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RGCT2.2-OCT03-O
Table of Contents
1
Introduction..........................................................................1-2
Introduction..........................................................................2-3
2.2
2.3
2.4
2.5
2.6
Henrys Law.......................................................................2-11
2.7
2.8
2.9
3.2
Activity Models...................................................................3-93
3.3
3.4
4.2
4.3
COSTALD Method.............................................................4-11
4.4
Viscosity ............................................................................4-14
4.5
Thermal Conductivity.........................................................4-18
4.6
4.7
iii
5.2
5.3
5.4
Introduction..........................................................................6-2
6.2
6.3
6.4
Introduction..........................................................................7-2
7.2
7.3
iv
Introducing COMThermo
1-1
1 Introducing COMThermo
1.1 Introduction......................................................................................2
1-1
1-2
Introduction
1.1 Introduction
The use of process simulation has expanded from its origins in
engineering design to applications in real time optimization, dynamic
simulation and control studies, performance monitoring, operator
training systems and others. At every stage of the lifecycle there is a need
for consistent results such that the modeling efforts can be leveraged in
those many applications.
Accurate thermophysical properties of fluids are essential for design and
operation in the chemical process industries. The need of having a good
thermophysical model is widely recognized in this context. All process
models rely on physical properties to represent the behavior of unit
operations, and the transformations that process streams undergo in a
process. Properties are calculated from models created and fine-tuned
to mimic the behaviour of the process substances at the operating
conditions
COMThermo is a complete thermodynamics package that encompasses
property methods, flash calculations, property databases, and property
estimation. The package is fully componentized, and therefore fully
extensible to the level of detail that allows the user to utilize,
supplement, or replace any of the components. The objective of this
package is to improve the engineering workflow by providing an open
structure that can be used in many different software applications and
obtain consistent results.
1-2
Introducing COMThermo
1-3
1-3
1-4
1-4
Introduction
Thermodynamic Principles
2-1
2 Thermodynamic Principles
2.1 Introduction......................................................................................3
2.2 Chemical Potential & Fugacity .......................................................6
2.3 Chemical Potential for Ideal Gas....................................................6
2.4 Chemical Potential & Fugacity for a Real Gas ..............................8
2.5 Fugacity & Activity Coefficients.....................................................9
2.6 Henrys Law....................................................................................11
2.6.1 Non-Condensable Components .............................................13
2.6.2 Estimation of Henrys constants .............................................13
2.7 Gibbs-Duhem Equation.................................................................15
2.7.1 Simplifications on Liquid Fugacity using Activity Coeff...........17
2.8 Association in Vapour Phase - Ideal Gas ....................................19
2.9 Equilibrium Calculations...............................................................23
2.10 Basic Models for VLE & LLE.......................................................24
2.10.1
2.10.2
2.10.3
2.10.4
2.10.5
2-1
2-2
2-2
Thermodynamic Principles
2-3
2.1 Introduction
To determine the actual state of a mixture defined by its components
and two intensive variables (usually pressure and temperature), a
unique set of conditions and equations defining equilibrium is required.
Consider a closed, multi-component and multi-phase system whose
phases are in thermal, mechanical, and mass transfer equilibrium. At
this state, the internal energy of the system is at a minimum, and any
variation in U at constant entropy and volume vanishes (1Prausnitz et al,
1986):
dU = TdS PdV
(2.1)
( dU ) S, V = 0
(2.2)
dU =
T
j=1
where:
dS
nc
P dV + i dni
j
j=1
(2.3)
j=1i=1
j = Phase (from 1 to )
i = Component (from 1 to nc)
ij = Chemical potential of component i in phase j, defined as
U
j
i =
ni S, V, n j
k1
(2.4)
2-3
2-4
Introduction
dS =
dS
= 0
(2.5)
j=1
dV
dV =
= 0
(2.6)
j=1
dni = 0
j
i = 1, ..., nc
(2.7)
j=1
dS = dS
1
(2.8)
j=2
dV = dV
1
(2.9)
j=2
dn i =
dni
j=2
2-4
(2.10)
Thermodynamic Principles
2-5
where:
nc
(T T ) dS
( P P ) dV +
( i i )dni
j>1
j>1
j > 1 i= 1
dU =
(2.11)
U
------- = 0
V
U
------- = 0
n i
2U
---------2 = 0
S
(2.12)
Therefore:
1
T = T
j = 2, ...,
(2.13)
Repeating the same argument for all of the independent variables, the
general conditions necessary for thermodynamic equilibrium between
heterogeneous phases are established (for all i):
T1 = T 2 =...=T
(2.14)
P1 = P 2 =...=P
(2.15)
i1 = i2 =...= i
(2.16)
From now on, it is assumed that Equations (2.14) and (2.15) are always
satisfied. The equilibrium condition established in Equation (2.16) will
be discussed in more detail. Note that the description of equilibrium
according to Equations (2.13), (2.14), (2.15), and (2.16) is at best
incomplete, since other intensive variables could be important in the
process being analysed. For example, the electric or magnetic fields in
the equations, or area affects are not being considered.
