 shows the P - T proj ect i on of the critical curve
cal cul at ed with par amet er s found by Or bey and
Sandl er (1995), using i sot hermal VLE dat a measured
by Brunner and Hfi l t enschmi dt (1990) at 298.15 K. An
at t empt to si mul t aneousl y also use dat a avai l abl e at
higher t emperat ures to est i mat e the par amet er s of the
model led t o si mi l ar critical poi nt projections. The
cal cul at ed branch of the critical line t hat starts at pure
met hane is ext remel y short, which is also found in the
experi ment al dat a, whereas the branch t hat st art s at
pure et hanol proceeds t owar ds high pressures as the
t emper at ur e decreases, and t hen passes t hr ough
a maxi mum. We coul d not find experi ment al dat a to
test these results. It shoul d be not ed t hat the cal-
cul at ed critical t emper at ur e goes bel ow the melting
poi nt of pure et hanol at at mospher i c pressure, which
occurs at 159.1 K, and t here is the possi bi l i t y of form-
ing a solid phase. Shoul d this happen, par t of the
cal cul at ed critical branch woul d be unstable. Our
i mpl ement at i on of the gl obal st abi l i t y cri t eri on di d
not test for the possible f or mat i on of solid phases.
The P - T proj ect i on for the system et hane +
et hanol is present ed in Fig. 2. As in the met hane +
et hanol system, the critical lines were cal cul at ed using
par amet er s est i mat ed by Or bey and Sandl er (1995)
from i sot hermal VLE dat a at 348.15 K measured by
Brunner and Ht i l t enschmi dt (1990), and an at t empt to
Table 1. Parameters for the systems studied
Component 1 Component 2 ~ gl2/R (K) gzl/R (K) k12
Methane Ethanol 0.90 165.8 238.4 0.000
Ethane Ethanol 0.50 2263.0 435.2 0.101
n-Butane Ethanol 0.47 1132.0 305.8 0.152
n-Pentane Ethanol 0.60 805.8 240.8 0.252
Propane Methanol 0.39 2353.0 660.2 0.150
n-Hexane Methanol 0.55 1720.0 2952.0 0.411
n-Pentane Acetone 0.60 468.7 207.1 0.126
Carbon dioxide Water 0.33 382.8 1167.0 0.309
Water n-Dodecane 0.52 - 1161.0 1727.0 0.491
Methane n-Hexane 0.60 - 54.0 38.6 0.0045
3582 M. Castier and S. I. Sandier
9 0 0
8 0 0
700
6 0 0
vx~ 5 0 0
4 0 0
o .
30O
2 0 0
1 0 0
- - C a l c u l a t e d
B r u n n e r a n d
H O l t e n s c h m i d t (1 g 9 0 )
0 M e t h a n e
6 5
I C a l c u l a t e d I

6O
5 5
~ s o
45
40
3 5 r ~ ~ ~ 0 - -
100 150 900 250 300 350 400 450 500 550 400 420 440 460 480 500 520
T e m p e r a t u r e (K) T e m p e r a t u r e (K)
Fig. 1. Critical curve of the system methane + ethanol: pres- Fig. 3. Critical curve of the system n-butane + ethanol: pres-
sure-temperature projection, sure-temperature projection.
1 3 0 6 5
1 2 0
1 1 0
1 0 0
& 90
~ 80
a.
70
60
517
40
250
C a l c u l a t e d --7
J B r u n n e r a n d [
H01tenschmidt ( 1 9 9 0 ) 1
I I I I
3 0 0 3 5 0 4 0 0 4 5 0 5 0 0
T e m p e r a t u r e (K)
5 5 0
Fig. 2. Critical curve of the system ethane + ethanol: pres-
sure-temperature projection.
60
55
so
~ 45
4 0
3 5
3 0
4 5 0 5 2 0
- - C a l c u l a t e d ]
M
q r ~ i i f
4 6 0 4 7 0 4 8 0 4 9 0 5 0 0 5 1 0
Te mpe r a t ur e ( ~
Fig. 4. Critical curve of the system n-pentane + ethanol:
pressure-temperature projection.
simultaneously use data at other temperatures in the
parameter estimation procedure produced similar re-
sults. Even though the maximum in critical pressure is
overestimated, the model correctly predicts the dis-
continuity in the vapor-liquid critical line with the
occurrence of upper and lower critical endpoints.
