SELECTION OF EQUATIONS OF STATE MODELS FOR PROCESS

SIMULATOR

Chorng H. Twu* , John E. Coon, Melinda G. Kusch, and Allan H. Harvey

Simulation Sciences, Inc., 601 South Valencia Avenue, Brea, CA 92621 (USA)
(Workbook meeting 7/26/94; Outline from MGK 7/28/94, Revised form 8/3/94)

INTRODUCTION
There are two traditional classes of thermodynamic models for phase
equilibrium calculations: one is liquid activity coefficient and the other is
equation-of-state models. Activity coefficient models can be used to describe
mixtures of any complexity, but only as a liquid well below its critical
temperature. What is an equation of state ? Any mathematical relation between
volume, pressure, temperature, and composition is called the equation of state
and most forms of the equation of state are of the pressure-explicit type. Many
equations of state have been proposed, but most all of them are essentially
empirical in nature. The virial equation of state has a sound theoretical
foundation and is free of arbitrary assumption. However, the virial equation is
appropriate only for the description of properties of gases at low to moderate
densities. The virial equaions of state are polynomials in density. The simplest
useful polynomial equation of state is cubic, for such an expression is capable
of yielding the ideal gas equation as volume goes to infinite and of representing
both liquid-like and vapor-like molar volumes at low temperatures. This latter
feature is necessary for the application of an equation of state to the calculation
of vapor-liquid equilibria.

A cubic equation of state (CEOS) usually contains 2 or 3 parameters. These

parameters in the CEOS are constrained to satisfy the critical point conditions.
As a result, the cubic equations of state provide an exact duplication of the
critical temperature and critical pressure which is the end point of the vapor
pressure curve. These constraints also lay out a foundation for the alpha (α)

*
Corresponding author

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function (Wilson, 1964, 1966; Soave, 1972). One of the important features in
applying a cubic equation of state is that the α function in the cubic equation of
state can be adjusted to provide an accurate description of the vapor pressure of
any nonpolar and polar components from the triple point to the critical point.
This feature is important because the accurate prediction of pure component
vapor pressures is prerequisite for accurate vapor-liquid calculations.

The success of correlating vapor-liquid equilibrium data using a cubic equation

of state also depends on the mixing rules upon which the accuracy of predicting
mixture properties relies. Cubic equations of state, with the usual van der Waals
one-fluid mixing rule, can be used for the description of phase behavior of
nonpolar and slightly polar systems (i.e., hydrocarbons and inorganic gases).
On the other hand, using asymmetric mixing rules allows cubic equations of
state to be used for a broad range of nonideal mixtures which previously could
only be described by activity coefficient models. Therefore, if a CEOS is
equipped with a flexible α function and an advanced mixing rule, then the CEOS
is applicable to important systems encountered in industry practice.

EQUATION-OF-STATE ADVANTAGES
The equation-of-state has an inherent advantage over the traditional liquid
activity coefficient methods in that it is able to directly handle supercritical
components which do not form liquid (hence, liquid activity coefficients cannnot
be determined and Henry's constants are required), to handle both vapor and
liquid phases in large ranges of temperature and pressure, to adequately handle
high pressure systems, to predict a critical point of mixtures, to properly
calculate K-values near or at the critical point, and to generate all thermodynamic
properties, such as enthalpy, in a consistent way.

SOAVE-REDLICH-KWONG EQUATION OF STATE

The first CEOS that represented both vapor and liquid phases was proposed
by van der Waals (1873) over a century ago. Redlich and Kwong (1949)
proposed the first vdW modification that was used extensively for engineering
calculations for vapor phase properties of mixtures containing nonpolar
components. The equation of state starts gaining popularity in the computation
of equilibrium K-values since Soave modified the Redlich-Kwong cubic

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equation of state (SRK CEOS) in 1972. Wilson (1964) however, was the first to
introduce a general form of the temperature dependence of the "a" parameter in
the Redlich-Kwong equation of state:
RT a
P= − (1)
v −b v ( v + b)

with

a ( T ) = α ( T ) a ( Tc ) (2)

