SELECTION GUIDE FOR EQUATION OF STATE OR ACTIVITY MODEL DEFINITION

Liquid activity coefficient methods for phase equilibrium calculations are fundamentally different from the equation-of-state (EOS) methods. Whereas the EOS methods are
based on liquid and vapor fugacity coefficients referenced to the ideal gas state, the liquid activity methods use the pure liquid at the mixture temperature and pressure as
the reference state for each component in the liquid phase. The liquid activity coefficient method is useful for systems comprised of components of similar
volatility with highly non-ideal liquid behavior. However, the method meshes very poorly near the mixture critical point and an equation of state method must be used
under these conditions.

Part. Tipo Nombre Aplicación Observaciones

This equation has been found to give accurate predictions for non-polar mixtures of
1 EOS Soave-Redlich-Kwong (SRK) hydrocarbons. It does not give accurate predictions for polar components. PRO/II Density by API method
contains correlations for 's for systems with hydrocarbons and N2, H2S and CO2.
Is a modification that improve the prediction of vapor-liquid-liquid phase equilibria for
hydrocarbon systems with water. Natural gas systems at high pressures which
SRK-Kabadi-Danner (SRKKD)
2 EOS contain water. Hydrocarbon systems with water where prediction of the Density by API method
hydrocarbons dissolved in the water is important. This method is poor at
predicting the solubility of hydrogen in the aqueous phase.
Is a modification that improve the predicted phase behavior of strongly non-ideal
3 EOS SRK-Huron-Vidal (SRKH) Density by API method
mixtures.
Two adjustable interaction parameters are used, kij and kji. This significantly improves
SRK-Panagiotopoulos-Reid
the accuracy of predictions for mixtures of polar and non-polar components. Specific
4 EOS (SRKP) Density by API method
systems of polar compounds for which the Panagiotopoulos-Reid parameters are
available or can be determined by regressing experimental data.

For polar-nonpolar systems, where the nonideality is large or strongly

asymmetric. Three phase separators for water-hydrocarbon systems, such as
SRK-Modified Panagiotopoulos-
those found in FCC gas plants and hydrocrackers. Lube oil and solvent dewaxing
5 EOS Reid (SRKM) Density by API method
units. Natural gas systems containing polar compounds such as methanol. Any
chemicals operation for which the parameters are supplied by PRO/II or may be
determined by regression.
Four adjustable parameters are used, with the mixing rule designed to produce good
SRK-SimSci (SRKS)
6 EOS results for mixtures of polar and nonpolar compounds. Application is same as those Density by API method
for SRK-Modified Panagiotopoulos-Reid (SRKM).
it is used for HF alkylation processes and for refrigerant synthesis. HF alkylation
SRK-Hexamer
7 EOS columns in which HF is present such as the deisobutanizer, depropanizer and HF
stripper.
All light hydrocarbon processes such as natural gas processing and light ends
8 EOS Peng-Robinson (PR) Density by API method
processing in refinery gas plants.
It´s designed to improve the predicted phase behavior of strongly non-ideal mixtures.
PR-Huron-Vidal
9 EOS Specific systems for which the Huron-Vidal parameters are available or can be Density by API method
(PRH)
determined by regressing experimental data.
It significantly improves the accuracy of predictions for mixtures of polar and non-polar
PR-Panagiotopoulos-Reid
10 EOS components. Panagiotopoulos-Reid parameters for specific systems of polar Density by API method
(PRP)
compounds are available, or may be determined by regressing experimental data.
 For polar-nonpolar systems , where the nonideality is large or strongly asymmetric.
PR-Modified-Panagiotopoulos- Three phase separators for water-hydrocarbon systems, such as those found in FCC
11 EOS Reid (PRM) gas plants and hydrocrackers. Lube oil and solvent de-waxing units. Natural gas Density by API method
systems containing polar compounds such as methanol. Any chemicals operation for
which the parameters are supplied by PRO/II or may be determined by regression.
The BWR equation was modified by Starling in 1973 to improve the accuracy for light
Benedict-Webb-Rubin-Starling
12 EOS hydrocarbons in cryogenic liquid, gas and dense fluid regions and also at high
(BWRS)
temperatures. Light hydrocarbon systems at less than critical conditions.
Non-ionic chemicals systems at high pressures for which interaction data are not
13 EOS Uniwaals (UNIWAALS) available. Also recommended for chemicals systems in which more than 5 mole Density by API method
percent of supercritical gases are present.
Excellent representation of vapor-liquid equilibria can be made. The prediction of
equilibria at low densities is reasonable, and the EOS can be expected to yield better
14 EOS Twu-Bluck-Coon
results at higher pressures, because the mixing rules have been derived at the zero
pressure limit of the excess Gibbs free energy.

