Ind. Eng. Chem. Process Des. Dev.
1983, 22, 385-391
n - 1 = tray n - 1
i = component i
D = distillate
Literature Cited
BubbleTray Design Manual; American Institute of Chemical Engineers,
New Ycfk, 1958.
Colbwn, A. P. Ind. Eng. Chem. 1936, 28, 526.
A Versatile Phase Equilibrium Equation of State
Paul 1111. Mathlas
Energy Laboretfny and Chemical Engineering Department, Massachusetts Instftute of T e c h n o w ,
C a m b r m , Massachusetts 02139
The Soave modification of the Redlich-Kwong equation has been very effective for conelating the phase equilibrium
of systems containing nonpolar and slightly polar substances. In this work further modiflcations are introduced
which retain the simplicity and robustness of the Soave equation but extend its application to systems containing
highly polar substances such as water. Appllcations shown in the work include systems of interest in coal processing
and some common systems containing water.
Introduction
The increased use of computers for chemical process
design has stirred great interest in the analytic repre-
sentation of the phase behavior of multicomponent sys-
tems. This analytic description must, of course, be
quantitatively accurate, but it should also possess the
qualities of few and easily attainable correlation parame-
ters, never predicting physically absurd results and being
computationally robust and efficient.
Very broadly, practical methods to represent phase
behavior can be divided into activity coefficient and
equation of state approaches. In the activity coefficient
method an activity coefficient model, say the UNIQUAC
equation, is used to represent the nonideality of the liquid
phase($ while a different model, usually an equation of
state, is used to describe the departure from the ideal gas
reference state of the vapor phase. The latter approach
uses the same equation of state to represent all coexisting
phases. The equation of state approach has been effective
in describing systems containing only nonpolar and slightly
polar components, but the common consensus appears to
be that the additional flexibility of activity coefficient
models is necessary to correlate highly nonideal systems
which contain polar substances.
The activity coefficient approach has been found to
correlate a wide variety of complicated phase behavior, but
this has been at the expense of a large number of param-
eters which extrapolate poorly with temperature.
Another-and more serious-disadvantage is that anom-
alous results are obtained in the critical region since dif-
ferent models are employed for vapor and liquid phases.
On the other hand, the equation of state approach predicta
critical regions quite naturally, and even relatively simple
equations like those of Soave (1972) and Peng and Rob-
inson (1976) are capable of satisfactory predictions of
complicated critical region phase behavior (e.g., see
Heidemann and Khalil, 1979).
*Air Products and Chemicals, Inc., Box 538, Allentown, PA
18105.
0198-430518311122-0385$01.50/0
385
King, C. J. Separation Process, 2nd ed.; McGraw-Hill, Inc; New York,
1981; p 472
Lewis, W. K. Ind. Eng. Chem. 1936, 28. 399.
Mohan, T. M.Tech. Thesis, I.I.T., Kanpur, India, 1981.
Received for review May 27, 1981
Revised manuscript received October 21,1982
Accepted December 16,1982
Thus it would be very useful to have an equation of state
applicable to systems containing polar substances. One
attempt to achieve this goal was that by Gmehling et al.
(1979), who assumed a chemical equilibrium hypothesis.
In their work, Gmehling et al. assumed that polar species
form dimers, and by fitting data to determine a stand-
ard-state enthalpy and entropy of dimerization they cor-
related vapor-liquid equilibria for many polar mixtures.
However, this approach has several disadvantages.
Whiting and Prausnitz (1981) point out three of them.
First, experimental evidence supports the existence of
dimers only in rare cases. Second, application of chemical
theory greatly increases the computational load since it
requires the solution of chemical-as well as phase-
equilibrium. Third, the number of pure-component and
binary parameters increases because standard-state en-
thalpies and entropies of dimerization are required. An
important disadvantage not cited by Whiting and Praus-
nitz (1981) concerns applications at severe conditions, say
in the retrograde region or even approaching the critical
point. Under these conditions even the use of relatively
simple models like Soave (1972) have presented severe
computational challenges requiring sophisticated solutions
(Michelson, 1980; Asselineau et al., 1979; Mathias et al.,
1981; and Chan and Boston, 1981). Models employing
chemical theory may well be pathological to computational
robustness.
A remarkable success in the design of an equation of
state for the correlation of fluid-phase equilibrium has been
the simple idea of Soave (1972). He recognized that a
prerequisite for the correlation of phase equilibria of
mixtures is the correlation of the vapor pressures of pure
substances. The Soave modification of the Redlich-Kwong
(1949) equation has been very successful in correlating the
phase behavior of multicomponent systems containing
nonpolar and slightly polar substances. In this work, the
Soave approach is used to extend the Redlich-Kwong-
Soave equation to systems containing highly polar sub-
stances such as water and the alcohols.
The work also utilizes the modification of the Soave
equation suggested by Boston and Mathias (1980) to im-
@ 1983 American Chemical Society
388 Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 3, 1983