Brunner and Hiiltenschmidt (1990) experimentally de-
termined that the upper and lower critical endpoints
occur at 314.36 K, 55.37 bar and 308.72 K, 49.52 bar,
respectively, whereas our calculations predicted these
values to be 314.3 K, 63.9 bar and 314.0 K, 54.1 bar.
To represent the system n-butane + ethanol, we
used all the experimental VLE data available at
several temperatures in the work of De~k e t a l . (1995).
The P - T projection of the vapor-liquid critical line is
shown in Fig. 3. In agreement with experimental data,
the model predicts a continuous vapor-liquid critical
line connecting the critical points of the two pure
components. For the system n-pentane + ethanol, the
parameters were estimated using experimental VLE
data available at 422.6 K from Campbell e t a l . (1987).
This system also exhibits a continuous critical line
between the two pure components and our predic-
tions in Fig. 4 show good agreement with the very
limited experimental information available for this
system (McCracken e t a l . , 1960). Another set of para-
meters determined using all the VLE data from
Campbell e t a l . , at 372.7, 397.7 and 422.6 K, leads to
predictions of a similar, though less accurate repres-
entation of the critical line.
Critical points with the Wong-Sandler mixing rule--II 3583
~g
o-
100
90 t "
80
70
60
50
40
30
340 360
- - C a lc u la te d
B ru n n er (1 9 8 5 )
3 8 0 4 0 0 4 2 0 4 4 0 4 6 0 4 8 0 5 0 0 5 2 0 5 4 0
9 0
8 0
70
6 0
o~
5 0
O.
4 0
3o
I I I I I I 2 0 I I I I
4 7 0 4 8 0 4 9 0 5 0 0 5 1 0
Temperature (K) Temperature (10
- - C a lc u la te d [
d e L o o s e t a l. (1 9 8 8 ) I
o Z a w ~ ~
o
i
5 2 0
Fig. 5. Critical curve of the system propane + methanol: Fig. 6. Critical curve of the system n-hexane + methanol:
pressure-temperature projection, pressure-temperature projection.
The system propane + methanol was particularly
difficult to model. Orbey and Sandler (1995) observed
t hat when VLE dat a (Galivel-Solastiouk e t al . , 1986)
were used t o fit the parameters, the model predicts
false liquid-liquid phase splitting. Consequently, they
used dat a at 313.1 K while imposing local stability as
proposed by Englezos e t al . (1989) to estimate para-
meters. When used for critical point calculations, their
parameter values predict the occurrence of critical
endpoints which were not observed experimentally by
Brunner (1985). We were able to improve the predic-
tion of the critical line by estimating the model para-
meters using experimental VLE dat a at all the
temperatures (313.1, 343.1 and 373.1 K) t hat were
available in the paper by Galivel-Solastiouk e t al . The
P - T projection of our calculated critical line and the
experimental critical dat a measured by Brunner
(1985) are shown in Fig. 5. A fairly good quantitative
representation of the P - T projection of the critical
line was obtained, even t hough the model predicts the
existence of critical endpoints. Therefore, al t hough
our parameter estimation procedure prevented false
liquid-liquid phase splitting at all dat a points for the
three different temperatures, a liquid-liquid split oc-
curred along the vapor-l i qui d critical line. This
behavior suggests t hat this system provides a parti-
cularly stringent test of the accuracy of equations of
state, their mixing rules, and the parameter values
used.
The system n-hexane + met hanol was also difficult
t o model, even t hough qualitative agreement with the
experimental data, in terms of a continuous critical
line connecting the two critical points of the pure
components, was achieved in our two attempts to
represent this system. In the first attempt, parameters
were estimated using dat a measured by Zawisza
(1985) at 448.15 K, and in the second using dat a
measured by de Loos e t al . (1988) at several temper-
atures. The P - T projection of the vapor-l i qui d criti-
cal line calculated using the first set of parameters
(shown in Table 1) is presented in Fig. 6. The results
with the second parameter were similar in behavior to
the first set, but provided a less accurate representa-
tion of the critical line. The n-hexane + methanol
system also has a liquid-liquid critical line t hat goes
to high pressures, as observed by H61scher e t al .
