VARIOUS THERMODYNAMIC MODELS (APPLICABILITY & LIMIT

Prepared By : Mehul P
Equation of State (EOS) Models
Soave modified Redlich Kwang (SRK)
Peng Robinson (PR)
Modified SRK (Modified Panagiotopoulos-Reid modifications to SRK) (SRKM)
Modified PR (Panagiotopoulos-Reid modifications to PR) (PRM)
Benedict Webb Rubin Starling (BWRS)
Lee Kesler Plocker (LKP)
UNIWAALS
SRK-SIMSCI
SRK-Kabadi-Danner (SRKKD)
PRMHV2 / PRWS
PSRK
RKSMHV2
RKSWS
Nothnagel
Hayden-O'Connell

Liquid Activity co-efficient Models Generalized Co

2 Suffix Margules IDEAL
3 Suffix Margules Sour Water (SWAT)
van Laar GPA Sour Water (GPSWAT
WILSON Grayson Steered (GS)
UNIQUAC Improved Grayson Steer
NRTL Braun K 10 (BK 10)
UNIFAC Chao-Seader (CS)
Modified UNIFAC (Lyngby) (UFT1) ERBAR modification to C
Modified UNIFAC (Dortmund) (UFT2)
Henry's Law
CABILITY & LIMITATIONS)
Prepared By : Mehul Patel

SRK) (SRKM)

Generalized Correlations / Special Packages

Sour Water (SWAT)

GPA Sour Water (GPSWAT)
Grayson Steered (GS)
Improved Grayson Steered (IGS)
Braun K 10 (BK 10)
Chao-Seader (CS)
ERBAR modification to Chao-Seader (CSE)
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
All
or mildly polar All
Soave pressures
mixtures. Eg. H/C and temperature
modified upto
light gases, such as s upto
Redlich Cubic critical -
CO2, H2S & H2. critical point.
Kwang point. R :
Suitable in high Tempt R : -460 to
(SRK) 0 to
and high Pressure 1200
5000
regions, such as in HC
processing
applications or
supercritical
extractions.
 Thermodynamic
Assumptio Limitation Phase(s Mixtur Properties
Pure
ns Involved s / Pitfalls ) e
Vapor Liquid
mixture mixture

Not useful
for Non- K value,
ideal Enthalpy, K value,
systems. Entropy, Enthalpy,
Results are Fugacity Entropy,
least coefficien Fugacity
- V&L Yes Yes
accurate in t, coefficien
the region Density, t, Gibbs
near the Gibbs free
mixture free energy
critical energy
point.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

SRK equation
calculates all Free water
MW, Tc, Pc,
TD properties Decant -
Accentric
with option to Supported.
factor,
improve liquid VLLE - Not
Ideal Vapor
molar volume recommen
enthalpy
using volume ded
correction.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
All All
or mildly polar
temperature pressures
mixtures. Eg. H/C and
Peng s upto upto
light gases, such as
Robinson Cubic critical critical -
CO2, H2S & H2.
(PR) point. R : point. R :
Suitable in high Tempt
-460 to 0 to
and high Pressure
1200 5000
regions, such as in HC
processing
applications or
supercritical
extractions.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Not useful
for Non- K value,
ideal Enthalpy, K value,
systems. Entropy, Enthalpy,
Results are Fugacity Entropy,
least coefficien Fugacity
- V&L Yes Yes
accurate in t, coefficien
the region Density, t, Gibbs
near the Gibbs free
mixture free energy
critical energy
point.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

PR equation
calculates all TD
properties except
Free water
liquid molar MW, Tc, Pc,
Decant -
volume. API Accentric
Supported.
method for liquid factor,
VLLE - Not
molar volume of Ideal Vapor
recommen
pseudocomponan enthalpy
ded
ts and Rackett
model for real
componenents.
Equation of State (EOS) Model

Applicabl
Applicable e
Component
Model Name Type Applicable systems Tempt. Pressure
s
Range, °F Range,
psi A
Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
or mildly polar
mixtures. Eg. H/C and
Modified SRK All All
light gases, such as
(Modified temperature pressures
CO2, H2S & H2.
Panagiotopoul s upto upto
Suitable in high Tempt
os-Reid Cubic critical critical -
and high Pressure
modifications point. R : point. R :
regions, such as in HC
to SRK) -460 to 0 to
processing
(SRKM) 1200 5000
applications or
supercritical
extractions.
Applicable to Non
ideal systems. VLLE
behaviour can be
predicted.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

