Ind. Eng. Chem. Process Des. Dev.

1986, 25,477-481 477

Methanol Synthesis Reactions: Calculations of

Equilibrium Conversions Using Equations of State
Te Chang,+ Ronald W. Rousseau," and Peter K. Kllpatrlck
Department of Chemical Engineering, North Carolina State University, Raleigh, North Carolina 27695-7905

Potential errors associated with the estimation of vapor-phase fugacity coefficients are illustrated for the constituents in
methanol synthesis reactions. Corrections to the equilibrium constants of reactions producing methanol from
CO and from COP were estimated (a) from pure-component fugacity coefficients determined from either a gen-
eralized chart or from the Soave-Redlich-Kwong (SRK) and Peng-Robinson (PR) equations of state and (b) from fugacity
coefficients determined from SRK and PR equations of state for mixtures of species in the methanol reactor.
Comparisons of the estimation procedures were made by examining conversions of CO and CO, and vol
% methanol in the effluent from the synthesis reactor. Significant differences among the methods used to
calculate the conversion of COPand production of methanol were noted. These differences were most
significant at conditions often found in low-pressure methanol synthesis reactors.

Conventional methanol production uses a feed stock of
reformed methane that contains hydrogen, carbon mon-
oxide, and carbon dioxide in a ratio of NHz/(2Nco + 3Nc0z)
close to the stoichiometric ratio of unity. Both the re-
versible methanol synthesis reaction (shown as eq 1)and
the water-gas shift reaction (shown as eq 2) occur in the
vapor phase and proceed to appreciable extents. The
reactions are given by the stoichiometric relationships
CO + 2Hz - CH,OH
COZ + Hz - CO + HzO
Conversions of H2, CO, and C02 and the methanol pro-
duction can be estimated by solving the two reaction
equilibrium expressions simultaneously. These expressions
equate the products of vapor -phase fugacities raised to
powers corresponding to the stoichiometric coefficients
with the equilibrium constants for reactions 1 and 2, Kal
and Ka21
NCdvH~O
Ka2 = [ NCOzNHz ]K4z
where Ni is the number of moles of component i in the
mixture, NT is the total number of moles of the mixture,
and K,, and K$z are correction factors defined in terms
of the vapor-phase fugacity coefficients of i, @i:
These correction factors account for the deviation of the
system from ideal gas behavior, and Smith and Missen
(1982) discuss the various ways by which they can be es-
t Present address: ARC0 Chemical Co., Newtown Square,
PA 19703.
* To whom correspondence should be addressed.
0196-4305/86/1125-0477$01.50/00 1986 American Chemical Society
timated. If the gas mixture is assumed to behave ideally,
then the fugacity coefficients are all unity, but it is clear
that such an approximation is incorrect in systems that
are at elevated pressure and/or include polar components.
A second commonly used approximation is to assume ap-
plicability of the Lewis fugacity rule, which equates & to
(4JpureThe. pure-component fugacity coefficient can then
be evaluated from generalized compressibility charts or
(1)
from an equation of state for the pure compounds. A more
rigorous approach is to use a thermodynamic model for
(2) the gas mixture that accounts for the compositional de-
pendence of &.
The method chosen for estimating fugacity coefficients
will depend on the desired simplicity of the calculations
and the potential for error associated with using either the
ideal gas mixture or Lewis fugacity rule approximation.
Vonka and Holub (1975) used the Redlich-Kwong equa-
tion of state to examine the effect of these approximations
on calculated equilibrium compositions for the water-gas
shift reaction, the addition of ammonia to ethylene, and
the formation of ethanediol and diethyl sulfide from eth-
(3) anol, hydrogen, and sulfur. Each of the methods for es-
timating the fugacity coefficients for use in determining
the composition of an equilibrium mixture has its advan-
tages, but unless care is exercised, serious errors can result
(4) through misapplication of the simplified calculations.
At a chosen operating condition, such as a temperature
between 200 and 300 "C,and a pressure between 5 and 35
MPa, the vapor-phase fugacity coefficients for pure water
and pure methanol cannot be found in a generalized chart
(Hougen et al., 1964) or calculated from the equation of
state because these two pure components do not exist as
stable vapor at these conditions. The estimation of fu-
(5) gacity with either of these procedures gives values for the
pure liquids; mistakenly using these values in place of the
fugacity coefficients of pure-component vapors can lead
to significant errors in the estimation of methanol pro-
duction. Specifically, the vapor-phase fugacity coefficients
should be those in a vapor mixture at the equilibrium
composition. Such vapor-phase fugacity coefficients are
functions of temperature, pressure, and composition (in-
cluding inert species in the system), and they can be
evaluated only from a thermodynamic description of the
compositional dependence of nonidealities.
In this paper, equilibrium correction factors for the
methanol synthesis and water-gas shift reactions are cal-
478 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2. 1986
c
.'.... .... .......,. ,,, ,
0 l
00.0 20 0
10.0 30.0
Pressure (MPa)
Figure 1. Fugacity coefficients for methanol: (-) calculated from the
P R equation of state for the pure compound; (-) calculated from the P
R equation of state for a mixture that is 10 mol % CH30H,6 mol %
CO, 79 mol % H,, 4 mol % CO,, and 1 mol % HzO.
culated, and comparisons are made between values of these
factors calculated from mixture fugacity coefficients and