The constants a(T c) and b for SRK CEOS are obtained from the critical
constraints. Wilson later (1966) expressed α(T) as a function of the reduced
temperature, Tr = T/Tc, and the acentric factor ω for the Redlich-Kwong CEOS,
but was not successful. The α(T) function that gained widespread popularity
was proposed by Soave (1972) as an equation of the form:

α =[ 1 + m ( 1 − T r 0.5 ) ] 2 (3)

The m parameter was obtained by forcing the equation to reproduce the vapor
pressure for nonpolar hydrocarbon compounds at Tr = 0.7 and was correlated
as a function of ω for the SRK CEOS:

m = 0.480 + 1.574 ω − 0.175ω 2 (4)

Soave's development of eqns.(3) and (4) represented a significant progress in

the application of a CEOS.

PENG-ROBINSON EQUATION OF STATE

Peng and Robinson (1976) proposed the the following CEOS, which is
slightly different from eqn.(1) in the volume function:
RT a
P= − (5)
v −b v ( v + b) + b( v − b)

The PR CEOS improves the calculation of liquid density for mid-range

hydrocarbons relative to the RK CEOS. For example the liquid density
calculation is better for n-hexane, but worse for methane.

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 Although the Soave's α function is found to be incorrect at high reduced
temperatures as it does not always decrease monotonically with increasing
temperature, the Soave approach was subsequently used in the work by Peng
and Robinson (1976). This helped the Peng-Robinson cubic equation of state
(PR CEOS) to also become one of the most widely used equations of state in
industry for correlating the vapor-liquid equilibria of systems containing
nonpolar and slightly polar components

SRK OR PR CEOS WITH FREE WATER DECANT

METHODOLOGY
Refinery systems often contain both water and hydrocarbons. Mixtures with
water and hydrocarbons will form two liquid phases, one is water-rich phase and
the other is hydrocarbon-rich phase. The free water option is a simplication of
the thermodynamics treatment for water-hydroacrbon systems. For the free
water or decant option, water is considered as forming an immiscible phase with
the hydrocarbon-rich liquid phase The free water option is a convenient,
efficient method to simulate the three phase behavior exhibited by hydrocarbon-
water systems when the solubility of hydrocarbons in the water liquid phase can
be neglected. It is adequate for most hydrocarbon calculations such as refinery
columns with steam stripping and natural gasoline plants. The following
example shows how to use the decant option for refinery columns in the water-
hydrocarbon calculations:

TITLE PROBLEM=DECANT, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1, H2O / 2, H2 / 3, N2 / 4, CO2 / 5,H2S/6, C1 / 7, ETHENE / *
8, C2 / 9, PROPENE / 10, 1BUTENE / 11, BTC2 / 12, IBTE / *
13, 13BD / 14, NC4 / 15, IC4 / 16, NC5
THERMO DATA
METHOD SYSTEM = SRK, SET = SET01, DEFAULT
WATER DECANT = ON

The free water technology is a semi-rigorous three phase (VLLE) calculations.

The vapor is first saturated with water at its vapor pressure. Water is then

4
dissolved in the hydrocarbon liquid up to its solubility limit, and any remaining
water is decanted as a free water phase. The K-value of water in the
hydrocarbon-rich liquid phase can then be computed from water partial
pressure, pw, the solubility of water in the hydrocarbon-rich liquid phase, xw, and
system pressure, P, using the following equation:
pw
Kw = x (6)
wP

The water partial pressure is calculated from either Antoine vapor pressure
equation with coefficients properly stored for different temperature ranges or
Figure 15-14 in the GPSA Data Book (1976).

The GPSA Figure 15-14, which relates the partial pressure of water vapor in
natural gas to temperature and pressure, is recommended for natural gas
mixtures above 2000 psia and Antoine saturated water vapor pressure is proper
for most problems.

The water solubility in the hydrocarbon-rich liquid phase can be computed by

either the method developed by SimSci, Figure 9A1.2 in the API Technical Data
Book (1982), which relates the solubility of water in kerosene to temperature, or
the cubic equation of state.

The K-value of water in the hydrocarbon-rich liquid phase is computed in the

way just mentioned above. On the other hand, the properties of pure water
phase including vapor pressure, enthalpy, entropy and density are predicted
either from saturated condition, which is the default and adequate for most
problems, or from steam table (i.e. the Keenan and Keyes equation of state,
1969). The Keenan and Keyes equation of state is recommended for
superheated water vapor.