K value,
Enthalpy, K value,
Liquid density
Entropy, Enthalpy,
calculation
Fugacity Entropy,
not
coefficien Fugacity
- recommende V&L Yes Yes
t, coefficien
d. Free water
Density, t, Gibbs
decant not
Gibbs free
supported.
free energy
energy
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

MW, Tc, Pc,

Recommended
Accentric
for polar/polar
factor (if Free water
and/or
accentric Decant -
polar/non-
alfa Not
polar systems
formulatio Supported.
which the
n VLLE -
standard SRK
selected), Supported.
or PR EOS
Ideal Vapor
cannot handle.
enthalpy
Equation of State (EOS) Model

Applicabl
Applicable e
Component
Model Name Type Applicable systems Tempt. Pressure
s
Range, °F Range,
psi A
Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
or mildly polar
mixtures. Eg. H/C and
All All
light gases, such as
Modified PR temperature pressures
CO2, H2S & H2.
(Panagiotopoul s upto upto
Suitable in high Tempt
os-Reid Cubic critical critical -
and high Pressure
modifications to point. R : point. R :
regions, such as in HC
PR) (PRM) -460 to 0 to
processing
1200 5000
applications or
supercritical
extractions.
Applicable to Non
ideal systems. VLLE
behaviour can be
predicted.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

K value,
Enthalpy, K value,
Liquid density
Entropy, Enthalpy,
calculation
Fugacity Entropy,
not
coefficien Fugacity
- recommende V&L Yes Yes
t, coefficien
d. Free water
Density, t, Gibbs
decant not
Gibbs free
supported.
free energy
energy
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

MW, Tc, Pc,

Accentric
factor (if Free water
accentric Decant -
alfa Not
-
formulatio Supported.
n VLLE -
selected), Supported.
Ideal Vapor
enthalpy
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Gas processing, Refinery &

petrochemical
applications. Applicable to
non polar or mildly polar
mixtures & light gases. Eg.
H/C and light gases, such
All
as CO2, H2S & N2.
temperatur
Suitable in high Tempt and
es upto
high Pressure regions,
critical
such as in HC processing All
point.
Benedict applications or pressures
Suited for
Webb Virial supercritical extractions. upto
reduced T C1 &
Rubin (Non- Useful for light HC in the critical
as low as Heavier
Starling Cubic) cryogenic liquid region in point. R :
0.3 &
(BWRS) addition to higher tempt 0 to
reduced
region. Light to heavy 2000
density =
HCs. This method is
3.0. R :
particularly suited to
-460 to
mixtures common to
200.
natural gas processing
such as LPG and LNG and
predicts fluid
thermodynamic properties
including the cryogenic
liquid region.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

All TD
propertie
s & can
predict
liquid
Rigorous All TD molar
two liquid properties volume
phase / K value, &
- V&L Yes Yes
behaviour Enthalpy, enthalpy
is not Entropy, accurate
supported. Density than PR
& RKS / K
value,
Enthalpy,
Entropy,
Density
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

This method is
comparable to
PR, RKS, BWR-
LS & LKP EOS
MW, Tc, Pc, Free water
method.
Accentric Decant -
Excellent EOS
factor, Supported.
for predicting
Ideal Vapor VLLE - Not
properties of
enthalpy Supported.
pure HCs and
gases at any
tempt. &
pressure.
Equation of State (EOS) Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Gas processing,
Refinery,
petrochemical
applications &
reformer systems
containing high
Lee quantity of H2. Below
Light HCs.
Kesler Applicable to non polar reduced
Virial - HCs upto
Plocker or mildly polar temperatur
C8.
(LKP) mixtures. Eg. H/C and e of 0.96.
light gases, such as
CO2, H2S & H2. VLLE
behaviour can be
predicted. RKS & PR
methods are
preferred over LKP.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

All TD
properties
All TD except
properties liquid
/ K value, molar
- - V&L Yes Yes
Enthalpy, volume /
Entropy, K value,
Density Enthalpy,
Entropy,
Density
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Derived from MW, Tc, Pc, Free water

corresponding Accentric Decant -
state approach factor, Not
combined with Ideal Vapor Supported.
BWRS EOS enthalpy, VLLE -
model. Sp. Gr. Supported.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

It is most often useful

for highly non-ideal
systems if group
contributions Low to mid
UNIWAAL
Cubic parameters are temperature - -
S
supplied either from s
data banks or user.
VLLE behaviour can
be predicted.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