Table I. Vapor Pressures of Highly Polar Substances; Comparison between Original and Modified RKS
% dev,
% dev, p = 0 p fitted
temp range,
substance T,, K P c , atm w P K max ava max ava reference
water 647.3 218.3 0.3439 0.1277 273-647 -33.6 10.2 0.9 0.3 Meyer et al. (1967)
acetone 508.1 46.38 0.307 0.0715 259-508 -9.1 2.5 0.9 0.4 Ambroseetal. (1974)
methanol 512.64 79.91 0.565 0.2359 288-513 -19.4 4.6 0.9 0.4 Ambrose and Sprake (1970)
Ambrose et al. (1975)
ethanol 513.92 60.68 0.646 0.1006 293-514 -9.4 1.5 1.7 0.7 Ambrose and Sprake (1970)
Ambrose et ai. (1975)
l-pentanol 588.15 38.58 0.585 -0.2615 348-512 17.9 5.3 1.7 0.7 Ambrose and Sprake (1970)
Ambrose et al. (1975)
l-octanol 652.50 28.23 0.598 -0.2109 386-554 17.9 4.0 4.5 2.2 Ambrose and Sprake (1970)
Ambrose et al. (1975)
Average absolute percentage deviation = Z i Ipiemfl- piCad I/(no. of data points).