(1986). Although not shown in the figure,
a liquid-liquid critical line for this system was found
in our calculations, but its agreement with the avail-
able experimental dat a was not satisfactory.
n - P e n t a n e + a c e t o n e s y s t e m
Experimental VLE dat a available at three different
temperatures (372.7, 397.7 and 422.6 K) from Camp-
bell e t al . (1986) were used for parameter estimation.
The critical dat a measured by Hajjar e t al . (1986)
shows t hat this system has a continuous critical line
between the two pure component s with a mi ni mum in
temperature, and this behavior is correctly predicted
by the EOS model (Fig. 7). It should be mentioned,
though, t hat the shape of this critical line is very
sensitive t o the EOS parameter values that are used.
When we used other parameter sets that provided
similar accuracy in the correlation of the relatively
low pressure VLE dat a of Campbell e t al . (1986), we
found t hat either pressure minima or maxi ma could
be predicted in the critical line, but they are not
observed in the experimental data,
C a r b o n d i o x i d e + w a t e r s y s t e m
The VLE dat a measured by Toedheide and Franck
(1963), as reported by Knapp e t al . (1982), were used
for parameter estimation. These dat a go to very high
pressure, up to 3500 bar, which we could not fit to the
EOS model. For this reason, data points above
1000 bar were not included in the parameter estimation
3584 M. Castier and S. I. Sandier
48
46
44
,~, 42
~ 4 0
~ 38
36
34
32
460 470 480 490 500 510
Temperature (K)
4000
3500
3000 -
~, 2500
v
2000
1500
1000
500
I
250
(a)
Toedheide and
Franck (1963)
Takenou~i and
Kennedy (1964)
Calculated
- - Calculated
300 350 400 450 500 550 600 650
Temperature (K)
700
Fig. 7. Critical curve of the system n-pentane + acetone:
pressure-temperature projection.
900
800
procedure, as well as some of the data points between 700
500 and 1000 bar. The P - T and T - x projections of
the critical loci are shown in Figs 8(a) and (b). In the ~ 600
P - T projection, as the critical pressure increases, the
critical temperature first decreases and then starts to E g 500
increase, a pattern that is also present in the data of
Toedheide and Franck (1963). However, the T - x pro- 400
jection shows that the EOS predicts multiple critical
points in the 0.22 ~< Xco2 <<-0.29 composition range
300
that are not observed in the experimental data, and at
a mole fraction of carbon dioxide equal to 0.4 the
calculated critical temperature is more than 200 K 200
above the experimental value. Compared to the ex-
perimental data at this composition, the calculated (b)
critical pressure has a far higher value. We also ob-
served that the critical curve was fairly well represent-
ed up to approximately 750 bar, which corresponds
to the pressure range of most of the VLE data used
for parameter estimation. As the model could not
correlate the VLE data above 1000 bar for this sys-
tem, the critical point predictions clearly could not be
expected to be quantitatively accurate at very high
pressures.
Wat er + n-dodecane syst em
The VLE data measured by Stevenson et al. (1994),
but not their liquid-liquid data, were used to fit the
parameters of the model for this very asymmetric
system. Even after parameter fitting, relatively large
deviations were obtained between the measured and
calculated VLE data. We see in Fig. 9 that even
though a type III diagram is correctly predicted, the
P - T projection of this system is not quantitatively
accurate. The calculated critical branch that starts at
pure n-dodecane ends at an upper critical endpoint
whose values of temperature and pressure are higher
than the experimental data. The calculated critical
branch that starts at pure water proceeds to high
T q 7 q
Toedheide and
Franck (1963)
O Takenouchi and
Kennedy (1964)
- - Calculated
o Calculated
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction of carbon dioxide
Fig. 8. Critical curve of the system carbon dioxide + water:
(a) pressure-temperature projection; (b) temperature-mole
fraction projection.
pressures passing through a minimum in temperature
but does not pass through a pressure minimum.
Met hane + n-hexane syst em
The methane + n-hexane system was chosen for
study because it is formed from relatively simple
molecules of similar chemical nature but whose large
size difference is possibly the most important factor
contributing to its rather complex critical behavior.