The following example indicates that the K-value of water in the hydrocarbon-
rich liquid phase is calculated from GPSA and SimSci methods and the
properties of pure water liquid phase are calculated from the Keenan and Keyes
equation of state :

TITLE PROBLEM=DECANT, USER=SIMSCI

PRINT INPUT=FULL

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COMP DATA
LIBID 1, H2O/2, H2S/3, N2/4, CO2/5, C1/6, C2/7, C3/8, IC4/*
9, NC4/10,IC5/11, NC5/12, NC6
PETRO 13, CUT1,100,715.0,94.44/14, CUT2,164,820.3,204.44/*
15, CUT3,310,921.8,376.66
ASSAY CHAR=SIMSCI
THERMODYNAMIC DATA
METHOD SYSTEM=SRK,SET=SET01,DEFAULT
WATER DECANT=ON,GPSA,SOLUBILITY=SIMSCI,*
PROPERTY=STEAM

Note that all of the SRK and PR equations of state in PRO/II are capable of
predicting three phase behavior, however, not all these equations have the
necessary binary interaction parameters to do the proper split. When the
standard SRK or PR CEOS are selected for three phase calculations, the free
water (decant) option must be deactivated. The example given below shows
how to use SRK CEOS for three-phase (VLLE) calculations:

TITLE PROBLEM=VLLE, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1, H2 / 2, N2 / 3, CO / 4, CO2 / 5, C1 / 6, ETHENE / 7, C2 / *
8, PROPENE / 9, 1BUTENE / 10, BTC2 / 11, IBTE / 12, 13BD / *
13, NC5 / 14, H2O / 15, IC4 / 16, 3BT1 / 17, O2
THERMO DATA
METHOD SYSTEM(VLLE) = SRK, SET = SET01, DEFAULT
WATER DECANT = OFF

SRK CEOS WITH KABADI-DANNER MIXING RULE

Although for most refining and natural gas calculations, the free water option is
adequate to represent water-hydrocarbon phase behavior, however, the free
water phase contains no dissolved hydrocarbons or light gases. When
hydrocarbon or light gas solubility in the water phase is an important
consideration for the problem being analyzed, e.g., an enviromental question, the
free water option is not adequate and a rigorous three phase calculation must be
performed for hydrocarbon-water systems.

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 Kabadi and Danner (1985) proposed a two-parameter mixing rule for the SRK
equation of state. The rigorous three phase calculation can be performed for
hydrocarbon-water systems by using the Soave-Redlich-Kwong-Kabadi-Danner
(SRKKD) equation. The example given below shows how to use SRKKD for
three-phase (VLLE) calculations:

TITLE PROBLEM=SRKKD, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1, H2 / 2, N2 / 3, CO / 4, CO2 / 5, C1 / 6, ETHENE / 7, C2 / *
8, PROPENE / 9, 1BUTENE / 10, BTC2 / 11, IBTE / 12, 13BD / *
13, NC5 / 14, H2O / 15, IC4 / 16, 3BT1 / 17, O2
THERMO DATA
METHOD SYSTEM(VLLE) = SRKKD, SET = SET01, DEFAULT

Note that the SRKKD mixing rule leads to inconsistencies when a component is
split into two or more identical fractions. This method was also found to give
large errors for the aqueous phase.

ALPHA (α) FORMULATION

The accurate prediction of pure component vapor pressures is required for
accurate vapor-liquid calculations and the ability of predicting vapor pressure
from any CEOS is controlled by the selection of an appropriate temperature
dependent α function. In fact, vapor pressures of both nonpolar and polar
components can be very accurately represented by any cubic equation of state if
the temperature dependent α function is sufficiently flexible.