Calculation of
Fugacity
coefficients
are
cumbersome.
K value, K value,
Accuracy is
Enthalpy, Enthalpy,
- not better V&L Yes Yes
Entropy, Entropy,
than UNIFAC
Density Density
at low tempt
and accuracy
deteriorates
with increse in
temperature.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Liquid density
supported but
not
recommended.
A cubic EOS,
combined with
an excess gibbs
free energy
Free water
model. By using MW, Tc, Pc,
Decant -
this approach, Accentric
Not
the same factor,
Supported.
parameters of Ideal Vapor
VLLE -
the excess gibbs enthalpy
Supported.
free energy
model based on
low pressure
VLE data can be
extended to
apply to high
pressures using
EOS.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
or mildly polar
mixtures. Eg. H/C and
All All
light gases, such as
temperature pressures
CO2, H2S & H2.
s upto upto
SRK- Suitable in high Tempt
Cubic critical critical -
SIMSCI and high Pressure
point. R : point. R :
regions, such as in HC
-460 to 0 to
processing
1200 5000
applications or
supercritical
extractions.
Applicable to Non
ideal systems. VLLE
behaviour can be
predicted.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

K value,
Liquid
Enthalpy, K value,
density
Entropy, Enthalpy,
calculation
Fugacity Entropy,
not
coefficien Fugacity
- recommen V&L Yes Yes
t, coefficien
ded. Free
Density, t, Gibbs
water
Gibbs free
decant not
free energy
supported.
energy
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

SRKS is
recommended for
HF alkylation
process and the
manufacture of
refrigerents and MW, Tc, Pc,
other halogenated Accentric
compounds. It is factor (if Free water
also suitable for accentric Decant -
polar/polar and/or alfa Not
polar/non-polar formulatio Supported.
systems. Use of n VLLE -
either SRKM or selected), Supported.
SRKS for non-ideal Ideal Vapor
system is enthalpy
dependent on
availability of key
binary
components
parameters.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A
Gas processing,
Refinery &
petrochemical
applications.
Applicable to non polar
or mildly polar
mixtures. Eg. H/C and
light gases, such as
CO2, H2S & H2.
Suitable in high Tempt
All All
and high Pressure
temperature pressures
SRK- regions, such as in HC
s upto upto
Kabadi- processing
Cubic critical critical -
Danner applications or
point. R : point. R :
(SRKKD) supercritical
-460 to 0 to
extractions.
1200 5000
Applicable to Non
ideal systems. VLLE
behaviour can be
predicted. This
mixing rule is
especially
applicable when
dealing with water-
hydrocarbon
system.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

Liquid density
calculation not
recommended
. Free water
decant not K value,
supported. Enthalpy, K value,
Leads to Entropy, Enthalpy,
inconsistencie Fugacity Entropy,
s when a coefficien Fugacity
- V&L Yes Yes
component is t, coefficien
split into two Density, t, Gibbs
or more Gibbs free
identical free energy
fractions. energy
Gives large
errors for the
aqueous
phase.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

MW, Tc, Pc,

SRKKD mixing
Accentric
rule is
factor (if Free water
composition
accentric Decant -
dependent.
alfa Not
Developed
formulatio Supported.
specifically for
n VLLE -
water and well
selected), Supported.
defined light
Ideal Vapor
HC systems.
enthalpy
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable for
High Upto 2175
PRMHV2 Predictiv mixtures of non-polar
temperature psi (150 -
/ PRWS e EOS and polar components
s bar)
and light gases.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

Results are
least accurate
close to
critical point. Fugacity Fugacity
UNIFAC coefficien coefficien
interaction t, t,
parameters Density, Density,
- V&L - Yes
must be Enthalpy, Enthalpy,
available at Entropy, Entropy,
low pressure Gibbs Gibbs
for Energy Energy
corresponding
pair of
interactions.
 Required
pure Two liquid
Remarks componen phase
t behaviour
properties

It is an extension
of PR EOS and
uses UNIFAC
model (at low
Tc, Pc,
pressure) to
Omega,
predict
UNIFAC
interaction
function Free water
parameters at
group no. & Decant &
high pressures.
no. of VLLE
Accurate
occurances -Supported.
predictions (3-4%
, UNIFAC R
in pressure and
& Q
2% in mole
parameters
fraction) at a
given
temperature can
be made.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable for
High
Predictiv mixtures of non-polar High
PSRK temperature -
e EOS and polar components pressures
s
and light gases.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