2-5
2-6
dG = SdT + VdP +
i dni
i=1
2-6
(2.17)
Thermodynamic Principles
2-7
where:
G
i =
n i T, P, n
(2.18)
k1
The chemical potential is the partial molar Gibbs free energy, since
partial molar properties are defined at constant P and T. Note that the
chemical potential is not the partial molar internal energy, enthalpy or
Helmholtz energy. Since a partial molar property is used, the following
holds:
dG i = S i dT + V i dP
(2.19)
where:
G
G i = -------
n i T, P, n
k1
(2.20)
(2.21)
2-7
2-8
(2.22)
fi = fi = = fi
(2.23)
Vi
( ln f ) = -----i
P
RT
T
(2.24)
2-8
Thermodynamic Principles
2-9
RTd ln f = VdP
(2.25)
ideal
(2.26)
RTd ln P = V
dP
ideal
f
)dP
RTd ln --- = ( V V
P
(2.27)
You integrate from 0 to P, noting that the behaviour of any real gas
approaches the behaviour of an ideal gas at sufficiently low pressures
(the limit of f/P as PJ0 = 1):
P
ln --f- =
P
ideal
- ------ -----RT RT
V
dP
(2.28)
f
ln --- =
P
(Z 1)
- dP
---------------P
(2.29)
The ratio f/P measures the deviation of a real gas from ideal gas
behaviour, and is called the fugacity coefficient:
f
= --P
(2.30)
2-9
2-10
fi
ln ------- =
Px i
( Zi 1 )
- dP
----------------P
(2.31)
ki
PV i
P V
= -------
= --------RT n i T, P, njk i
RT
(2.32)
fi
1
RT
ln ------- = ------- V i ------- dP
RT
P
Px i
(2.33)
(2.34)
V, pure
(2.35)
L, pure
(2.36)
fi = yi fi
fi = xi fi
where:
2-10
Thermodynamic Principles
2-11
The definition used by Lewis and Randall defines an ideal solution, not
the ideal gas behaviour for the fugacities. Therefore, the fugacities of
each pure component may be given by an accurate equation of state,
while the mixture assumes that different molecules do not interact.
Although very few mixtures actually obey ideal solution behaviour,
approximate equilibrium charts (nomographs) using the Lewis-Randall
rule were calculated in the 1940s and 50s, and were successfully used in
the design of hydrocarbon distillation towers.
Generalizing Equation (2.36) for an arbitrary standard state, the activity
coefficient for component i can written as:
fi
i = -------------------L, pure
fi
xi
(2.37)
fi
lim -------------------- = lim i = 1
,
L
pure
xi1 f
xi1
xi
i
(2.38)
However, the definition does not apply for components that cannot
exist as pure liquids at the conditions of the system. Sometimes, for
components like carbon dioxide at near ambient conditions, a
reasonably correct hypothetical liquid fugacity can be extrapolated. But
for components like hydrogen and nitrogen, this extrapolated liquid
behaviour has little physical significance.