The resulting equation correlates the liquid activity coefficient for each binary in terms
of three parameters. The expressions for the parameters may be expanded to
15 AM Non-Random Two-Liquid (NRTL) incorporate temperature dependence. Depending on the expressions used for the
parameters, the equation may have three, five, six, or eight constants. This method
has been used extensively to fit a wide variety of VLE and LLE systems.

Similar to the Wilson and NRTL models, local compositions are used. Two binary
Universal Quasi-Chemical
16 AM parameters are used in the computation of the residual portion of the activity
(UNIQUAC)
coefficient.
This method estimates activity coefficients with a group contribution concept. The
functional group concept is a convenient way to represent thousands of chemical
Universal Functional Activity compounds with a reasonable number of functional groups. This method is very
17 AM
Coefficient (UNIFAC) useful when no activity coefficient data are available for a component pair since
it is predictive when the group interaction data are available for the groups
comprising the component pair.
was derived from a polynomial expansion, with the form proposed by Redlich and
18 AM Margules
Kister (1948) being the most popular form.
The Wilson method has been used successfully to correlate mixtures containing polar
components. However, it cannot describe local maxima and minima in the activity
19 AM Wilson Equation coefficient. Its largest limitation, however, is that it is mathematically unable to predict
the splitting of a liquid into two partially miscible phases. Therefore, it is completely
unsuitable for systems which exhibit liquid-liquid phase splitting.
The van Laar equation is an old correlation which is still frequently used to compute
20 AM van Laar
liquid activity coefficients.
It is useful for mixtures of non-polar components, but should not be used for highly
21 AM Regular Solution
non-ideal mixtures, especially if they contain polar compounds.
22 AM Ideal Systems of similar components at low pressures and temperatures.
This model is useful for modeling polymer/solvent systems, especially if the molecules
23 AM Flory-Huggins POLYMER
are non-polar.
The free volume effect term is computed by using the molecular weights, mass
24 AM UNIFAC Free Volume densities and weight fractions for the components, as well as a constant to represent POLYMER
the effective degrees of freedom per molecule of solvent.
25 AM Advanced Lattice Model For polymer/solvent systems. POLYMER
The amine models are named after the amine component in the system. Typically, a
26 ELEC Amine Electrolyte Systems ELECTROLYTE
single amine and water should be present in the component slate.
ACID H2O, CO, CO2, H2, HCN, HCOOH, N2, NH3, H3PO4, HCL, CL2, HCLO, N2,
27 ELEC Acid Systems O2, SO2, H2SO3, H2SO4, SO2, H2PO4. Vapor/liquid equilibrium is considered for all ELECTROLYTE
components except H3PO4, H2SO3, H2SO4, PO4.
 SALT H2O, NACL, KCL, HCL, MGSO4, NA2SO4, NACL, H2SO4, CASO4, NAOH,
CACL2, MGCL2, CAOH2, MGOH2, CO2, CO, ETHANE, CH4, H2S, H2, N2,
PROPANE, NACHO3, NA2CO3, NAOH, CO2, CL2, HCLO, HCL, N2, O2, SO2,
NAOH, NACL, NAHCO3, NA2CO3, CO2, NH3, H2S, HCL, BACL2, CACL2, CUCL2,
FEIICL2, FEIIICL3, KCL, LICL, MGCL2, MNCL2, NACL, NA2S, NA2SO3, NA2SO4,
28 ELEC Mixed Salt Systems PBCL2, SRCL2, ZNCL2, NA4EDTA, CA2EDTA, BOH3, BACO3, BASO4, CACO3, ELECTROLYTE
CASO4, FE3O4, MGCO3, NH4SO4, SRCO3, SRSO4, CO2, HCL, NA2SO4,
NAHCO3, NA2CO3, MGCL2, BACL2, CACL2, NACL, NAOH, KCL, BASO4, CACO3,
CASO4, BACO3, CAOH2, K2CO3, K2SO4, KHCO3, MGCO3, MGOH2, BAOH2,
KOH, MGSO4, H2SO4. Vapor/liquid equilibrium is considered for H2O, HCL, CO2,
CO, ETHANE, CH4, H2S, H2, N2, PROPANE, CL2, HCLO, O2, SO2, NH3 and H2S.