UNIFAC
interaction
parameter Fugacity Fugacity
s must be coefficien coefficien
available t, t,
at low Density, Density,
- V&L - Yes
pressure Enthalpy, Enthalpy,
for Entropy, Entropy,
correspond Gibbs Gibbs
ing pair of Energy Energy
interaction
s.
 Required
pure Two liquid
Remarks componen phase
t behaviour
properties

It is an extension
of SRK EOS and
uses UNIFAC
model (at low Tc, Pc,
pressure) to Omega,
predict UNIFAC
interaction function Free water
parameters at group no. & Decant &
high pressures. no. of VLLE
Upto now, the occurances, -Supported.
interaction UNIFAC R &
parameters for Q
30 gases and 51 parameters
UNIFAC main
groups are
included.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable for
High Upto 2175
RKSMHV Predictiv mixtures of non-polar
temperature psi (150 -
2 e EOS and polar components
s bar)
and light gases.
 Thermodynamic
Assumptio Limitations Phase(s Mixtur Properties
Pure
ns Involved / Pitfalls ) e
Vapor Liquid
mixture mixture

Results are
least
accurate
close to
critical point.
Fugacity Fugacity
Lyngby
coefficien coefficien
modified
t, t,
UNIFAC
Density, Density,
- interaction V&L - Yes
Enthalpy, Enthalpy,
parameters
Entropy, Entropy,
must be
Gibbs Gibbs
available at
Energy Energy
low pressure
for
correspondin
g pair of
interactions.
 Required
Two liquid
pure
Remarks phase
component
behaviour
properties

It is an extension
of RKS EOS and
uses Lyngby
modified UNIFAC
model (at low Tc, Pc,
pressure) to Omega,
predict UNIFAC
interaction function Free water
parameters at group no. & Decant &
high pressures. no. of VLLE
Accurate occurances, -Supported.
predictions (3- UNIFAC R &
4% in pressure Q
and 2% in mole parameters
fraction) at a
given
temperature can
be made.
Equation of State (EOS) Model

Applicabl
Applicable e
Model Component
Type Applicable systems Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable for
High Upto 2175
Predictiv mixtures of non-polar
RKSWS temperature psi (150 -
e EOS and polar components
s bar)
and light gases.
 Thermodynamic
Assumptio Limitations Phase(s Mixtur Properties
Pure
ns Involved / Pitfalls ) e
Vapor Liquid
mixture mixture

Results are
least
accurate
close to
Fugacity Fugacity
critical point.
coefficien coefficien
UNIFAC
t, t,
interaction
Density, Density,
- parameters V&L - Yes
Enthalpy, Enthalpy,
must be
Entropy, Entropy,
available at
Gibbs Gibbs
low pressure
Energy Energy
for
correspondin
g pair of
interactions.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s
It is an extension
of SRK EOS and
uses UNIFAC
model (at low Tc, Pc,
pressure) to Omega,
predict UNIFAC
interaction function
Free water
parameters at group no.
Decant &
high pressures. & no. of
VLLE
Accurate occurances
-Supported.
predictions (3-4% , UNIFAC R
in pressure and & Q
2% in mole parameter
fraction) at a s
given
temperature can
be made.
Equation of State (EOS) Model

Applicable
Applicabl
Model Pressure Component
Type Applicable systems e Tempt.
Name Range, psi s
Range, °F
A

Applicable to mixtures
Low pressure
containing carboxylic
Nothnag upto several Carboxylic
EOS acids where -
el atmospheres acids
dimerization in the
.
vapor phase occurs.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Not
Fugacity
suitable at
coefficien
medium or
t,
high
Density,
- pressure V - Yes -
Enthalpy,
vapor
Entropy,
phase
Gibbs
association
Energy
.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Not preferable
over Hayden-
O'Connell EOS.
Dimerization
affects VLE;
vapor phase
properties,
- -
such as
enthalpy and
density; and
liquid phase
properties,
such as
enthalpy.
Equation of State (EOS) Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable to mixtures Medium

containing carboxylic pressures
acids where solvation around
Hayden- Carboxylic
EOS of polar compounds - 150 to
O'Connell acids
and dimerization in 225 psi
the vapor phase (10-15
occurs. atm).
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Fugacity
coefficien
t,
Density,
- - V - Yes -
Enthalpy,
Entropy,
Gibbs
Energy
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Preferable over
Nothanagel
EOS.
Dimerization
affects VLE;
vapor phase
- -
properties, such
as enthalpy and
density; and
liquid phase
properties, such
as enthalpy.
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable to systems Use at or