Numerous α functions have been proposed for this purposed. They contain
usually 1 to 3 empirical parameters to be derived from vapor pressures of
individual compounds. Among them, a two-parameter α function proposed by
Twu (1988) and a three-parameter α function proposed by Twu et al.(1991) are
recognized as the most flexible ones with correct extrapolation to high reduced
temperatures. These two α functions, which become SimSci α functions, are:

α = Tr 2 ( M −1) e L ( 1− Tr
2M
) (7)

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α = Tr N ( M −1) e L ( 1− Tr
N M
) (8)

where the integer 2 in eqn.(6) has been replaced by a parameter N to improve

vapor pressure prediction for highly polar substances with high normal boiling
point temperatures, such as glycols. PRO/II allows the user to utilize a choice
of 12 different alpha formulations for SRK, PR, ans vdW cubic equations of
state. To use component-dependent α function in the calculations,
ALPHA=SIMSCI must be specified for SRK or PR CEOS in the input file as
shown below:

TITLE PROBLEM=ALPHA, USER=SIMSCI

PRINT INPUT=FULL
COMPONENT DATA
LIBID 1,NITROGEN/2,CO2/3,METHANE/4,ETHANE/ *
5,PROPANE/6,IBUTANE/7,BUTANE/8,IPENTANE/ *
9,PENTANE/10,HEXANE/11,HEPTANE, BANK=PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK,SET=SET01,DEFAULT
KVALUE ALPHA=SIMSCI, BANK=PROCESS

CLASSICAL QUADRATIC MIXING RULES

The success of correlating vapor-liquid equilibrium data using a cubic equation
of state primarily depends on two things: one is the α function, which is
described in the previous section; the other is the mixing rules upon which the
accuracy of predicting mixture properties relies. The mixing rules originally
proposed for a CEOS are derived from van der Waals one-fluid approximation:

a= ∑ ∑ x x aij i j (9)

where

aij = ( aiaj ) (1 / 2 ) (1 − kij ) (10)

The Kay’s mixing rule was applied to the constant b:

b= ∑xb i i (11)

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 The quadratic mixing rule is the most widely used for equations of state. The
standard method for introducing a binary interaction parameter, kij, into this
classical mixing rule is to correct the assumed geometric mean rule for the "aij"
parameter in the eqn.(10). The cubic equations of state with classical quadratic
mixing rules are capable of accurately representing vapor-liquid equilibria for
non-polar hydrocarbon systems with only one adjustable binary parameter.

The quadratic mixing rule is used for standard SRK and PR cubic equations
of state. The SYSTEM=SRK in previous examples are standard SRK equation
of state.

ADVANCED MIXING RULES

Equations of state with the classical mixing rules are applicable only to the
computation of phase equilibria in mixtures of nonpolar and weakly polar
systems. While this is a good approximation for hydrocarbon mixtures, it
cannot be applied to systems containing strongly polar or associating
components.

Therefore, in the 1970's and 1980's, equations of state were used virtually only
for nonpolar hydrocarbons and slightly polar components. Since the equation-
of-state method does not effectively model strongly polar/polar and/or
polar/nonpolar systems, liquid activity coefficient methods are typically ultilized
for such kind of chemical systems.

Chemical systems consisting of components with varying chemical nature can

exhibit highly non-ideal phase behavior and thus are difficult to predict.
Interactions are strong between different chemical types, and the standard SRK
or PR CEOS do not work well for prediction of such highly non-ideal phase
behavior. For predicting such highly non-ideal systems, the advanced mixing
rules in addition to the advanced α function are required for the equations of
state. Over the past decade, the equations of state have significantly progress in
the development of the most appropriate α functions and advanced asymmetric
mixing rules for systems containing strongly polar components. An appropriate
temperature dependent α function is required to represent accurately the vapor
pressure of pure components and a proper mixing rule is essential to correctly

9
predict vapor-liquid and/or vapor-liquid-liquid phase behavior of highly non-
ideal chemical systems.

The inability of classical quadratic mixing rules to represent the phase behavior
of strongly nonideal mixtures can be explained in terms of infinite dilution
activity coefficients (Twu et al., 1992). The derivation of the infinite dilution
activity coefficients from the equation of state indicates that k12 or k21 is directly
related to the infinite dilution activity coefficients γ 1 ∞ or γ 2 ∞ , respectively. While
it is a good approximation for hydrocarbon mixtures to assume that k12 = k21,
this assumption cannot be applied to highly asymmetric systems containing
strongly polar or associating components.
The failure of classical quadratic mixing rules for strongly nonideal mixtures
can therefore be overcome by using two binary parameters and accurate results
can be obtained for such mixtures when different values of binary parameters are
used for, for example, the water-rich and hydrocarbon-rich phases. The mixing
rule proposed by Kabadi and Danner (1985) is an example of using two binary
parameters, although it is not quite successful in the aqueous phase.