prove VLE calculations of systems containing highly su-
percritical substances. We show that this modification
successfully correlates the VLE of systems containing
substances such as hydrogen, methane, and carbon dioxide
at temperatures much above their respective critical tem-
peratures. Incidentally, these systems are of interest in
coal conversion processes.
A comment about the importance of fundamental con-
siderations is in order. Many authors (e.g., see Henderson,
1979) have pointed out that the theoretical basis of the
Redlich-Kwong equation is weak. There is a valid sepa-
ration of the attractive and repulsive contributions, but
the expression for repulsive contributions is correct only
for a one-dimensional system of hard rods. Further, the
equation gives a universal value of the critical compres-
sibility factor of 1/3 which is too large for all substances,
leading to poor liquid molar volumes. However, perhaps
due to a fortunate cancellation of errors and certainly due
to the clever parameterization of Soave (1972), it has been
successfully used for the prediction of multicomponent
phase equilibria in a wide variety of process design ap-
plications. It should also be mentioned that the approach
of this work will probably yield similar results with the
Peng-Robinson (1976) or Martin (Martin, 1979; Joffe,
1981) equations.
Description of the Equation
Pure Fluids. The Soave equation is
p = - -RT
- U
u - b U(U + b )
In order to reproduce the critical temperature and pres-
sure, the constants a and b are given by
R2Pd
ai(TCi)= = 0.42747-
Pci
RTci
bi = 0.08664-
Pci
Following Soave, we keep b as a constant and make a a
function of temperature such that the vapor pressure of
the pure substance is well correlated. Thus
ai(T) aciai(T) (4)
where ai(7') is an adimensional fador which takes the value
of unity at T = Tci. A good correlation for ai is given by
aP5 = 1 + mi(l - - pi(l - TR)(0.7 - TRi) (5)
where T a = T/T,is the reduced temperature of compo-
nent i.
The second term on the right side of eq 5 was introduced
by Soave to reproduce the vapor pressures of nonpolar
substances. He correlated the characteristic constant m
as a function of the acentric factor. The correlation used
in this work was obtained by Graboski and Daubert (1978).
It is very similar to that of Soave but is slightly better since
it was regressed from a larger data set. The correlation
for m is given by
mi = 0.48508 + 1 . 5 5 1 9 1 ~
- ~0.15613wt (6)
The Soave equation for a (eq 6 and only the first two terms
on the right side of eq 5) adequately correlates the vapor
pressures of nonpolar and slightly polar substances (Gra-
boski and Daubert, 1978). However, it was found that the
agreement with vapor pressure data of polar substances
is seriously in error. By definition, the Soave equation
reproduces the vapor pressures of all substances at the
critical temperature and a reduced temperature of 0.7.
Comparison with experimental data for polar substances
shows that the Soave equation over-predicts the vapor
pressure at reduced temperatures between 0.7 and 1.0 and
under-predicts it at reduced temperature less than 0.7, or
vice versa. One of the simplest empirical terms which
corrects this is the third term on the right side of eq 5, and
fortunately it is found to work very well.
Table I shows the significant improvement in vapor
pressure correlation obtained by wing the polar parameter
p for some common polar substances. We note that the
critical temperature and pressure used are the best ex-
perimental value and the acentric factor is that which
reproduced the experimental vapor pressure at a reduced
temperature of 0.7 using the Soave equation. Finally, the
polar parameter p was fitted to the experimental vapor
pressure data.
The polar parameter p introduced in eq 5 is highly em-
pirical. It is unlikely that p can be correlated in terms of
other quantities such as the dipole moment since ita value
is probably a lumped result of many different effecta-
including the inadequacy of the Redlich-Kwong equation.
(Note that ita value even changes sign as one goes to the
(3)
higher normal alcohols.) However, there is only one ad-
ditional parameter whose value could probably be obtained
from few experimental vapor pressure data. Further, the
simple form of the Redlich-Kwong equation is retained,
and this is important for the computational robustness and
efficiency essential to process design applications.
CY for Supercritical Substances. Since the CY ex-
pression was obtained by matching pure component data,
use of the same expression a t supercritical temperatures
(T> TJ represents extrapolation into an unknown region.
Boston and Mathias (1980) have suggested the following
extrapolation at supercritical temperatures
up5 = exp[ci(l - TRd')]
(7)
where