whose components near
have similar molar temperatu
2 Suffix Max. upto
Activity volumes (size, shape res where -
Margules 10 bar.
& chemical nature) & parameter
slightly non-ideal s were
systems. fitted.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture
Not applicable
to systems
whose
components do
not have
Equations
similar molar Used to predict VLE
parameters
volumes. & VLLE phase
are not L&S No Yes
Binary behaviour. K values
tempt
parameters do of every species.
dependent.
not have any
physical
significance.
LLE is not
predicted.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Based on
Wohl's Vapor
equation. press., Tc, Free water
Should be Pc, Decant -
cautious in Accentric Not
using in the factor, Supported.
tempt range Liquid VLLE -
where binary molar Supported.
parameters volume
are fitted.
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Applicable to systems Use at or

whose components near
have similar molar temperatu
3 Suffix Max. upto
Activity volumes (size, shape res where -
Margules 10 bar.
& chemical nature) & parameter
slightly non-ideal s were
systems. fitted.
 Thermodynamic
Assumptio Limitations / Phase(s Mixtur Properties
Pure
ns Involved Pitfalls ) e
Vapor Liquid
mixture mixture

Not applicable to
systems whose
components do
Equations not have similar
Used to predict VLE
parameters molar volumes.
& VLLE phase
are not Binary L&S No Yes
behaviour. K values
tempt parameters do
of every species.
dependent. not have any
physical
significance. LLE
is not predicted.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Based on
Wohl's Vapor
equation. press., Tc, Free water
Should be Pc, Decant -
cautious in Accentric Not
using in the factor, Supported.
tempt range Liquid VLLE -
where binary molar Supported.
parameters volume
are fitted.
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Use for
Use for chemically
chemically
similar components & Max. upto
van Laar Activity - similar
slightly non-ideal 10 bar.
components
systems.
.
 Thermodynamic
Assumptio Limitation Phase(s Mixtur Properties
Pure
ns Involved s / Pitfalls ) e
Vapor Liquid
mixture mixture

Not useful
Equations for strongly
Used to predict VLE
parameters non-ideal /
& VLLE phase
are not polar L No Yes
behaviour. K values
temperature systems.
of every species.
dependent. LLE is not
predicted.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Based on
Vapor
Wohl's
press., Tc, Free water
equation.
Pc, Decant -
Mixtures of
Accentric Not
alcohols and
factor, Supported.
hydrocarbons
Liquid VLLE -
should not be
molar Supported.
modeled using
volume
this method.
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Particularly useful for

solutions of polar or
associating
components (e.g.
alcohols) in nonpolar
solvents. Applicable
only for systems that Max. upto
WILSON Activity - -
are completely 10 bar.
miscible or else for
those limited regions
of partially miscible
sytems where only
one liquid phase is
present.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Not
Equations applicable
Used to predict VLE
parameters to partially
phase behaviour. K
are not miscible L No Yes
values of every
temperature soltions.
species.
dependent. LLE is not
predicted.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Vapor
Wider tempt press., Tc, Free water
range as Pc, Decant -
compare to Accentric Not
van Laar and factor, Supported.
Margules Liquid VLLE - Not
equation. molar Supported.
volume
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Nonelectrolyt
e liquid
mixtures
containing
Useful for non
nonpolar or
electrolyte &/or non-
polar fluids
ideal systems,
Max. upto such as HCs,
UNIQUAC Activity especially for partially -
10 bar. alcohols,
immiscible system.
nitrils,
Useful for completely
ketones,alde
miscible systems also.
hydes,
organic
acids, etc.
and water.
 Thermodynamic
Assumptio Limitations Phase(s Mixtur Properties
Pure
ns Involved / Pitfalls ) e
Vapor Liquid
mixture mixture

Does not
support
water
Equations Used to predict VLE
decant. Not
parameters and/or LLE or VLLE
applicable
are L, L1 & L2 No Yes phase behaviour. K
near critical
temperature values of every
temperature
dependent. species.
of any
components
.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Vapor
press., Tc,
Applicable to Pc,
Free water
non random Accentric
Decant -
mixtures to factor, van
Not
solutions derwaals
Supported.
containing area and
VLLE -
molecules of volume,
Supported.
different size. Liquid
molar
volume
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Useful for non-ideal

systems, especially for
Applicable
partially immiscible Max. upto
NRTL Activity - apart from
system. Useful for 10 bar.
HCs.
completely miscible
systems also.
 Thermodynamic
Assumptio Limitation Phase(s Mixtur Properties
Pure
ns Involved s / Pitfalls ) e
Vapor Liquid
mixture mixture
Does not
support
water
Equations Used to predict VLE
decant. Not
parameters and/or LLE or VLLE
applicable
are L, L1 & L2 No Yes phase behaviour. K
near critical
temperature values of every
temperatur
dependent. species.
e of any
components
.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Vapor
press., Tc, Free water
Pc, Decant -
Accentric Not
-
factor, Supported.
Liquid VLLE -
molar Supported.
volume
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Useful for non-ideal