Here, we estimated the model parameters using the
VLE data measured by Lin et al. (1977), but not their
LLE, VLLE or critical data. No parameter set was
found that would insure global phase stability for all
experimental data points and this requirement was
dropped from the parameter estimation scheme for
this system. In the P - T projection, this system has
a discontinuous gas-liquid critical line with a long
branch that starts at pure n-hexane ending at a lower
critical endpoint, and a short branch that goes from
Critical points with the Wong-Sandler mixing rul e--II
3585
3 5 0 -
3 0 0
2 5 0
200
150
o.
1 0 0
5 0
1
B r u n n e r ( 1990) [
Calculated
J
~ o ~
q F T ~ T F
2 5 0
2 0 0
150
to
~. l oo
50
0 0
560 580 600 520 640 6 6 0 680 700 150
Temperature (K) (a)
i
L2=G, Lin e t a l . (1977
~" El =L2, Lin e t a l . (1977) \
LI=G, Lin e t a l . (1977) \
H i c k s and Young (1975) \
M e th a n e
n-Hexane
- - Calculated
I I I I I
2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0
Temperature (K)
550
Fig. 9. Critical curve of the system water + n-dodecane:
pressure-temperature projection.
2 5 0
200
pur e met hane to an upper cri t i cal endpoi nt . I n t he
T - x a nd P - x proj ect i ons, t he dat a of Li n e t al. (1977)
show t hree br anches i n the critical line, t wo of whi ch ~ v 150
combi ne i n t he P - T pl ane i nt o a c ont i nuous proj ec-
t i on. Fi gur es 10(a) and (b) show cal cul at ed pr oj ect i ons
100
of t he cri t i cal loci, t he exper i ment al critical dat a of Li n
et al. (1977) a nd dat a from t he compi l at i on of Hi cks
a nd Young (1975). The P - T pr oj ect i on shows satisfac- 50
t or y agr eement bet ween t he cal cul at ed a nd experi-
ment al values, but t he P - x pr oj ect i on shows t hat t he
model does not predi ct t he l i qui d- l i qui d cri t i cal l i ne i n
0
t he 0.8900 ~< Xc, , ~< 0.9286 compos i t i on r ange re- 0.0
por t ed by Li n e t al. I nst ead, t he cal cul at ed critical l i ne
(b)
t hat st art s at pur e n- hexane under goes a cont i nuous
t r ans i t i on from a gas - l i qui d cri t i cal l i ne to
a l i qui d- l i qui d- l i ke cri t i cal l i ne i n t he vi ci ni t y of pur e lo0 -
met hane. Fi gur e 10(c), whi ch pr ovi des a magni fi ca-
t i on of t he P - T pr oj ect i on close t o pur e met hane, 90 -
shows t hat t he cal cul at ed cri t i cal br anch t hat orig-
i nat es from pur e n- hexane agrees fairly well wi t h the
8 0 -
exper i ment al cri t i cal poi nt s despi t e a syst emat i c devi- ~,
at i on. The predi ct ed coor di nat es of the l ower cri t i cal
endpoi nt are XcH, = 0.9337, 182.50 K and 34.85 bar ~ 70
a nd t he exper i ment al val ues are Xcn, = 0.9286, .~
a. 60
182.46 K and 34.15 bar. Lar ger devi at i on was f ound
at t he upper cri t i cal e ndpoi nt where t he critical
50
br anch t hat st art s at pur e met hane ends: t he cal-
cul at ed coor di nat es are XcH, = 0.9987, 192.70 K and
40
48.32 bar a nd t he exper i ment al val ues are
XCH, = 0.9976, 195.91 K and 52.06 bar.
3 0
Si mi l arl y to some of t he ot her syst ems t hat we have
180
st udi ed here, some of t he fine det ai l s of t he critical
phase di agr ams coul d not be predi ct ed by t he model . (c)
I n this case, it is t he i sol at ed l i qui d- l i qui d critical l i ne
t hat occurs over a nar r ow compos i t i on range. I nt er -
estingly, however, t he overal l r epr esent at i on of t he
syst em is fair, a nd even quant i t at i ve agr eement is
L2=G, Linetal. (1977) I
L 1 = L 2 , L i n a t a/. ( 1 9 7 7 ) I
LI=G, Lin e t a / . (1977) I
H i c k s and Young (1975)
C a culated
~7
0.2 0.4 0.6 0.8
M ole fraction o f methane
1.0
1 /
L2=G, Lin e t a / . (1977) I J
L1 =L2, Lin e t a l . (1977)
LI=G, Lin e t a / . , 1977
M e th a n e
- - Calculated
~7 ~7
i I I i i
185 190 195 2 0 0 2 0 5
Temperature (K)
210 215
Fig. 10. Critical curve of the system methane + n-hexane:
(a) pressure-temperature projection; (b) pressure-mole frac-
tion projection; (c) magnification of the pressure-temper-
ature projection close to pure methane.