from pure-component fugacity coefficients. The Soave-
Redlich-Kwong, referred to as SRK (Soave, 1972;
Graboski and Daubert, 1978), and Peng-Robinson, referred
to as PR (1976), equations have been used in both mixture
and pure-component cases to evaluate vapor-phase fugacity
coefficients in the reaction equilibrium calculations. The
mixing rules prescribed by Soave (1972) and by Peng and
Ftobinson (1976) for the equation of state parameters a and
b have been used in this paper. Expressions for the fu-gacity
coefficient as a function of temperature, pressure, and
composition can be found in the two references. Results of
these calculations are compared with each other and with the
results calculated by Wade et al. (1981). Conditions used in
the present calculations are typical of those found in methanol
synthesis reactors. Moreover, the approach to be described has
been used successfully in the analysis of a commercial
methanol synthesis plant, but the details of the facility and
comparisons with data from the plant are proprietary.
Vapor-Phase Fugacity Coefficients
Fugacity coefficients are a measure of the deviation from
ideal gas behavior, and these quantities can be estimated
from an exact thermodynamic relationship using an
equation of state. Mixtures found in methanol synthesis
reactions include CO, Ha, COS, H20, and CH30H. The
components CO, H2, and COz exhibit nearly ideal behavior
because the reaction temperature, 200-400 "C, is much
higher than the respective pure-component critical tem-
peratures. As a consequence, there is little variation in the
values of the vapor- phase fugacity coefficients of these
components with the method of estimation. Methanol and
water vapors, on the other hand, are highly nonideal at the
indicated reaction temperatures, and the method used to
estimate the fugacity coefficients of these compounds is
important. As described earlier, fugacity coefficients of
methanol and water in a reaction mixture will differ from
the pure-component fugacity coefficients; the accuracy in
predictions of mixture fugacity coefficients will vary from
one equation of state to another, especially since the system
contains polar compounds. Tarakad et al. (1979) give a
good comparison of the use of equations of state in
predicting vapor-phase fugacity coefficients.
Figures 1 and 2 show fugacity coefficients of methanol
and water, respectively, that were calculated as functions of
temperature and pressure from the PR equation of state.
The solid curves represent fugacity coefficients of the pure
component; the curved segments below and to the right of
the discontinuity in the slope represent fugacity coef-
1
0
0.0 10.0 20.0 30.0
Pressure (MPa)
Figure 2. Fugacity Coefficients for water: (-) calculated from the PR
equation of state for the pure compound; calculated from the P R
(-a)
equation of state for a mixture that is 10 mol % CH,OH, 6 mol
% CO, 79 mol % Hz, 4 mol % COP,and 1 mol % H,O.
ficients of the pure liquids. These liquid-phase fugacity
coefficients correspond to those given in the generalized
fugacity coefficient chart at these conditions based on the
theory of corresponding states (Hougen et al., 1964).
However, they are often mistakenly read as vapor- phase
fugacity coefficients. The point of discontinuity in slope,
where the plot of vapor-phase fugacity coefficients inter-
sects the plot of liquid-phase fugacity coefficients, repre-
sents the saturation conditions for the pure component. The
extensions of both liquid and vapor segments of the curve
through the discontinuity represent fugacity coef-ficients of
metastable superheated liquid and subcooled vapor. The
dotted curves in Figures 1 and 2 represent vapor-phase
fugacity coefficients of methanol and water, respectively,
in a mixture that is 10 mol % CH,OH, 6 mol
% CO, 79 mol % H2,4 mol % COz, and 1 mol % H20,a
composition in the range of that found in methanol syn-
thesis reactions.
Methanol and water in a vapor-phase mixture rich in
H2, COz, and CO behave more like ideal gases than they
do in the pure vapor states. As a result, there are signif-
icant differences between correction factors for reaction
equilibrium constants calculated from pure-component
fugacity coefficients and those based on fugacity coeffi-
cients calculated from mixture properties. These differ-
ences become more significant as the concentrations of
methanol and water increase. Furthermore, when these
concentrations become sufficiently high, at a fixed tem-
perature and pressure, the mixture reaches a dew point and
condensation of the vapor begins. This vapor is unstable
globally at a pressure higher than the dew point, and
calculation of vapor-phase fugacity coefficients of
methanol and water in that mixture will give a fugacity
coefficient for either a supersaturated, metastable vapor-
phase or a liquid-phase solution. This can be seen easily for
a pure compound. As a result, care must be used in
identifying the state of the component for which the fu-
gacity coefficient is calculated.
Correction Factors for Methanol Synthesis
Reactions
The correction factor for a gas-phase reaction equilib-
rium is a ratio of vapor-phase hgacity coefficients of
products to that of reactants, each of which is raised to a
power corresponding to the respective stoichiometric
coefficients. Figures 3 and 4 give values of K,l and K$z
that have been calculated by using vapor-phase fugacity
coefficients determined from the PR equation for mixtures
as well as for pure compounds. These two figures are quite
similar to Figures 1 and 2, respectively, because the dom-
inant contributions to these correction factors are the fu-
 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
479