2-11
2-12
Henrys Law
fi
lim ----------- = lim i = 1
ref
xi0 f x
xi 0
i
i
(2.39)
This equation implies that the fugacity of component i in a multicomponent mixture approaches the product of the mole fraction and
standard state fugacity in very dilute solutions of component i. Using
the definition of i* it can be shown that:
L
ref
fi
where:
f
= lim ---i- = H ij
xi0 xi
(2.40)
Therefore, the Henrys constant is the standard state fugacity for a noncondensable component in a specific solvent. Usually the Henrys
constant is a rather strong function of temperature, but a weak function
of the pressure and composition. The extension of Henrys law into
more concentrated solutions and at higher pressures is represented by
the Kritchevsky-Ilinskaya equation:
ln H ij =
where:
Pj
ln H ij
Sat
sat
A ij 2
Vi ( P Pj )
+ ------- ( x j 1 ) + -------------------------------RT
RT
(2.41)
2-12
Thermodynamic Principles
2-13
(2.42)
nc
j =1 , j i
ln H i, mixture = ---------------------------------------------2
nc
(2.43)
--3
x j V c, j
j =1 , j i
g = g + g
II
(2.44)
2-13
2-14
Henrys Law
L, pure
fi
I
g = RT ln --------------G
fi
g
II
(2.45)
= RT ln i x i
(2.46)
Since the gas dissolved in the liquid is in equilibrium with the gas in the
gas phase:
L, pure
(2.47)
fi = i xi fi
and therefore:
g = 0
(2.48)
(2.49)
RT ln i = i ( j i ) j
2 2
i ( j i ) j
fi
L, pure
H ij = ----- = f i
exp ---------------------------------RT
xi
(2.50)
i ( i j )
fi
L, pure
H ij = ----- = f i
exp ---------------------------RT
xi
2-14
(2.51)
Thermodynamic Principles
2-15
xi d ln i = 0
(2.52)
i=1
P
i
ref
P
i exp
ref
Vi
------- dP
RT
(2.53)
2-15
2-16
Gibbs-Duhem Equation
fi = i xi fi
ref
or
fi = i
ref
ref
x i f i exp
Vi
------- dP
RT
ref
(2.54)
The definition of the standard state fugacity now comes directly from
the Gibbs-Duhem equation using the normalization condition for a
condensable component; i.e., firef is the fugacity of component i in the
pure state at the mixture temperature and reference pressure
preference. The standard state fugacity can be conveniently represented
as a departure from the saturated conditions:
fi
ref
vap sat
Pi i
Pref
Vi
exp ------- dP
RT
Pvap
(2.55)
P
L
fi =
vap sat
Pi i
exp
ref
Vi Vi
------- + ------- dP
RT RT
vap
(2.56)
Pi
This equation is the basis for practically all low to moderate pressure
engineering equilibrium calculations using activity coefficients. The
exponential correction in Equations (2.54) and (2.55) is often called the
Poynting correction, and takes into account the fact that the liquid is at a
different pressure than the saturation pressure. The Poynting correction
at low to moderate pressures is very close to unity.
2-16
Thermodynamic Principles
2-17
Ideal Gas
When ideal gas behaviour is assumed, this usually implies that the
Poynting correction is dropped. Also, since the gas is ideal, isat = 1:
L
vap
(2.57)
vap
(2.58)
fi = i xi Pi
fi
ref
= Pi
vap sat
i xi Pi i
exp
vap
Vi
------ dP
RT
(2.59)
Pi
vap sat
i xi Pi i
exp
Vi
------ dP
RT
(2.60)
vap
Pi
2-17
2-18
Gibbs-Duhem Equation
vap
vap sat
i
fi = i xi Pi
Vi ( P Pi )
exp ------------------------------RT
(2.61)
vap
fi
ref
vap sat
i
= Pi
Vi ( P Pi )
exp ------------------------------RT
(2.62)
This is the equation used when taking into account vapour phase nonideality. Sometimes, Equation (2.60) is simplified even further,
assuming that the Poynting correction is equal to 1:
L
vap sat
i
fi = i xi Pi
fi
ref
vap sat
i
= Pi
(2.63)
(2.64)
Equations (2.57), (2.60) and (2.61) form the basis used to name several
of the activity coefficient based property packages.