applications at low
pressures. Generally
restricted to
components with 10 or
All
fewer different
Group components
structural groups & R : 32 - Max. upto
UNIFAC Contributio well below
system containing low 300 10 bar.
n method their critical
MW polymers.
point.
Applicable for any
combination of polar
and non-polar
compounds upto very
strong nonideality.
 Thermodynamic
Assumptio Limitation Phase(s Mixtur Properties
Pure
ns Involved s / Pitfalls ) e
Vapor Liquid
mixture mixture

Does not
support
water
Equations
decant. Not Used to predict VLE
parameters
applicable L, L1 & and VLLE phase
are not No Yes
near critical L2 behaviour. K values
temperature
temperature of every species.
dependent.
of any
components
.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s
Estimate
activity
Vapor
coefficients
press., Tc,
based on
Pc,
group
Accentric
contribution Free water
factor, van
concept Decant -
derwaals
followed by Not
area and
ASOG model. Supported.
volume,
Interaction b/n VLLE -
Liquid
two molecules Supported.
molar
are assumed
volume,
to be a
Structural
function of
groups
group group
interactions.
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Modified Group
Useful for non-ideal
UNIFAC Contrib R : 70 - Max. upto
applications at low -
(Lyngby) ution 300 10 bar.
pressures.
(UFT1) method
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Equations
Used to predict VLE
parameters
L, L1 & and VLLE phase
are not - No Yes
L2 behaviour. K values
temperature
of every species.
dependent.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Vapor
press., Tc,
Pc,
Free water
Accentric
Decant -
Refer : Lyngby factor, van
Not
model of Dr. derwaals
Supported.
Larsen et al. area and
VLLE -
volume,
Supported.
Liquid
molar
volume
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Modified
Group Useful for non-ideal
UNIFAC R : 70 - Max. upto
Contributio applications at low -
(Dortmun 300 10 bar.
n method pressures.
d) (UFT2)
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Equations
Used to predict VLE
parameters
L, L1 & and VLLE phase
are not - No Yes
L2 behaviour. K values
temperature
of every species.
dependent.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Vapor
press., Tc,
Pc,
Free water
Accentric
Refer : Decant -
factor, van
Dortmund Not
derwaals
model of Dr. Supported.
area and
Gmehling. VLLE -
volume,
Supported.
Liquid
molar
volume
Liquid Activity Co-efficient Model

Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
psi A

Used to predict gas

solubilities, especially
for modelling
supercritical/non- Super
condensible critical
components using a Less than gases, trace
Henry's liquid activity critical R:P< organics in
Generalized
Law method.Especially point of 10 atm water.
useful for solvent. Concentratio
environmental n less than 5
applications such as mole %.
modelling trace
organics in aqueous
streams.
 Thermodynamic
Limitatio Properties
Assumptio Phase(s Mixtur
ns / Pure
ns Involved ) e
Pitfalls
Vapor Liquid
mixture mixture

Does not
include
Poynting
correction,
Returns heat
of mixing of - L Yes Yes - K values
zero, & is
used to
initialize
FLASH
algoritham.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

A liquid activity
method system
must be chosen if Free water
HENRY option is to Decant - Not
be used. PRO-II Supported.
provides HENRY's VLLE - The
data for following HENRY option
components pair only
Vapor
with Water : CO, H2, calculates
pressure
Ar, N2, O2, CO2, gas
H2S, NH3, SO2, CH4 solubilities.
and many more However,
components. As Xi VLLE
approaches to zero, methods may
Activity coefficient also be used.
approaches unity
value.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

Useful to light to mid

range refinery HCs. It
is also useful for
Grayson R : -100
vacuum column & R:P<
Steered Generalized <T< -
coker simulation when 3000
(GS) 800
API 87 is used. For
Hydrogen rich system,
it is recommended.
Assumptio Limitations Phase(s Mixtur Thermodynamic
Pure
ns Involved / Pitfalls ) e Properties

Vapor Liquid
mixture mixture
Upto 20 mol
% of other
dissolved
gases in the
K values,
liquid.
Fugacity
Incapable of
coefficien K values,
predicting
t, Fugacity
the
Density, coefficien
- composition L Yes No
Enthalpy, t, Gibbs
of the water
Entropy, free
rich phase.
Gibbs energy
They should
free
be used at T
energy
below 60 °F
and pressure
above 600
psia.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