Bissett (1977) and by Cherednichenko (1953), respectively:

K,, = 9.740 X exp 21.225
+ 9143.6
--
T

7.492 In T + 4.076 X 10-3T - 7.161 X lO-*T2 1 (7)

13.148 - -5639*5- 1.077 In T - 5.44 X
T
-
0.0 10.0 20.0 30.0
10-4~ + 1.125 x 10-7~2+ -4g170] (8)
Pressure (MPa) - T2
Figure 3. Kmlfor the reaction CO + 2Hz CH30H: (-) calculated by These equations can be used to calculate equilibrium
using the P R equation of state for the pure components; (-.) conversion by first defining X as the moles of CH,OH
calculated from the P R equation of state for a mixture that is 10 mol formed and Y as the moles of HzO formed and then
% CH30H, 6 mol % GO, 79 mol % H,, 4 mol % CO,, and 1 mol %
H20. writing material balances around the methanol reactor:
N C H ~ O= HN I C H ~ O+ HX (9)
Nco = NIco - X +Y (10)
NH, = NIH, - 2X - Y (11)

\ NH20 = NIH,O + (13)

NT = NIT - 2X (14)
where NI, is the initial number of moles of component i,
NIT is the number of total moles of the initial mixture, and
0 ’ X and Yare the extents of reaction for reactions 1 and 2,
0.0 10.0 20.0- 30.0 respectively. Substitution of eq 7-14 into eq 3 and 4
Pressure (MPa)
yields two equations in the two unknown extents of
Figure 4. K,, for the reaction CO, + H z CO + HzO: (-) cal- reaction, X and Y. These equations can be solved
culated by using the P R equation of state for the pure components; (- numerically, but it has been found advantageous to work
.) calculated from the P R equation of state for a mixture that is 10 mol
% CH,OH, 6 mol % CO, 79 mol % H,,4 mol % COP, and 1 mol % with the loga-rithms of both sides of eq 3 and 4. The
H20 . resulting equations used in the calculations are
gacity coefficients of methanol and water. The solid curves
are correction factors calculated by using the vapor -phase
fugacity coefficients for pure compounds; curves to the
right and below the discontinuity in slope were determined
by using the liquid-phase fugacity coefficients for methanol
and water. The extensions of the vapor and liquid portions
F 2 ( X , Y )= In K,, - In (22;) -In K,,
(16)
=0