Equations 7,8, and 9 were obtained by splining eq 7 with
eq 5 at TRi= 1; the value and first derivative have been
matched and the second derivative of with respect to
TRihas been set to zero. The Boston and Mathias ex-
trapolation has been adopted in this work.
As explained in the Introduction, this work aims to
design an equation of state to produce good agreement
with experimental phase equilibrium behavior. Given a
simple equation such as the Redlich-Kwong equation, this
necessarily means a compromise, albeit small, in other
quantities such as molar densities. Thus it is not appro-
priate to choose the supercritical a by enhancing agree-
ment with PVT data. The Boston and Mathias extrapo-
lation provides better agreement with VLE data than the
Soave equation for common nonpolar binaries (Boaton and
Mathias, 1980). Further, eq 7 produces a qualitatively
correct high-temperature limit while the Soave equation
does not. This is illustrated in Figure 1, which shows
second and third virial coefficients for nitrogen. The Soave
a produces better agreement with experimental second
virial coefficient data but does go through a qualitatively
incorrect maximum a t a temperature of about lo00 K.
(We should note that this temperature is high enough to
be of little practical interest and this is generally true for
all substances.) For the third virial coefficient it is hard
to tell whether the Soave a is better than eq 7 given the
sparse available data. Again, the Soave a produces an
unphysical minimum at a temperature of about 1000 K.
Extension to Mixtures. The one-fluid theory has been
chosen to extend the pure fluid equation to mixture. Thus
the form of eq 1 is retained in the mixture case but the
parameters are obtained as simple quadratic mole fraction
averages of the pure component values
a = CCXiXjUi, (10)
i l
and
The binary parameter k,O is the one commonly used in the
Soave equation. Binary parameters have been assumed
for both a and b and each is linear in temperature giving
a total of four binary parameters. Use of four binary
parameters for each binary might be considered
excessive-and indeed this is so-but they have been de-
fmed since different kinds of applications require different
subsets. For example, hydrogen VLE is well correlated
using the parameters kbo and kbl. Further, all the appli-
cations in this work have assumed a zero value for kal. It
is expected that nollzero values of k, will be required only
for immiscible systems; these systems will be addressed
in future work.
Recently, more theoretically justifiable mixing rules have
been suggested based on the local composition concept
(Huron and Vidal, 1979; Whiting and Prausnitz, 1981).
These have not been employed since good quantitative
success has been obtained with the simple mixing rules
Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 3, 1983 387
3Or I I
I
Original RKS I---- GLL
Points Experimentoi D a t a
(Dymond and S m i t h ,
2000 ::
19691 8
1500 -I
>- 5
IO00 f
I 1 I I I I I
t
50 I00 200 500 1000 3000 5000
TEMPERATURE, K
Figure 1. Virial coefficienta of nitrogen calculated by original and
modified Soave equations.
used. Perhaps the results of this work could be used as
a benchmark against which the more sophisticated mixing
rules may be evaluated.
It should also be noted that the simple mixing rules
defined by eq 10-13 have been found to work very well.
For example, zero values for all binary parameters produce
good results for hydrocarbon mixtures, even those with
large size disparities (Graboski and Daubert, 1978).
Applications