2-18
Thermodynamic Principles
2-19
(2.65)
the equilibrium constant for the chemical reaction can be written as:
[ A2 ]
K = ----------2[A]
(2.66)
Assuming that the species in the vapour phase behave like ideal gases:
[ Pd ]
K = -------------2[ Pm ]
where:
(2.67)
(2.68)
2-19
2-20
e
y d = ----------2e
where:
(2.69)
PA yd
Pd
e( 2 e)
e(2 e)
- = ------------------------2- = --------------------------------- = ---------------------------------2K = -----2 vap
2
vap
vap
Pm
( 2 2e ) P A
4P A ( 1 e )
( PA ym )
(2.70)
e =
1
--------------------------vap
1 + 4KP A
(2.71)
PA
= Pm
+ Pd = Pm
+ K [ Pm
]
(2.72)
vap
1 + 4KP A 1
= ----------------------------------------Pm
2K
(2.73)
2-20
(2.74)
Thermodynamic Principles
2-21
Note that in the working equations the mole fraction of dimer is not
included. The associating substance is used when calculating the
number of moles in the vapour phase:
w A = n m M m + 2n d M m
where:
(2.75)
Dividing by Mm:
n A = n m + 2n d
(2.76)
Since there are nt total number of moles in the vapour phase, the mass
balance is expressed as:
x m + 2x d + x 2 = 1
where:
(2.77)
P A = P m + 2P d + P 2
where:
(2.78)
Knowing that:
P = Pm + Pd + P2
(2.79)
2-21
2-22
You have:
P m + 2P d
P m + 2P d
y A = ----------------------------------- = ----------------------P m + 2P d + P 2
P + Pd
(2.80)
vap
P2
P2
2 x2 P2
y 2 = ----------------------------------- = ---------------- = ---------------------P m + 2P d + P 2
P + Pd
P + Pd
(2.81)
P
L
f dimerizing = ---------------- P m ( 1 + 2KP m )
P + Pd
P
vap
L
f non d imerizing = ---------------- Pnon dimerizing
P + Pd
(2.82)
(2.83)
For example, NRTL-Dimer is the property package which uses NRTL for
the activity coefficient calculations and the carboxylic acid dimer
assuming ideal gas phase behaviour. The following carboxylic acids are
supported:
2-22
Formic Acid
Acetic Acid
Acrylic Acid
Propionic Acid
Butyric Acid
IsoButyric Acid
Valeric Acid
Hexanoic Acid
Thermodynamic Principles
2-23
(2.84)
(2.85)
(2.86)
fi = i yi P
fi = i xi P
and therefore:
L
i
K i = -----Vi
(2.87)
ref
f i = i x i P = i x i fi
(2.88)
and therefore:
ref
i fi
L
i = -----------P
(2.89)
2-24
2-24
Thermodynamic Principles
2-25
2-25
2-26
Temperature, F
Pressure, psia
PR
SRK
2-26
Thermodynamic Principles
2-27
TEG Dehydration
PR
PR, PRSV
Air Separation
PR, PRSV
Reservoir Systems
PR, PR Options
Kabadi Danner
2-27
2-28
The Property Package methods are divided into eight basic categories,
as shown in the following table. Listed with each of the property
methods are the available methods for VLE and Enthalpy/Entropy
calculations.
VLE Calculation
Enthalpy/Entropy
Calculation
PR
PR
PR
SRK
SRK
SRK
PRSV
PRSV
PRSV
Kabadi Danner
Kabadi Danner
SRK
RK-Zudekevitch-Joffee
RK-Zudekevitch-Joffee
RK-Zudekevitch-Joffee
Margules
Margules
Cavett
Van Laar
Van Laar
Cavett
Wilson
Wilson
Cavett
Property Method
Equations of State
Activity Models
Liquid
NRTL
NRTL
Cavett
UNIQUAC
UNIQUAC
Cavett
Chien Null
Chien Null
Cavett
Ideal Gas
Ideal Gas
Ideal Gas
Ideal Gas/Dimer
Ideal Gas/Dimer
Ideal Gas
RK
RK
RK
Peng Robinson
Peng Robinson
Peng Robinson
Virial
Virial
Virial
Vapour
2-28
Thermodynamic Principles
2-29
Ideal
The ideal gas law will be used to model the vapour phase. This model is
appropriate for low pressures and for a vapour phase with little
intermolecular interaction.