MW, Pc, Tc,

Liquid
molar Free water
Recommended
volume, Decant -
over BK 10 for
Accentric Supported.
the streams
factor, VLLE - Not
containing H2.
Water Supported.
Solubility
parameter.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

Generally useful for

ERBAR
petroleum refinery
modificatio
Generalize applications. It offers R: <3000
n to Chao- R: 0 - 800 -
d improved liquid psia
Seader
fugacity coefficients for
(CSE)
N2, H2S & CO2.
Assumptio Limitations / Phase(s Mixtur Thermodynamic
Pure
ns Involved Pitfalls ) e Properties

Vapor Liquid
mixture mixture

H2S correlation
cannot be used
in any cases
where an
azeotrope may
exist (e.g.
H2S/C3H8
Only K Only K
- mixtures), as - - -
value value
the azeotrope
will not be
predicted. Can
not support
rigorous 3
phase
calculations.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Improved
Grayson
Streed (IGS)
method is
preferable
over CS. When
Free-water
SYSTEM=CSE
MW, Tc, Pc, Decant -
is chosen, GS
Accentric Supported.
K-values, Curl-
factor VLLE - Not
Pitzer (CP)
Supported.
enthalpies, CP
entropies, API
liquid densities
& SRK vapor
densities are
default.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Applicable Component
Type e Tempt. Pressure
Name systems s
Range, °F Range,
bar A

For C2 &
For C2 &
Generally useful for Higher:
Higher: 0
Chao- light to mid-range <2000
Generalize to 800 °F.
Seader refinery HC & light psia. For -
d For H2 &
(CS) gases such as CO2 H2 & C1:
C1: -100
& H2S. <8000
to 500 °F.
psia.
Assumptio Phase(s Mixtur Thermodynamic
Limitations / Pitfalls Pure
ns Involved ) e Properties

Vapor Liquid
mixture mixture

For all HCs;

Pressure: upto 2000
psia but NOT exceeding
0.8 of the critical
pressure of the system.
Temperature: -100 to
500 °F &
pseudoreduced temp,
Tr, of the equilibrium
liquid mixture less than
0.93. Tr is based on the
Only K Only K
- molar avg of the critical V&L Yes Yes
value value
T of the components.
Concentration: upto
20 mole % of other
dissolved gases in the
liquid. In addition, the
method is NOT suitable
for other non-HC
components such as
N2, H2S, CO2, etc. It is
NOT recommended for
systems containing H2.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Grayson streed
method is
preferable over
CS. When
SYSTEM=CS is
chosen, CS K-
values, Curl-Pitzer
(CP) enthalpies,
CP entropies, API MW, Tc, Pc,
liquid densities & Liq. Molar Free-water
SRK vapor volume, Decant -
densities are Accentric Supported.
assumed. Don't factor, VLLE - Not
use this property Solubility Supported.
method at very parameter
high pressures,
especially near
the mixture
critical point,
because of
anomalous
behaviour in these
regions.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

Used for heavy

Braun K refinary HCs at
Generalize R : 100 < R : 0 < P
10 (BK vacuum & low C6 & heavier
d T < 1200 < 100
10) pressure applications
(upto several atm).
Assumptio Limitations / Phase(s Mixtur Thermodynamic
Pure
ns Involved Pitfalls ) e Properties

Vapor Liquid
mixture mixture

For mixtures of
aliphatic &
aromatic
compounds, or
naphthenic
mixtures, the
accuracy
decreses which
- cause - - - K values K values
nonidealities &
form
azeotropes. Not
recommended
for streams
containing
significant
amount of H2.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

MW, Pc, Tc,

Free water
Accentric
Decant -
factor,
- Supported.
Normal
VLLE - Not
boiling
Supported.
point.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

For HC-water mixtures,

IGS accurately predict
the phase behaviour
of the HC rich phase.
For Hydrogen rich
Improved system, it is
Grayson recommended. Useful R : 0 < T R:P<
Generalized -
Steered for petroleum refinary < 800 3000
(IGS) applications at
medium pressures.It
offers improved liquid
fugacity coefficients
for N2, H2S, CO, H2O,
O2 & CO2.
Assumptio Limitations Phase(s Mixtur Thermodynamic
Pure
ns Involved / Pitfalls ) e Properties