3586 M. Castier and S. I. Sandier
achieved in portions the critical phase diagrams, al-
though we have only used VLE data for parameter a
estimation. It would be interesting to study whether
a better representation could be obtained from this b
model with a more complex parameter estimation c
that would use not only VLE data but also LLE and
VLLE data.
CONCLUSIONS
This and the preceding paper had as their objective
a study of the critical loci of binary mixtures com-
puted using cubic equations of state and excess free-
energy model-based mixing rules. In this paper, the
Stryjek and Vera version of the Peng-Robinson EOS
and the modified NRTL model (Huron and Vidal,
1979) were combined using the Won~Sandl er mixing
rule. The model parameters were fitted using experi-
mental vapor-liquid equilibrium data, but no critical
point data were directly employed, except in some
instances to provide guidance as to which parameter
set to use for some systems whose VLE data could be
equally well represented by several sets of parameters.
The model was then used to predict critical points of
some highly non-ideal systems and for most of them,
the shape of the critical lines was correctly predicted.
Notable exceptions were the propane + methanol
system for which a discontinuous vapo~liquid critical
line was predicted while the experimental critical data
indicate that this system exhibits a continuous critical
line, and the methane + n-hexane and n-hexane +
methanol systems for which isolated liquid-liquid
critical lines observed experimentally were not pre-
dicted to occur. For the carbon dioxide + water sys-
tem, the critical curve was well represented up to
750 bar, but was not quantitatively correct at higher
pressures. While the model studied here has been able
to quantitatively predict the critical behavior of some
highly non-ideal systems involving compounds such
as water, acetone and alkanols, for some highly asym-
metric and non-ideal mixtures, such as water + n-
dodecane, only qualitatively correct critical behavior
could be predicted.
Since it is well known that cubic equations of state
are not accurate in the critical region for pure fluids,
perhaps the most surprising result of this study is that
the predictions for complex critical phenomena in
mixtures with a simple equation of state and the
Wong-Sandler mixing rule are as good as they are.
However, a word of caution. We have also found that
the predictions are quite sensitive to the values of the
parameters used.
Dw~
f
Yij
ki)
rl c
np
nuns
P
Qws
R
T
/)
xi
wi
Acknowledgments
The preparation of this manuscript was supported, in part,
by Grant No. DE-FG02-85ER13436 from the U.S. Depart-
ment of Energy, and Grant No. CTS-9123434 from the U.S.
National Science Foundation, both to the University of
Delaware. M. C. acknowledges the financial support of the
Brazilian Ministry of Education (CAPES) and of the
Brazilian Conselho Nacional de Desenvolvimento
Cientifico e Tecnol6gico (CNPq)
NOTATION
molar Helmholtz free-energy or EOS
attractive parameter
EOS covolume parameter
characteristic parameter of the equation of
state ( 2 -0. 62323 for the PR and PRSV
EOS)
minimum 'distance' in the global stability
test
auxiliary parameter of the Wong-Sandler
mixing rule
objective function for parameter estimation
interaction parameter in the NRTL model
binary interaction parameter
number of components
number of experimental data points
number of globally unstable points during
parameter estimation
penalty term in the objective function for
parameter estimation
pressure
auxiliary parameter of the Wong-Sandler
mixing rule
universal gas constant
temperature
molar volume
mole fraction of component i
mole fraction of component i
Greek letters
c~ NRTL nonrandomness parameter
~w auxiliary term in the Peng-Robinson equa-
tion of state
q scaling factor
parameter of the PR and PRSV equations
Ko, xl parameters of PRSV equation
qS~ fugacity coefficient of component i
o~ acentric factor
Subscripts
c critical property
i, j refer respectively to components i and j
R reduced property
property at infinite pressure
Superscripts
c calculated
e experimental
E excess property
EOS equation of state
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