Henrys Law
For systems containing non-condensable components, you can supply
Henrys law information via the extended Henrys law equations.
The program considers the following components as noncondensable:
Component
Simulation Name
C1
Methane
C2
Ethane
C2=
Ethylene
C2#
Acetylene
H2
Hydrogen
He
Helium
Argon
Argon
N2
Nitrogen
O2
Oxygen
2-29
2-30
Component
Simulation Name
NitricOxide
Nitric Oxide
CO
Carbon Monoxide
CO2
Carbon Dioxide
H2S
Hydrogen Sulfide
(2.90)
2-30
Thermodynamic Principles
2-31
II
III
fi = fi = fi
(2.91)
= GG
ID
nc
fi
= RT x i ln i = RT x i ln ------------ref
xi fi
i=1
(2.92)
P, E
xi Gi
P
xi G Ei;
(2.93)
j =1 i
2-31
2-32
Phase Stability
is smaller than:
np 1 nc
j =1
where:
P, E
xi Gi
(2.94)
np = number of phases
The former condition is more stable than the latter one. If GE for two
phases is smaller than GE for one phase, then a solution with two phases
is more stable than the solution with one. This is represented
graphically as shown in the following figures.
Figure 2.1
2-32
Thermodynamic Principles
2-33
Figure 2.2
G1
dG1
dx
0.5
xi
0.5
xi
If you have a binary mixture of bulk composition xi, the Gibbs Free
Energy of the mixture will be G1 = Gixi + Gjxj. If you consider that two
phases can exist, the mass and energy balance tells us that:
I
xi xi
= ---------------II
I
xi xi
where:
G G
= -------------------I
II
G G
and
(2.95)
Therefore, (G2, xi), (GI, xiI) and (GII, xiII) are co-linear points and you can
calculate G2 = GI + (1-)GII.
where:
G = G ( x i , x j , P, T )
II
II
II
II
= G ( x i , x j , P, T )
(2.96)
x i T, P
and
G 1
= 0
2
x i T, P
(2.97)
2-33
2-34
Phase Stability
If you use
= GG
ID
nc
= RT x i ln i
(2.98)
i=1
and you use the simple Margules one-parameter expression, you have:
G = G
G
ID
ID
+G
= G
ID
+ Ax i x j
(2.99)
xi Gi + RTxi ln xi + RTxj ln xj
and
G =
xi Gi + RT ( xi ln xi + xj ln xj ) + Axi xj
xi
G
= A 2Ax i + RT ln ---- + G i G j
x i T, P
xj
(2.100)
G
T
= 2A + R -------
xj xi
x i T, P
G
RT
= 2A + -------- < 0
xj xi
x i T, P
(2.101)
RT
--------
- > 2 . A similar
minimum value of A for which phase splitting occurs is -----RT
analysis can be performed for the other activity coefficient models for
the binary case. The multi-component problem is more complex and
useful discussions can be found in the book by 3Modell and Reid (1983)
and in the works of 4Michelsen (1982) and 5Seider (1979).