of the curves past the discontinuities in slope represent

correction factors calculated from fugacity coefficients for
metastable methanol and water. The dotted curves rep-
resent correction factors calculated from fugacity coeffi-
cients obtained from the mixture equation of state. For
reaction 2, there are sharp differences between the cor-
rection factors calculated from the two procedures when the
temperature is between 200 and 300 O C and at a pressure
higher than 5 MPa. For reaction 1, these dif-ferences are
significant at 200 “C and pressures higher than 10 MPa.
This is because the pure -component fugacity coefficients for
methanol and water are those for liquids.
When the correction factors K,, and K,, are expressed as
functions of temperature, pressure, and composition, they
can be estimated accurately. More importantly, these
correction factors lead to a correct determination of the
composition of the reaction mixture a t equilibrium. The
equations used in these calculations provide the basis for a
more complete model of a methanol synthesis process that
can be used to optimize reaction conditions.
Equilibrium Calculations for Methanol Synthesis
Reactions
The equilibrium constants, K,, and Kaz,were deter-
mined to be functions of temperature (T in kelvin) by
where K,, and K,, can be estimated in two ways: first, through
estimations of pure-component fugacity coeffi-cients and
application of the Lewis fugacity rule, and second, from an
equation of state for the reaction mixture. The former
procedure has only temperature and pressure as variables,
while the latter adds composition as a variable.
Table I summarizes the results of example calculations
for a typical feed composition of 15 mol 70CO, 8 mol 7’0
CO,,74 mol % HP,and 3 mol 70CH4. Methane is included
in the total number of moles of the mixture, NT and
NIT, as an inert component. The percent conversion of
CO and CO, and the percentage of the exit stream that is
methanol are calculated by the equations
% co conversion = X-’ x 100% (17)
NICO
% CO, conversion = -x 100% (18)
NICO,
X
vol % of exit CH,OH = - X 100% (19)
N T
The results calculated by Wade et al. (1981) are used as a
base case for each temperature and pressure examined and
are indicated in Table I as “chart” values. Table I also
480 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986

Table I. Eauilibrium Conversions and Exit CH-OH Concentration"

CO conversion (%) C 0 2 conversion (%) exit CH,OH (vol %)
source 5MPa 10MPa 30MPa 5MPa 10MPa 30MPa 5MPa 10MPa 30MPa