Vapor Liquid
mixture mixture

Don't support
rigorous 3
phase
calculations.
These
methods are K values,
not Fugacity
recommende coefficien K values,
d for t, Fugacity
modelling Density, coefficien
- L1 & L2 Yes No
separations Enthalpy, t, Gibbs
of close Entropy, free
boiling Gibbs energy
components free
(e.g. energy
isomers). Not
useful at high
pressure near
mixture
critical point.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Recommended
over BK 10 for
the streams
containing H2.
When
MW, Pc, Tc,
SYSTEM=IGS Free water
Accentric
is chosen, GS Decant -
factor,
K-values, Curl- Supported.
Water
Pitzer (CP) VLLE -
Solubility
enthalpies, CP Supported.
parameter.
entropies, API
liquid densities
& SRK vapor
densities are
default.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

XNH3 < 0.4.

PCO2 +
PH2S <
Uses GPSWAT for sour
1200 psia.
system containing
(H2O, H2S,
GPA Sour components H2O,
R : 68 < R:P< CO2, NH3
Water Special H2S, CO2, NH3, CO,
T < 600 2000 required).
(GPSWAT) CS2, MeSH, EtSH.
Where P is
SRKM is used for other
the partial
components.
pressure of i
in vapor
phase.
 Limitatio
Assumptio Phase(s Mixtur Thermodynamic
ns / Pure
ns Involved ) e Properties
Pitfalls

Vapor Liquid
mixture mixture

Predicts K
values, VLE
&/or LLE phase
behaviour.
Vapor enthalpy
& density,
Vapor and
- - V, L & L1 - Yes liquid entropy -
are calculated
by SRKM EOS,
while liquid
enthalpy &
density are
calculated by
Ideal methods.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

Wider range in
terms of T, P &
composition as
compared to
SOUR Free water
package. NH3, Decant - Not
H2S, CO2 & Supported.
Tc, Pc,
H2O must be VLLE -
Accentric
included in Supported but
facor
component list not
when using recommended
GPSWATER .
method. VLLE
supported but
not
recommended.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Componen
Type Applicable systems e Tempt. Pressure
Name ts
Range, °F Range,
bar A

This method is
combination of the
API/EPA SWEQ (Sour
Water Equilibrium)
XNH3+XCO
model for sour water
2+XH2S <
components (H2O,
Sour 0.3 where
H2S, CO2, & NH3) & R : 68 < R:P<
Water Special Xi is the wt
SRKM for all other T < 300 1500
(SWAT) fraction in
components. Useful
aqueous
for applications
phase.
involving sour water
containing less than
30% by weight of sour
components.
 Limitatio
Assumptio Phase(s Mixtur Thermodynamic
ns / Pure
ns Involved ) e Properties
Pitfalls

Vapor Liquid
mixture mixture
Short
range of P,
T &
compositio
n as
Predicts K values,
compared
VLE &/or LLE phase
to GPA
behaviour. Vapor
sour water.
enthalpy & density,
Has an
Vapor and liquid
overall
- V, L & L1 - Yes entropy are
error b/n
calculated by SRKM
measured
EOS, while liquid
&
enthalpy & density
predicted
are calculated by
partial
Ideal methods.
pressures
of about
30% for
NH3, CO2
& H2S.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

NH3 and water

must be
present when
using this Free water
method. Decant - Not
Recommended Supported.
Tc, Pc,
over GPS VLLE -
Accentric
Water when Supported
facor
CPU time is a but not
consideration. recommende
VLLE d.
supported but
not
recommended.
Generalized Correlations / Special Packages
Applicabl
Applicabl e
Model Component
Type Applicable systems e Tempt. Pressure
Name s
Range, °F Range,
bar A

Useful for non-polar

HCs. Should be used
Low
IDEAL Generalized with pure component - -
pressures.
stream and stream
with pure components.
 Limitatio
Assumptio Phase(s Mixtur Thermodynamic
ns / Pure
ns Involved ) e Properties
Pitfalls

Vapor Liquid
mixture mixture

Does not
include
Poynting
correction,
Returns heat K value, K value,
of mixing of - L No Yes density & density &
zero, & is enthalpy. enthalpy.
used to
initialize
FLASH
algoritham.
 Required
pure
Two liquid
compone
Remarks phase
nt
behaviour
propertie
s

K values,
Follow Raoult's Vapor &
Free water
law. As Xi Liquid
Decant -
approaches to enthalpy,
Not
unity, Activity Vapor &
Supported.
coefficient Liquid
VLLE - Not
approaches density,
Supported.
unity value. Liquid
entropy.