2-34
Thermodynamic Principles
2-35
PV = RT
where:
or
RT
V = ------P
(2.102)
erm
Isoth
erm
Isoth
Isobar 1
Ideal Gas
Pressure
Isobar 2
Enthalpy
2-35
2-36
A A = P dV
(2.103)
A A = P dV
P dV
(2.104)
The second integral refers to the ideal gas, and can be immediately
evaluated:
RT
P = ------V
and
P dV =
RT
- dV
-----V
(2.105)
It is interesting to note that A-Ao for an ideal gas is not zero. The A-Ao
V
RT
term can be rearranged by adding and subtracting ------- dV and the final
V
result is:
V
RT
V
A A = P ------- dV RT ln -----
V
V
(2.106)
S S =
( A A ) V =
T
V
P R
--- dV + R ln ----- T V V
V
H H = ( A A ) + T ( S S ) + RT ( Z 1 )
2-36
(2.107)
Thermodynamic Principles
2-37
H
Cp =
T P
C p = T V
P T
T2 P
and
2
(2.108)
V
dC p = T 2 dP
T P
V
C p C p = T 2 dP
T P
P
or
P 2
T ------
P
T V
C p C p = T 2 dV ------------------- R
P
T V
----
T T
V
(2.109)
mix
nc
xi Ii
(2.110)
i=1
2-37
2-38
T
L
Hi
nc
Cp i dT
and
H =
T, ref
xi Hi
+ H mix
(2.111)
i=1
where:
(2.112)
2-38
Thermodynamic Principles
2-39
Molar Enthalpy H
A
re
ressu
P
ero
at Z
r
u
Vapo
Heat of
Vapourization
P =
as)
l G
a
e
d
0 (I
C
P =
m P
Syste
D
pressure to
compress the
liquid
T
Absolute Temperature T
Tc
Critical Temperature
2-39
2-40
2-40
3-1
3 Thermodynamic Calculation
Models
3.1 Equations of State ...........................................................................2
3.1.1 Ideal Gas Equation of State .....................................................3
3.1.2 Peng-Robinson Equation of State ............................................7
3.1.3 HysysPR Equation of State ....................................................16
3.1.4 Peng-Robinson Stryjek-Vera ..................................................24
3.1.5 Soave-Redlich-Kwong Equation of State ...............................35
3.1.6 Redlich-Kwong Equation of State...........................................44
3.1.7 Zudkevitch-Joffee Equation of State ......................................53
3.1.8 Kabadi-Danner Equation of State...........................................61
3.1.9 The Virial Equation of State....................................................72
3.1.10 Lee-Kesler Equation of State ...............................................87
3.1.11 Lee-Kesler-Plcker ...............................................................91
3.2 Activity Models ..............................................................................93
3.2.1 Ideal Solution Model...............................................................96
3.2.2 Regular Solution Model ........................................................100
3.2.3 van Laar Model.....................................................................104
3.2.4 Margules Model.................................................................... 115
3.2.5 Wilson Model........................................................................122
3.2.6 NRTL Model .........................................................................132
3.2.7 HypNRTL Model...................................................................144
3.2.8 The General NRTL Model ....................................................145
3.2.9 HYSYS - General NRTL.......................................................147
3.2.10 UNIQUAC Model ................................................................148
3.2.11 UNIFAC Model....................................................................158
3.2.12 Chien-Null Model................................................................169
3.3 Chao-Seader Model .....................................................................178
3.4 Grayson-Streed Model ................................................................179
3-1
3-2
Equations of State
3-2
3-3
(3.1)
The Ideal Gas equation, while very useful in some applications and as a
limiting case, is restricted from the practical point of view. The primary
drawbacks of the ideal gas equation stem from the fact that in its
derivation two major simplifications are assumed:
Figure 3.1
1.
2.
For further information on the derivation of the Ideal Gas law from first
principles, see 8Feynman (1966).
3-3
3-4
Equations of State
Property Methods
A quick reference of calculation methods is shown in the table below for
Ideal Gas.
Calculation Method
Applicable Phase
Molar Volume
Vapour
COTHIGVolume Class
Enthalpy
Vapour
COTHIGEnthalpy Class
Entropy
Vapour
COTHIGEntropy Class
Vapour
COTHIGCp Class
Vapour
COTHIGLnFugacityCoeff Class
Fugacity calculation
Vapour
COTHIGLnFugacity Class
The calculation methods from the table are described in the following
sections.
IG Molar Volume
The following relation calculates the Molar Volume for a specific phase.
RT
V = ------P
3-4
Applicable Phase
COTHIGVolume Class
Vapour
(3.2)
3-5
IG Enthalpy
The following relation calculates enthalpy.
xi Hi
IG
H =
where:
(3.3)
Applicable Phase
COTHIGEnthalpy Class
Vapour
IG Entropy
The following relation calculates entropy.