200 "C
chartb 95.6 99.0 99.9 44.1 82.5 99.0 27.8 37.6 42.3
SRK(P)' 96.3 99.0 99.9 28.W 83.0 99.5 25.1 37.7 42.4
PR(P)d 96.3 99.0 99.9 29.09 83.5 99.5 25.2 37.8 42.4
SRK(M)e 96.0 99.0 25.98 58.54 24.6 32.19
PR(M)f 96.0 99.0 26.54 59.79 24.7 32.39
250 "C
chartb 72.1 90.9 98.9 18.0 46.2 91.0 16.2 26.5 39.7
SRK(P)c 73.0 90.6 99.0 14.49 45.1 92.4 16.0 26.2 40.0
PR(P)d 73.0 91.4 98.9 14.78 37.78 92.9 16.0 25.1 40.2
SRK(M)' 71.2 90.6 99.5 12.88 29.39 89.1 15.3 23.49 39.4
PR(M)f 71.2 90.6 99.4 13.28 30.P 89.7 15.3 23.69 39.6
300 "C
chartb 25.7 60.6 92.8 14.3 24.6 71.1 5.6 14.2 32.2
SRK(P)' 25.4 60.7 92.8 14.1 22.3 71.0 5.5 13.9 32.2
PR(P)d 25.4 60.6 92.6 14.4 22.9 72.4 5.5 14.0 32.4
SRK(MIP 23.5 57.3 93.8 12.8g 18.79 58.19 5.09 12.69 29.9
PR(M)f 23.6 57.3 93.7 13.2 19.59 60.49 5.09 12.89 30.3
350 "C
chartb -2.3 16.9 73.0 19.8 23.6 52.1 1.3 4.8 21.7
SRK(P)' -2.3 16.7 71.9 19.8 23.1 50.0 1.3 4.8 21.0
PR(P)d -2.4 16.6 71.4 20.1 23.7 51.8 1.3 4.8 21.1
SRK (M)e -2.3 14.79 70.7 18.5 20.29 36.79 1.2 4.19 18.69
PR(M)f -2.5 14.68 70.4 18.9 21.09 39.39 1.2 4.29 1a.v
400 "C
chartb -12.8 -7.2 38.1 27.9 30.1 44.2 0.3 1.4 11.4
SRK(P)' -12.8 -7.3 34.19 27.7 29.3 41.0 0.3 1.3 10.1
PR(P)d -12.9 -7.6 33.49 28.1 30.0 42.9 0.3 1.3 10.1
SRK(M)' -12.3 -6.9 30.54 26.5 26.79 31.Y 0.3 1.19 8.39
PR(M)f -12.5 -7.3 30.29 26.9 27.6 34.09 0.3 1.18 8.58
nFeed composition: 15% CO, 870 COz, 74% H2,and 3% CHI. 'Wade et al. (1981) from Hougen et al. (1964). 'Component fugacity
coefficients calculated from the SRK equation of state for pure substance. Component fugacity coefficients calculated from the P R equation of
state for pure substance. 'Component fugacity coefficients calculated from the SRK equation of state for the mixture at eauilibrium comDosition. f
ComDonent fuaacitv coefficients calculated from the PR equation of state for the mixture at equilibrium com-position. 9Diference between v k u e
and &art is greater than 10%
lists the results that use correction factors calculated by would be expected to become more severe.
using the fugacity coefficients from the SRK and PR The use of the SRK or PR equations for the gas mix-
equations of state for the mixture (designated as tures shows that methanol production and COz conversion
SRK(M) and PR(M), respectively) and for the pure are less than would be predicted by use of the pure -com-
components (designated as SRK(P) and PR(P)). In ponent fugacity coefficients calculated from these equa-
vapor- liquid equilibrium calculations far from critical tions or from the chart. This is caused by increases in the
conditions, Chang (1984) found that the primary effect of correction factors, K,, and K4z,which reduce the equilib-
the binary SRK and P R interaction parameters was to rium concentrations of methanol and water. As can be seen
correct for liquid-phase nonidealities. For computational in Figures 3 and 4,the differences in both correction
convenience, therefore, the interaction parameters in the factors as predicted by the two methods can be as large as
SRK and PR equations were assumed to be zero. an order of magnitude. Conversions of CO, in general, are
Examination of Table I shows that essentially identical not affected significantly because CO is a reactant in the
results are obtained for use of the pure-component fugacity methanol synthesis reaction and a product in the water-gas
coefficients from the SRK(P), PR(P), and chart, except for shift reaction; as a result, nonidealities of methanol and
C 0 2 conversions a t 200 and 250 "C and 5 MPa. At these water cancel at most conditions in evaluating CO
latter conditions, calculations based on the chart used conversion. COz conversions in the cases of SRK(M) and
liquid-phase fugacity coefficients of water, and the SRK(P) PR(M) at nearly every temperature are significantly less
and PR(P) used fugacity coefficients of subcooled water than those predicted with the use of chart values. The
vapor in a metastable state. As a result, the chart gives discrepancies result because liquid -phase fugacity coef-
predictions significantly in error, while the SRK(P) and ficients of pure methanol and pure water are given erro-
PR(P) predictions are much closer to the presumed correct neously by the chart at these conditions.
results given by the mixture equations of state. An in- Exit CH30H percentages in the cases of SRK(M) and
teresting result was obtained at 250 OC and 10 MPa, where PR(M) at every temperature differ by more than 10% from
C02conversions calculated from the two pure-component those given by the chart; significant differences in C 0
equations of state differed substantially. Apparently, the 2conversions and methanol productions also exist be-tween
SRK(P) equation of state evaluated a fugacity coefficient SRK(M) and SRK(P) as well as between PR(M) and PR(P)
for condensed water at these conditions. At a reaction a t these conditions. This, again, can be at-tributed to the
temperature of 400 "C and pressure of 30 MPa, the con- mistaken use of liquid-phase fugacity coefficients for
version of CO predicted by SRK(P) and PR(P) differed by methanol and water at these conditions when using the
more than 10% from the value predicted from the chart. As pure-component equations of state. It is clear from Table I
the pressure increases, differences of this kind that as total pressure is increased and
 Ind. Eng. Chem. Process Des. Dev. 1986,25, 481-486 481