Another particular example of using two binary interaction parameters was

proposed by Panagiotopoulos and Reid (1986). They have proposed modified
classical quadratic mixing rules that use composition-dependent binary
interaction parameters.

aij = ( aiaj ) ( 1 / 2) [(1 − kij ) + ( kij − kji ) x i ] (12)

If kij = kji, the classical quadratic mixing rule is recovered.

The Panagiotopoulos-Reid mixing rule provides an excellent representation of

the phase equilibria of highly non-ideal binary mixtures. Unfortunately, however,
it should not be extended to multicomponent mixtures because it is not invariant
when a component is split into two or more identical fractions (Michesen and
Kistenmacher, 1990).

Because the Panagiotopoulos-Reid mixing rule is very powerful and yet very
simple, and can make use of available binary interaction parameters for SRK
CEOS, SimSci has modified the Panagiotopoulos-Reid mixing rule to reduce the
dilution effect to a minimum for better prediction of phase behavior of

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multicomponent mixtures. This modified Panagiotopoulos-Reid mixing rule is
named as SRKM mixing rule. The SRKM mixing rule is given below:

aij = ( aiaj ) (1 / 2 )[(1 − kij ) + ( k ij − kji )( xi / ( x i + xi )) cij ] (13)

As mentioned previously, typical natural gas processing plants are best

represented with the SRK and PR equations of state. These methods also have
been found to be quite accurate for cryogenic processes such as nitrogen
rejection plants and air separation plants. When accurate calculations are needed
for natural gas mixtures with e.g. methanol and water, the SRKM method is
recommended. The follwoing example shows that the SRKM mixing rule is
applied to natural gas mixtures with methanol and water:

TITLE PROBLEM=SRKM, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1, H2O/2, MEOH/3, N2/4, CO2/5, C1/6, C2/7, C3/ *
8, NC4/9, NC5/10, NC6
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=SRKM, SET=01, DEFAULT,*
L1KEY=10, L2KEY=1
KVALUE BANK=SIMSCI

Although the SRKM mixing rule reduces the dilution effect, the variance
problem still exists. Twu et al. (1991) have proposed a mixing rule not only to
overcome the flaw for multicomponent mixtures as exhibited by the
Panagiotopoulos-Reid mixing rule, but also to reproduce the activity coefficients
in the infinite dilution region as well as to model phase behavior throughout the
finite range of concentration. The mixing rule proposed by Twu et al. (1991)
was called SRKS mixing rule.

SRKS mixing rule and SimSci α function are applied to a highly non-ideal
system in following example. The binary interaction parameters between ethanol
and benzene, which was not found in SIMSCI databank, should be input
through SRKS keyword to improve the calculation results.

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TITLE PROBLEM=SRKS, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBI 1,ETOH/2,BNZN/3,H2O
THERMO DATA
METHOD SYSTEM(VLLE)=SRKS, LIKEY=2, L2KEY=3
KVALUE ALPHA=SIMSCI
SRKS 1, 2, 0.275771, 1.00971, -42.9063, -322.428, *
0, 0, -3.68601, -0.998951

HEXAMER EQUATION OF STATE

Hydrogen fluoride is an important chemical in the chemical industry. It is used
in the HF alkylation process and in the manufacture of refrigerants and other
halogenated compounds. Hydrogen fluoride strongly associated by hydrogen
bonding and strong evidence indicates that the vapor exists primarily as
monomer and hexamer. A monomer-hexamer chemical equilibrium model is
built into the cubic equation of state to account for association of hydrogen
fluoride (Twu et al., 1993). The SRKS mixing rule proposed by Twu et al.
(1991) was used in the hexamer equation of state. PRO/II has a large bank of
binary interaction parameters for hexamer equation of state for HF alkylation
process and manufacture of refrigerants.