S =
where:
xi Si
IG
R x i ln x i
(3.4)
Applicable Phase
COTHIGEntropy Class
Vapour
3-5
3-6
Equations of State
IG Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
Cp =
where:
xi Cp
IG
i
(3.5)
Applicable Phase
COTHIGCp Class
Vapour
IG Fugacity Coefficient
The following relation calculates the fugacity coefficient.
ln i = 0
3-6
Applicable Phase
COTHIGLnFugacityCoeff Class
Vapour
(3.6)
3-7
IG Fugacity
The following relation calculates the fugacity for a specific phase.
(3.7)
fi = yi P
Applicable Phase
COTHIGLnFugacity Class
Vapour
(3.8)
where:
a = ac
2 2
R Tc
a c = 0.45724 -----------Pc
(3.9)
RT c
b = 0.077480 --------Pc
3-7
3-8
Equations of State
= 1 + ( 1 Tr )
Principle of corresponding
states
First successful modification
for engineering - RK
The property that is usually
required for engineering
calculations is vapour
pressure.
The SRK and RK EOS
propose modifications which
improve the vapour pressure
calculations for relatively
simple gases and
hydrocarbons.
(3.10)
The accuracy of the PR and SRK equations of state are approximately the
same. However, the PR EOS represents the density of the liquid phase
more accurately due to the lower critical compressibility factor.
These equations were originally developed for pure components. To
apply the PR EOS to mixtures, mixing rules are required for the a and
b terms in Equation (3.2). Refer to the Mixing Rules section on the
mixing rules available.
Property Methods
A quick reference of calculation methods is shown in the table below for
the PR EOS.
Calculation Method
Applicable Phase
Z Factor
COTHPRZFactor Class
Molar Volume
COTHPRVolume Class
Enthalpy
COTHPREnthalpy Class
Entropy
COTHPREntropy Class
COTHPRCp Class
COTHPRLnFugacityCoeff Class
Fugacity calculation
COTHPRLnFugacity Class
COTHPRCv Class
Mixing Rule 1
COTHPRab_1 Class
Mixing Rule 2
COTHPRab_2 Class
Mixing Rule 3
COTHPRab_3 Class
Mixing Rule 4
COTHPRab_4 Class
Mixing Rule 5
COTHPRab_5 Class
Mixing Rule 6
COTHPRab_6 Class
The calculation methods from the table are described in the following
sections.
3-8
3-9
PR Z Factor
The compressibility factor, Z, is calculated as the root for the following
equation:
3
Z ( 1 B )Z + Z ( A 3B 2B ) ( AB B B ) = 0
(3.11)
aP
A = ----------2 2
R T
(3.12)
bP
B = ------RT
(3.13)
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
PR Molar Volume
The following relation calculates the molar volume for a specific phase.
ZRT
V = ----------P
(3.14)
Applicable Phase
COTHPRVolume Class
3-9
3-10
Equations of State
PR Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
da
+ b(1 + 2)
= PV RT a ------ T ------------- ln V
dT 2 2b ---------------------------------V + b(1 2)
(3.15)
Applicable Phase
COTHPREnthalpy Class
PR Entropy
The following relation calculates the entropy.
SS
where:
3-10
IG
Vb
1
V + b ( 1 + 2 ) da
= R ln ------------ ------------- ln ---------------------------------- ----- RT 2b 2 V + b ( 1 2 ) dT
(3.16)
3-11
Applicable Phase
COTHPREntropy Class
PR Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
V
T ------
T P
2 P
= T --------2- dV + R + ------------------ T V
V
------
P T
2
IG
Cp Cp
where:
(3.17)
Applicable Phase
COTHPRCp Class
3-11
3-12
Equations of State
PR Fugacity Coefficient
The following relation calculates the fugacity coefficient.
a
V + b(1 + 2)
a b
b
ln i = ln ( V b ) + ------------ + ------------- ln ---------------------------------- 1 + --- + ---
a b
V b 2 2b V + b ( 1 2 )
(3.18)
n a
a = -----------n
(3.19)
nb
b = --------n
(3.20)
Applicable Phase
COTHPRLnFugacityCoeff Class
PR Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
3-12
(3.21)
3-13
Applicable Phase
COTHPRLnFugacity Class
PR Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
(3.22)
Applicable Phase
COTHPRCv Class
Mixing Rules
The mixing rules available for the PR EOS state are shown below.