A wide variety of applications are shown in this work
which demonstrate that the simple equation of state de-
fined by eq 1-13 is flexible enough to correlate difficult
phase behavior. No applications are shown for systems
exhibiting liquid immiscibility, but indications are that this
too can be satisfactorily correlated.
Experimental phase equilibrium data have been re-
greased by finding optimum values of the binary parameter
subset chosen through the use of the generalized least-
squares method of Britt and Luecke (1973). Values of
standard deviation chosen are 0.1 K for temperature and
2% for the other variables. In cases where vapor compo-
sition data were not available, estimated values were used
and the standard deviation made extremely large. For
mole fraction data there is a possibility that the model
values will move outside the range 0-1. Hence these
variables have been transformed by
The variable zi is used in the regression instead of xi since
it varies from -- to m as x i varies from 0 to 1.
While the generalized least-squares method provides a
flexible, powerful, and statistically correct way to regress
data, it creates ambiguity in reporting quantitatively the
goodness of fit. For example, if the standard deviations
in temperature and pressure are made large relative to
those for vapor and liquid composition, good apparent
agreement in K values could be obtained even with a poor
model. Hence in reporting average errors in this work,
errors in K values are given with the model value calculated
at the experimental conditions.
Since this equation of state defaults to the Soave
equation, all the good agreement with experimental data
for systems containing nonpolar, subcritical substances will
be obtained here. For systems containing some nonpolar,
supercritical substances superior agreement may be ex-
pected (Boston and Mathias, 1980). Further applications
are shown below.
388 Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 3, 1983
Table 11. Regression of Binary Vapor-Liquid Equilibrium: Systems with Hydrogen
Err. Err. temprange, rnaxP, no.
solvent kb kb' KH' K.q K atm data reference
methane 0.0335 0.0 2.49 0.89 91-117 125 20 Kirk and Ziegler (1965)
ethane 0.0230 0.0 6.25 9.54 103-283 545 38 Williams and Katz (1954)
propane 0.0071 0.0 5.11 12.87 88-297 546 48 Williams and Katz (1954)
m-butane 0.2770 0.8701 3.13 2.18 328-394 167 44 Klink et al. (1976)
n-hexane 0.1998 0.5849 5.78 12.92 278-478 681 47 Nichols et al. (1967)
n-octane 0.7840 1.7775 3.18 1.20 463-543 149 50 Connolly (1962)
benzene 0.4451 1.0722 2.38 1.62 433-633 176 49 Connolly (1962)
tetralin 0.2547 0.6100 3.36 4.96 463-662 250 24 Chao et al. (1980)
diphenylmethane 0.1378 0.3338 3.35 5.06 463-702 260 27 Chao et al. (1980)
m-cresol 0.2142 0.4534 3.53 2.48 462-662 250 41 Chao et al. (1980)
1-methylnaphthalene 0.1495 0.3574 3.49 4.06 462-702 250 27 Chao et al. (1980)
m-xylene 0.4095 0.9475 3.79 3.78 462-582 250 27 Chao et al. (1980)
quinoline 0.1241 0.2493 3.70 4.52 463-702 250 27 Chao et al. (1980)
n-decane 0.3683 0.8204 2.67 6.39 462-683 252 26 Chao et al. (1980)
bicy clohexyl 0.2526 0.5511 6.09 3.19 462-702 250 28 Chao et al. (1980)
toluene 0.4295 1.0140 3.78 4.58 462-575 250 25 Chao et al. (1980)
water 0.5063 0.8450 6.71 2.24 273-373 1000 20 Wiebe and Gaddy (1934)
ammonia 0.0640 0.1779 5.62 1.44 273-373 1000 32 Wiebe and Tremearne (1934)
methanol 0.2561 0.4677 2.45 0.60 294-413 300 15 Krichevskii et al. (1937)
Average absolute error in K value of hydrogen (see Table I).
Table 111. Prediction of Hydrogen-Coal Oil VLE. Data of Chao (1980)
~~