Hexamer equation of state provides a new method for calculating the

properties of HF mixtures. The calculated fugacity coefficient, vapor
compressibility factor, heat of vaporization, and enthalpy departure of HF
mixtures exhibit significant deviations from ideal behavior. Failure to take this
chemical association into account can lead to serious errors in vapor-liquid and
vapor-liquid-liquid equilibrium and energy balance calculations.

Alkylation processes and the manufacture of refrigerants simulated by the use

of hexamer equation of state are given by the following two examples:

TITLE PROBLEM=ALKYLATION, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1,HF/2,C3/3,NC4/4,IC4, BANK=PROCESS

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THERMO DATA
METHOD SYSTEM(VLLE)=HEXAMER

TITLE PROBLEM=REFRIGERANT, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1,HF/2,TFETH,,R134A, BANK=SIMSCI
THERMO DATA
METHOD SYSTEM(VLLE)=HEXAMER

BENEDICT-WEBB-RUBIN-STARLING EQUATION OF STATE

Although the cubic equations of state proved to be especially useful in their
simplicity, efficient computation time and reliability in the K-value calculations,
the accuracy of predicting liquid density and liquid enthalpy are not quite high
even for nonpolar hydrocarbons. On the other hand, the non-cubic equation of
state such as the Benedict-Webb-Rubin-Starling (BWRS) equation of state
(Starling, 1973) is capable of representing for both liquid and vapor phases the
density, enthalpy, and entropy, in addition to vapor pressure for hydrocarbons
in the cryogenic liquid region in addition to higher temperature regions.

However, unlike the constants (a and b) of cubic equation of state, which are
constrained to satisfy the critical point conditions, the constants (total is 11) of
Benedict-Webb-Rubin-Starling equation are not satisfied with the critical
contraints. Therefore, the K-value calculations from BWRS for hydrocarbons
near the critical point may not be as reliable as that from CEOS.

The BWRS is quite often employed to calculate K-value, enthalpy, entropy,

and density for hydrocarbon and industrial important gas systems in the
cryogenic liquid region in addition to higher temperature regions. One of the
typical examples is given below:

TITLE PROBLEM=BWRS, USER=SIMSCI

PRINT INPUT=FULL
COMP DATA
LIBID 1,H2/2,ETLN/3,IC4/4,HXE1,BANK=SIMSCI
THERMO DATA

13
 METHOD SYSTEM=BWRS
KVALUE BANK=SIMSCI

In general, the BWRS equation of state is better for representing pure fluid
properties and less attractive for mixtures because it does not offer any
advantages over cubic equations of state in K-value calculations. It may also
require considerably more computing times. The following example applies
BWRS equation of state to pure hydrocarbon for the prediction of properties at
any temperature and pressure:

TITLE PROBLEM=BWRS, USER=SIMSCI

DIME ENGLISH, PRES=PSIG
COMP DATA
LIBID 1,ETLN,BANK=SIMSCI
THERMO DATA
METHOD SYSTEM=BWRS

DATABANK: ALPHA
PRO/II allows the user to utilize a choice of 12 different alpha formulations for
SRK, PR, ans vdW cubic equations of state. SimSci has compiled a data bank
of α parameters for all the components in the SimSci component library using
the α functions given by eqn.(7) and (8) for SRK, PR, and vdW CEOS. The
following is an example showing how to retrieve component-dependent α
parameters from SimSci databank and to input you own α parameters for SRK
CEOS:

TITLE PROJECT=TRAINING, PROBLEM=ALPHA, USER=SIMSCI

PRINT INPUT=FULL
COMPONENT DATA
LIBID 1,NITROGEN/2,CO2/3,METHANE/4,ETHANE/ *
5,PROPANE/6,IBUTANE/7,BUTANE/8,IPENTANE/ *
9,PENTANE/10,HEXANE/11,HEPTANE, BANK=PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK,SET=SET01,DEFAULT
KVALUE ALPHA=SIMSCI, BANK=PROCESS

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 SA06 11,0.340339,0.844963,2.38332

DATABANKS: BINARY INTERACTION PARAMETERS

The data bank of binary interaction parameters is essential in modelling
flowsheet. For hydrocarbon systems, which behave in an orderly fashion, the
Soave-Redlich-Kwong and Peng-Robinson equations of state are the proven
methods for most hydrocarbon applications involving mixtures of non-polar
hydrocarbons and non-hydrocarbon gases (e.g. CO2, H2S, N2, etc.).
However, for these cubic equations of state, the accuracy of the K-value
calculations can often be improved by supplying binary interaction parameters,
(kij, in eqn.10), to tune the classical quadratic mixing rule for the equation of
state.