temperature decreased, the production of methanol in-
creases. However, at sufficiently low temperatures or
high pressures, supersaturation and subsequent
condensation of liquid a t the equilibrium mixture
composition is pos-sible. There is thus a limit to
maximizing methanol pro-duction through the decrease
in temperature or increase in pressure. Moreover, the
equilibrium conversion cannot be predicted accurately
unless the equation of state cor-rectly models the
mixture liquid-vapor equilibria. In our computations, we
found that the cases of SRK(M) and PR(M) a t 200 "C
and 30 MPa did not converge. We at-tribute this to
liquid-phase condensation at these condi-tions.
Conclusions
With methanol synthesis reactions, C02conversion and
methanol production are always overestimated by using
correction factors calculated from pure-component fugacity
coefficients obtained from a generalized chart. Significant
errors in the estimation of C 0 2 conversion and CH,OH
formation are produced by mistakenly using the liquid-
phase fugacity coefficients as vapor-phase fugacity coef-
ficients for subcritical compounds. This mistake often has a
large effect on calculations involving methanol synthesis
reactions at temperatures from 200 to 300 "C and pressures
from 5 to 10 MPa. For accurate estimation, these calcu-
lations require the use of fugacity coefficients that depend
on composition to estimate the nonidealities of the coex-
isting species in a reaction mixture. This work shows that
either the Peng-Robinson or the Soave-Redlich-Kwong
equation of state can be used profitably for this purpose.
Nomenclature
K,i = equilibrium correction factor for reaction i
Kai = equilibrium constant for reaction i
Ni= moles of component i at equilibrium
NT = total moles of mixture at equilibrium
NIL= initial moles of component i in mixture
NIT = total moles of initial mixture
X = extent of reaction 1
Y = extent of reaction 2
q$ = vapor-phase fugacity coefficient of i
Registry No. CH,OH, 67-56-1;CO, 630-08-0;COP,124-38-9.
Literature Cited
Bissett, L. Chem. Eng. 1977, 84(21), 155.
Chang, T. Ph.D. Thesis, North Carolina State University, Raleigh, 1984.
Cherednichenko, V. M., Dissertation, Karpova, Physic0 Chemical Institute,
Moscow, U.S.S.R., 1953.
Graboski, M. S.; Daubert, T. E. Ind. Eng. Chem. Process Des. Dev. 1978,
17, 443.
Hougen, 0. A.; Watson, K. M.; Ragatz, R. A. "Chemical Process Principles",
3rd ed.; Wiley: New York, 1964.
Peng, D.-Y.; Robinson, D. 8. Ind. Eng. Chem. Fundam. 1976, 15, 59. Smith,
W. R.: Missen, R. W. "Chemical Reaction Equilibrium Analysis: Theory
and Algorithms"; Wiley: New York, 1982.
Soave, G. Chem. Eng. Sci. 1972, 27, 1197.
Tarakad, R. R.; Spencer, C. F.; Adler, S. B. Ind. Eng. Chem. Process Des.
Dev. 1979, 18, 726.
Vonka, P.; Holub, R. Collect. Czech. Chem. Commun. 1975, 4 0 , 931.
Wade, L. E.; Gengelbach, R. B.; Taumbley, J. L.; Hallhauer, W. L. "Kirk-0th-
mer Encyclopedia of Chemical Technology", 3rd ed.; Why: New York,
1981; Vol. 15, pp 398-415.
Received f o r review November 26, 1984
Accepted August 14, 1985

Prediction of Low-Pressure Vapor-Liquid Equilibria of

Nan-Hydrocarbon-Containing Systems-ASOG or UN IFAC
Parag A. Gupte and Thomas E. Daubert'
Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802

An extensive comparison of the two group-contribution methods for activity coefficients-UNIFAC and ASOG-is
presented. The methods are compared by carrying out bubble point and K-value calculations over a large low-
pressure VLE data base. Overall, the two methods yield equivalent results when the methods are compared
for various families of systems. However, for certain families, one method may be superior to the other.
Prediction results from Raoult's law are also obtained and compared with the more complex models.

Prediction of vapor-liquid equilibria is important for
design calculations in the chemical industry. Vapor-
liquid equilibria of hydrocarbon-containing systems are
com-monly predicted by using equations of state. In
such cases, the binary interaction parameters ki j are
either taken as zero or generalized in terms of readily
available input parameters like the critical properties.
This type of ap-proach yields consistent results for
nonpolar systems and for systems where the components
are chemically similar. The advantage of this approach is
that it can be extended to high pressures.
When the system contains non-hydrocarbon compounds
and when the components are chemically dissimilar (e.g.,
hydrocarbon-alcohol systems), the equation of state ap-
proach is not applicable. In such cases, the use of zero
* To whom correspondence should be addressed.
01 96-43051861 125-0481$01.50/0 0 1986
interaction constants leads to poor results. Furthermore,
interaction constants are not easily generalizable in
terms of simple molecular properties. In such cases, the
alter-native approach is to use GE models for the liquid
phase. At low pressures (less than 5 bar), the liquid-phase
fugacity is conveniently represented by using activity
coefficients. For subcritical components, this relation is
f , L = y. x f . "L
1 1 1 (1)
The activity coefficient yi is related to the excess Gibbs
energy of the system by the following well-known relation.
n
gE = RT Ex, In yI (2)
i=l
Several models for gE are available in the literature. The
more popular models are UNIQUAC (Abrams and
Prausnitz, 1975), NRTL (Renon and Prausnitz, 1968), and
American Chemical Society