solubil param,
solvent Tc, K Pc, atm W (cal/cm3)'' 2 Err. KH' Err. K s
tetralin 716.5 33.1 0.316 9.50 3.65 4.86
diphenylmethane 770.2 28.2 0.434 9.60 8.21 5.89
1-methylnaphalene 772.2 35.2 0.302 10.02 5.39 4.37
quinoline 782.0 45.0 0.333 10.90 4.31 4.62
m-cresol 705.9 45.0 0.466 10.78 3.93 2.29
m-xylene 617.0 35.0 0.331 8.82 3.80 3.76
toluene 562.1 48.3 0.212 8.92 4.85 6.42
Average absolute error in K value of hydrogen (see Table I).
Hydrogen-Containing Systems. There is ambiguity O \

about the values of critical constants for components such

as hydrogen and helium since quantum effects are quite 700 8
significant at their critical points. Chueh and Prausnitz u
(1967) have suggested using effective classical critical 600
constants. In this work the true critical constants as listed M odi f i ed R K S z
by Reid et al. (1977)have been used: T,= 33.2 K,P, = Paints Experimental Data

12.8 atm, and w = -0.22.

Figure 2 shows that the agreement with experimental
second and third virial coefficient data is reasonably good,
but more importantly, use of the true critical constants
leads to valuea of the binary parametere that are very close
to zero for binaries with the lower normal alkanes. Actu-
ally all this is nothing less than fortunate coincidence since -
eq 6 was regressed using only substances with positive 1 1 I I 1 I I
k

acentric factors. 20 50 100 200 504 1000 2000

Incidentally, we note that if the hydrogen critical
pressure is changed to 13.55 atm very good agreement is
obtained with PVT data. The average absolute error in
molar volume for 32 experimental data points covering a
temperature range of 223-773 K and pressures up to 400
atm is 0.06% (dataof Deming and Shupe, 1932). However,
this value of P, was not used since it was considered im-
portant to maintain consistency with reported values and
also since the change did not make much difference to the
more important VLE applications.
The binary parameters kbo and kb' were used to regress
the hydrogen binary data. Table I1 shows that good
agreement with data is obtained for a wide variety of
solvents-even highly polar solvents such as water and
methanol.
For many process design applications the solvents are
pseudocomponents generally representing a set of com-
ponents which boil within a narrow temperature range. In
this case binary parameters must be estimated by using
TEMPERATURE, K
Figure 2. Virial coefficienta of hydrogen calculated by modified
Soave equation.
only available quantities. To this end the data of Chao
et al. (1980)have been used to correlate the binary pa-
rameters with the solvent solubility parameter 6.
kbo = 1.061 - 0.8636 (15)
kb' = -2.79 + 0.236 (16)
Table I11 shows that the good agreement with experi-
mental data is retained even when this generalized cor-
relation is used. Further, the results are comparable with
those of the activity coefficient-approach correlation de-
veloped specifically for hydrogen systems by Chao et al.
(1980).
Systems ContainingMethane and Carbon Dioxide.
Recently some VLE data for methane and carbon dioxide
 Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 3, 1983 389
Table IV. Correlation of Methane-Coal Liquid VLE. Data of Chao (1980)
maX kbo fitted
temp range, preso ., no. kbo = -0.02
solvent K atm data kbo EKIa EK, EK, EK, EK, EK,
n-decane 311-583 272 64 -0.002 3.38 5.61 2.96 5.62 7.70 5.63
n-hexadecane 462-704 249 24 -0.003 5.22 4.40 5.02 4.43 7.15 9.25
tetralin 462-665 250 24 -0.003 3.53 4.85 8.70 4.96 4.64 4.89
diphenylmethane 462-703 250 25 -0.016 2.58 5.07 5.43 4.88 3.18 5.12
1-methylnaphthalene 464-704 248 27 -0.022 2.81 8.7 7 7.04 8.88 2.70 8.78
quinoline 46 3-70 3 250 28 t0.002 3.71 7.33 3.72 7.36 9.48 7.68
m-cresol 462-666 2 50 25 -0.017 2.72 3.78 5.92 3.55 3.22 3.83
m-xylene 461-582 199 22 -0.020 4.00 4.47 3.98 4.56 4.04 4.47
benzene 421-501 2 39 18 -0.019 3.47 6.97 3.73 6.84 3.49 6.97
toluene 422-543 2 49 26 -0.026 4.60 5.40 6.17 5.42 4.47 5.40
Average absolute error in K value of methane (see Table I). Low-temperature data of Reamer et al. (1942) also
included.
Table V. Correlation of Carbon Dioxide-Coal Liquid VLE.a Data of Chao (1980)
maX hao fitted hao = 0.13
temp range, press., no.
solvent K atm data kao EK, EK, EK,
n-decane 463-584 51 16 0.138 4.52 4.76 4.17 5.02
n-hexadecane 463-664 50 16 0.133 7.25 8.56 7.11 8.60
tetralin 462 -66 5 51 15 0.178 6.41 1.49 8.53 1.91
diphenylmethane 463-704 50 16 0.123 3.66 3.06 4.19 3.21
1-methylnaphthalene 463-704 50 15 0.144 2.00 6.93 2.88 7.39
quinoline 4 62-7 0 3 50 15 0.043 2.62 2.74 16.55 4.63
m-cresol 463-665 51 14 0.096 4.06 3.36 7.61 3.99
m-xylene 462 -58 3 52 16 0.135 4.04 1.79 3.79 1.77
toluene 393-543 51 21 0.166 3.22 5.10 5.06 5.11
Average absolute error in K value of CO, (see Table I).