H2O, CO2, H2S, NH3, CH4, C6H5OH, NAOH, NAHCO3, NA2CO3, ETHANE,
PROPANE, N2, HCL, HCN, H3PO4, NACL, NAHS, HCOOC, HCL, NACL, NAHS,
29 ELEC Sour Water Electrolyte Systems HCN, HACETATE, HCN, NBUTANE, NACL, NAHS, H2, O2, CO. Vapor/liquid ELECTROLYTE
equilibrium is considered for all components except H3PO4, NAHCO3, NA2CO3,
NAOH, NACL, NAHS and HACETATE.
CAUS H2O, CL2, HCLO, HCL, SO2, NACL, NA2SO3, NA2SO4, NAOH, H2SO4,
30 ELEC Caustic Systems NAOH, KOH. Vapor/liquid equilibrium is considered for H2O, CL2, HCLO, HCL and ELECTROLYTE
SO2.
H2O, CO2, CO, ETHANE, ETHYLENE, CH4, H2S, H2, N2, NH3, PROPANE, K2CO3,
31 ELEC Benfield Systems KHCO3, KHS, H3PO4, BOH3, KOH. Vapor/liquid equilibrium is not considered for ELECTROLYTE
K2CO3, KHCO3, KHS, H3PO4, BOH3 or KOH.
H2O, CO2, HCL, HCN, HCOOH, N2, O2, SO2, NAOH, CACO3, CACL2, NACL,
32 ELEC Scrubber Systems NA2CO3, NAHCO3, NACOOH, CAOH2. Vapor/liquid equilibrium is considered for ELECTROLYTE
H2O, CO2, HCL, HCN, HCOOH, N2, O2 and SO2.

H2O, CO2, H2S, NH3, CH4, C6H5OH, TOLUENE, NAOH, NAOH.1H2O, NA2CO3,
NA2CO3.10H2O, NA2CO3.1H2O, NA2CO3.7H2O, NAHCO3, NACL, NAHS, HCL,
CACL2, CACL2.1H2O, CALC2.2H2O, CALC2.4H2O, CALC2.6H2O, CAHCO32,
CACO3, CAOH2, NH4CL, NH4HCO3, NH4HS, NACL, NAHSO4, NA2SO4,
33 ELEC LLE and Hydrate Systems NA2SO4.10H2O, NAOH, NAOH.1H2O, CAHSO42, CASO4, CASO4.2H2O, CAOH2, ELECTROLYTE
HCL, N2, CH4, METHANOL, ETHANOL, MXYLENE, BENZENE, TOLUENE, CACL2,
CACL2.1H2O, CACL2.2H2O, CACL2.4H2O, CACL2.6H2O, HF, H2SO4, CAF2, NAF.
Vapor/liquid equilibrium is considered for H2O, CO2, H2S, NH3, CH4, C6H5OH,
TOLUENE, HCL, BENZENE, ETHANOL, HF, METHANOL, MXYLENE and N2.
 Vapor Liquid

K- Enthalp
Entropy Density Density
values y
Oil Refining and
Gas Processing
Soave-Redlich
Kwong (SRK) SRK SRK SRK SRK API

Peng-Robinson
(PR) PR PR PR PR API

Grayson-Streed
(GS) GS CP CP SRK API

Braun K-10
(BK10) BK10 JG CP Ideal API

Chemical
Processing
Vapor
Ideal Pressur Library -- Library Library
e

NRTL NRTL Library -- Library Library

UNIQUA
UNIQUAC Library -- Library Library
C

UNIFAC UNIFAC Library -- Library Library