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
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
(4Jpure. The pure-component fugacity coefficient can then

CO + 2Hz -
reactions are given by the stoichiometric relationships
CH,OH
be evaluated from generalized compressibility charts or
from an equation of state for the pure compounds. A more

COZ + Hz - CO + HzO
(1)
(2)
rigorous approach is to use a thermodynamic model for
the gas mixture that accounts for the compositional de-
pendence of &.
Conversions of H2, CO, and C 0 2 and the methanol pro- The method chosen for estimating fugacity coefficients
duction can be estimated by solving the two reaction will depend on the desired simplicity of the calculations
equilibrium expressions simultaneously. These expressions and the potential for error associated with using either the
equate the products of vapor-phase fugacities raised to ideal gas mixture or Lewis fugacity rule approximation.
powers corresponding to the stoichiometric coefficients Vonka and Holub (1975) used the Redlich-Kwong equa-
with the equilibrium constants for reactions 1 and 2, Kal tion of state to examine the effect of these approximations
and Ka21 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

Ka2 = [ NCdvH~O
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
(4)
the composition of an equilibrium mixture has its advan-
tages, but unless care is exercised, serious errors can result
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
0.0 10.0 20 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-
l 0
1
30.0 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; (-a)calculated from the
P R 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:

9143.6
K,, = 9.740 X exp 21.225 +- 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
-
+
1 0 - 4 ~ 1.125 x 10-7~2+ -
4g170] (8)
T2
0.0 10.0 20.0 30.0

-
Pressure (MPa)
Figure 3. Kmlfor the reaction CO + 2Hz CH30H: (-) calculated
by using the P R equation of state for the pure components; (-.)
These equations can be used to calculate equilibrium
conversion by first defining X as the moles of CH,OH
formed and Y as the moles of HzOformed and then writing
calculated from the P R equation of state for a mixture that is 10 mol material balances around the methanol reactor:
% CH30H, 6 mol % GO, 79 mol % H,, 4 mol % CO,, and 1 mol %
H20. NCH~O
=H +H
NICH~O X (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
X and Yare the extents of reaction for reactions 1 and 2,
0 ’ respectively. Substitution of eq 7-14 into eq 3 and 4 yields
0.0 10.0 20.0 30.0
two equations in the two unknown extents of reaction, X
Pressure (MPa)
+ - +
Figure 4. K,, for the reaction CO, H z CO HzO: (-) cal-
culated by using the P R equation of state for the pure components;
and Y. These equations can be solved numerically, but
it has been found advantageous to work with the loga-
rithms of both sides of eq 3 and 4. The resulting equations
(-.) 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 used in the calculations are
1 mol % H20.

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,, = 0 (16)

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)
NT
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 SRK(M) tures shows that methanol production and COz conversion
and PR(M), respectively) and for the pure components are less than would be predicted by use of the pure-com-
(designated as SRK(P) and PR(P)). In vapor-liquid ponent fugacity coefficients calculated from these equa-
equilibrium calculations far from critical conditions, Chang tions or from the chart. This is caused by increases in the
(1984) found that the primary effect of the binary SRK correction factors, K,, and K4z,which reduce the equilib-
and P R interaction parameters was to correct for liquid- rium concentrations of methanol and water. As can be
phase nonidealities. For computational convenience, seen in Figures 3 and 4,the differences in both correction
therefore, the interaction parameters in the SRK and PR factors as predicted by the two methods can be as large
equations were assumed to be zero. as an order of magnitude. Conversions of CO, in general,
Examination of Table I shows that essentially identical are not affected significantly because CO is a reactant in
results are obtained for use of the pure-component fugacity the methanol synthesis reaction and a product in the
coefficients from the SRK(P), PR(P), and chart, except water-gas shift reaction; as a result, nonidealities of
for C 0 2 conversions a t 200 and 250 "C and 5 MPa. At methanol and water cancel at most conditions in evaluating
these latter conditions, calculations based on the chart used CO conversion. COz conversions in the cases of SRK(M)
liquid-phase fugacity coefficients of water, and the SRK(P) and PR(M) at nearly every temperature are significantly
and PR(P) used fugacity coefficients of subcooled water less 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%
C02 conversions calculated from the two pure-component from those given by the chart; significant differences in
equations of state differed substantially. Apparently, the C 0 2 conversions and methanol productions also exist be-
SRK(P) equation of state evaluated a fugacity coefficient tween SRK(M) and SRK(P) as well as between PR(M)
for condensed water at these conditions. At a reaction and PR(P) a t these conditions. This, again, can be at-
temperature of 400 "C and pressure of 30 MPa, the con- tributed to the mistaken use of liquid-phase fugacity
version of CO predicted by SRK(P) and PR(P) differed coefficients for methanol and water at these conditions
by more than 10% from the value predicted from the when using the pure-component equations of state. It is
chart. As the pressure increases, differences of this kind clear from Table I 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, C02 conversion 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, 2 7 , 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.; W h y : 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 UNIFAC
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 kij 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.
0196-430518611 125-0481$01.50/0 0 1986 American Chemical Society
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
1 1 f."L
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