Table VI. Correlation of VLE of Binary Systems Containing Water

other temp range, max no.
component kao kbo kbl K press., atm data reference
hydrogen 0 0.5063 -0.8450 273-373 1000.0 20 Wiebe and Gaddy (1934)
nitrogen 0 0.4225 -0.6950 323-513 300.0 18 Saddington and Krase (1934)
methane 0 0.3849 -0.8391 298-444 444.0 42 Culberson and McKetta (1950)
ethane 0 0.3643 -0.9056 311-444 343.0 37 Culberson and McKetta (1951)
oxygen 0 0.4369 -1.0460 273-313 1.o 3 Tokunaga (1975)
methanol -0.0218 0.1494 -0.02474 298-373 3.0 44 Dechema(1977)
ethanol 0.0079 0.1354 -0.0703 313-623 183.0 104 Barr-David (1959)
Dechema (1977)
in solvents representative of coal liquids a t elevated tem-
peratures and pressure have become available (Chao et al., io-zc-Points Dolo of Saddington and
Calculated
KroSe ( 1 9 3 4 )
by m odi f i ed R K S

1980). In this section the present equation is used to 300 olm

correlate their data. 200 otm

Table I V shows the results of the correlation for binary
systems containing methane. The mast effective binary
parameter for the correlation if k$. In general it was found 100oIm

that a value of zero (all binary parameters equal to zero)

works quite well for the normal alkane solvents and a value
of -0.02 gives a good correlation for the heavy aromatic
solvents. An exception to this is quinoline, perhaps be-
cause it contains a nitrogen atom.
Table V shows similar results for the binary systems
containing carbon dioxide. In this case the most effective
binary parameter is .:k A universal value of 0.13 appears
to work quite well for all heavy solvents. Here two solvents
(quinoline and m-cresol) do not follow the common value,
perhaps due to relatively high polarity. A tentative con-
clusion may be made that the binary parameter can be
generalized for groups of substances.
Systems Containing Water. Systems containing water
provide a good test of any model since they generally ex-
hibit significant nonideality. Hence an attempt has been
made to correlate data for these systems. Table VI sum-
marizes the results.
Figure 3 shows the results obtained for the solubility of
nitrogen in liquid water. It is encouraging to note that a
300 400 500 600
T E M P E R A T U R E , 'K
Figure 3. Solubility of nitrogen in liquid water.
binary parameter that is linear in temperature (kboand kb')
can correlate the minimum in solubility shown by exper-
imental data.
Comparisons with experimental VLE data for the eth-
anol-water system are shown in Figure 4. The model
demonstrates good agreement with data over a wide range
of conditions.
Figures 5 and 6 show that the model can correlate dif-
ferent kinds of data with the same parameters. The model
300 Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 3, 1983