The binary interaction parameter, kij, are usually obtained from the regression
of PTXY data. PRO/II already contains a large data bank of binary interaction
parameters for SRK, PR, SRKM, and SRKS, equations which fit a wide range
of hydrocarbon applications and in most of cases does not require additional
input binary interaction parameters from the user.

The accuracy of the K-value calculation from BWRS can, as usually, be

improved by supplying binary interaction parameters to the BWRS mixing rules
(Starling, 1973). PRO/II has a data bank of binary interaction parameters
supplied in DECHEMA (1982) for the Benedict-Webb-Rubin-Starling equation.

It is good practice to inspect the reprint of binary interaction parameters and

verify that parameters are present for key binary components which accurate
calculations are needed. The following example shows all the binary interaction
parameters and their sources can be retrieved from SIMSCI databank by using
the INPUT=FULL in the input file:

TITLE PROBLEM=KIJ, USER=SIMSCI

PRINT INPUT=FULL
COMPONENT DATA
LIBI 1, H2/2, H2S/3, NC6/4, BNZN

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THER DATA
METHODS SYSTEM=SRK
KVALUE BANK=SIMSCI

The follwoing reprint from the simulation run indicates that all the binary
interaction parameters but one were found in SIMSCI databank. The
proprietary MW correlation was then used to estimate the binary parameter for
this binary which parameters were not found in the databank.

SRK INTERACTION PARAMETERS

KIJ = A(I,J) + B(I,J)/T + C(I,J)/T**2

I J A(I,J) B(I,J) C(I,J) UNITS FROM

--- --- ---------- ---------- ---------- --------- -------------------
1 2 0.0830 0.00 0.00 DEG K SIMSCI BANK
1 3 -0.0800 0.00 0.00 DEG K SIMSCI BANK
1 4 0.5000 0.00 0.00 DEG K SIMSCI BANK
2 3 0.0680 0.00 0.00 DEG K SIMSCI BANK
2 4 0.0600 0.00 0.00 DEG K MW CORRELATION
3 4 0.0141 0.00 0.00 DEG K SIMSCI BANK

APPLICATION GUIDELINES
We have discussed that the success of correlating vapor-liquid equilibrium
data using a cubic equation of state primarily depends on two things: one is the
α function; the other is the mixing rule. A flexible α function and an advanced
mixing rule allow cubic equation of state to be used for a broad range of
nonideal mixtures which previously could only be described by activity
coefficient models. Having these two elements, the key application guideline of
a CEOS primarily depends upon the availability of binary interaction parameters
for the system.

Soave-Redlich-Kwong and Peng-Robinson equations of state are

recommended for most hydrocarbon applications involving mixtures of non-
polar hydrocarbons and inorganic gases such as H2S, CO2, H2, etc.

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 BWRS is an excellent equation of state for predicting properties of pure
hydrocarbons and gases at any temperature and pressure and is suitable for the
application to non-polar hydrocarbon and industrial gas mixtures.

The SRK-Kabadi-Danner mixing rule is composition dependent. It was

developed specifically for water and well-defined light hydrocarbon systems.
Although SRKKD is recommended in API Technical Data Book (1982) for
water and light hydrocarbons mixtures, the calculated results may not be reliable
due to the inconsistency problem in its mixing rule.

SRKM is recommended for polar/polar and/or polar/nonpolar systems which

the standard SRK or PR equation of state cannot handle. SRKM is reduced to
the standard SRK CEOS for nonpolar mixtures (e.g. hydrocarbons and
inorganic gases).

SRKS is recommended for HF alkylation process and the manufacture of

refrigerants and other halogenated compounds. SRKS is also suitable for
polar/polar and/or polar/nonpolar systems. The success of applying either
SRKM or SRKS equation of state to nonideal systems is to verify that
parameters are present for key binary components.

REFERENCES
API Technical Data Book-Petroleum Refining, American Petroleum Inst., New
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