62315K
Male Fraction average
Colculoted b y
modified R K S
20000 20000

4- 0000
473 15K
1
5000

3000
2000

Ln
w
IO+
Point5 Experimental Data
Calculated by modlfled R K S
I 1000

5000

3000

. 2 000

1000

5000

10-1

0 02 04 06 08
MOLE FRACTION E T H A N O L
IO
2ooo~

too0
, , , I I:f
02 04 06 08 10
Figure 4. Vapor-liquid equilibrium of the ethanol-water system MOLE FRACTION METHANOL
(data of Barr-David, 1959; and from Dechema, 1977). Figure 6. Henry constant of oxygen in the methanol-water mixed
solvent (binary parameters for oxygen-methanol: k 2 = 0.0527, kbl
5000r = -0,1732).
Poinls Experimental Data ( O e c h e m a i
I - Calculated bymodified R K S
range. Further, good description of binary phase equi-
librium does not guarantee a correspondingly improved
description of multicomponent systems. These issues will
be addressed in future work.
Acknowledgment
The author wishes to express his thanks to Dr, Joseph
F. Boston for helpful discussions. This work was part of
Advanced System for Process Engineering Project (AS-
PEN) supported by the U.S.Department of Energy under
Contract Number E(49-18)-2295.
Nomenclature
a = attraction parameter, eq 1
b = hard core volume, eq 1
c = constant, eq 7
d = constant, eq 7
k = binary parameter, eq 12 and 13
oc m = characteristic constant, eq 5
2
i p = polar parameter, eq 5
P = pressure
lo 02
04 d6 l o
R = gas constant
MOLE FRACTION METHANOL T = absolute temperature, K
Figure 5. Vapor-liquid equilibrium of the methanol-water system. u = molar volume
r = mole fraction
can correlate VLE data for the methanol-water syatem and z = transformed mole fraction, eq 14
the Henry constant for oxygen in the methanol-water Greek Letters
mixed solvent. In the latter case, the model is inadequate a = adimensional factor for a, eq 4
at low methanol concentrations but is in good agreement 6 = solubility parameter, ( c a l / ~ m ~ ) l / ~
with data for the rest of the concentration range. w = acentric factor
Conclusions Subscripts
The results shown in the work demonstrate that a simple c = critical property
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Accepted October 13, 1982

Close Approximations of Global Optima of Process Design Problems

C. Y. Lut and J. Welsman"

Department of Chemiai & Nuclear Engineering, University of Cincinnati, Cincinnati, Ohio 4522 1

Procedures are devised for transforming process optimization problems Into signomlal programming problems. An
investigation of the various algorithms proposed for finding the global optimum of such a signomiai programming
problem showed the Falk algorithm to be most suitable. When the Falk procedure is coupled to an efficient
optimization program, global optima to small size problems are readily obtained. In a moderate size problem,
a close approximation of the global optimum can be obtained with reasonable computing effort.

Introduction
The use of formal optimization or mathematical pro-
gramming procedures has become quite common in process
engineering design. A number of large size, nonlinear,
constrained optimization computer programs are generally
available. Such programs are capable of efficiently solving
problems of the form
max ( m i d f(x) (1)
subject to
g i ( m = bi (i = 1, 2, ..., 1) (24
gi(X){S,ZJbi +
(i = 1 + 1, 1 2, ..., m) (2b)
Nonlinear problems with more than 75 variables and a
similar number of constraints can now be readily handled.
A wide variety of optimal design problems have been
successfully solved by this approach.
Essentially all of the available optimization programs
are hill climbing (descending) techniques. They locate the
constrained mRnimum (or minimum) closest to the starting
point, but they will not necessarily determine the global
maximum (or minimum) if there are multiple extrema.
f Case Western Reserve University, Cleveland, OH 44106.
0196-4305/83/1122-0391$01.50/0
One can be certain that the global optimum has been
obtained only if a maximization problem is a concave
programming problem or a minimization problem is con-
vex. We have a convex programming problem if (a) the
function being minimized, f ( X ) is convex and (b) the
contrainta are only inequalities of the form gi(X)Ibi with
each g i ( X ) also being convex. A concave programming
problem is the maximization of concave objective function
subject to g i ( X )I bi where the g i ( X )are concave. Almost
all practical design problems are neither convex nor con-
cave and one cannot be certain that the global optimum
has been found.
Most designers have been willing to accept the fact that
they may not have located the global optimum providing
the minimum or maximum they have located is consid-
erably better than they would have achieved without the
use of the formal optimization procedure. However, in
many cases the system being designed is very costly and
an expediture of a considerable design effort can be jus-
tified to locate a better optimum. A common procedure
in this case is to repeat the optimization process for a series
of different starting points in the hope that one of the
chosen starting points will be in the vicinity of the global
optimum. This technique is often successful. However,
Wilde (1979) points out that in some real optimization
@ 1983 American Chemlcal Society