nc
a =
nc
( xi xj aij )
(3.23)
i =1 j =1
nc
b =
bi xi
(3.24)
i =1
3-13
3-14
Equations of State
a ij = ij a ci a cj i j
(3.25)
0.5
i = ( 1 i ) ( 1 T ri )
2
(3.26)
0.45724R T ci
a ci = --------------------------------P ci
(3.27)
0.07780RT ci
b i = ------------------------------P ci
(3.28)
i < 0.49
(3.29)
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
where:
(3.30)
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
where:
3-14
(3.31)
3-15
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as
2
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
(3.32)
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
(3.33)
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ij = 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where:
(3.34)
3-15
3-16
Equations of State
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
C ij
C ij
A + B T + ------ A + B ji T + -------
ij
ij
T ji
T
= 1 ----------------------------------------------------------------------------------------------------C
C ji
ij
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.35)
RT
a
P = ------------ ------------------------------------------------V b V(V + b) + b(V b)
(3.36)
where:
a = ac
2 2
R Tc
a c = 0.45724 -----------Pc
RT c
b = 0.077480 --------Pc
3-16
(3.37)
3-17
0.5
= 1 + S ( 1 Tr )
(3.38)
Property Methods
A quick reference of calculation methods is shown in the table below for
the HysysPR EOS.
Calculation Method
Applicable Phase
Z Factor
COTH_HYSYS_ZFactor Class
Molar Volume
COTH_HYSYS_Volume Class
Enthalpy
COTH_HYSYS_PREnthalpy Class
Entropy
COTH_HYSYS_Entropy Class
COTH_HYSYS_Cp Class
Fugacity coefficient
calculation
COTH_HYSYS_LnFugacityCoeff Class
Fugacity calculation
COTH_HYSYS_LnFugacity Class
COTH_HYSYS_Cv Class
The calculation methods from the table are described in the following
sections.
HysysPR Z Factor
The compressibility factor, Z, is calculated as the root for the following
equation:
3
Z ( 1 B )Z + Z ( A 3B 2B ) ( AB B B ) = 0
aP
A = ----------2 2
R T
(3.39)
(3.40)
3-17
3-18
Equations of State
bP
B = ------RT
(3.41)
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
(3.42)
Applicable Phase
COTH_HYSYS_Volume Class
3-18
3-19
HysysPR Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
da
+ b(1 + 2)
= PV RT a ------ T ------------- ln V
dT 2 2b ---------------------------------V + b(1 2)
(3.43)
Applicable Phase
COTH_HYSYS_Enthalpy Class
3-19
3-20
Equations of State
HysysPR Entropy
The following relation calculates the entropy.
SS
where:
IG
Vb
1
V + b ( 1 + 2 ) da
= R ln ------------ ------------- ln ---------------------------------- ----- RT 2b 2 V + b ( 1 2 ) dT
(3.44)
Applicable Phase
COTH_HYSYS_Entropy Class
V
T ------
T P
2 P
= T --------2- dV + R + ------------------ T V
V
------
P T
V
IG
Cp Cp
3-20
(3.45)
where:
3-21
Applicable Phase
COTH_HYSYS_Cp Class
(3.46)
n a
a = -----------n
(3.47)
nb
b = --------n
(3.48)
3-21
3-22
Equations of State
Applicable Phase
COTH_HYSYS_LnFugacityCoeff Class
HysysPR Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.49)
Applicable Phase
COTH_HYSYS_LnFugacity Class
HysysPR Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
3-22
(3.50)
3-23
Applicable Phase
COTH_HYSYS_Cv Class
Mixing Rules
The mixing rules available for the HysysPR EOS state are shown below.
nc
a =
nc
( xi xj aij )
(3.51)
i =1 j =1
nc
b =
bi xi
(3.52)
i =1
a ij = ( 1 k ij ) a ci a cj i j
0.5
i = ( 1 i ) ( 1 T ri )
2
(3.53)
(3.54)
0.45724R T ci
a ci = --------------------------------P ci
(3.55)
0.07780RT ci
b i = ------------------------------P ci
(3.56)
3-23
3-24
Equations of State
i =
2
3
0.37964 + 1.48503 i 0.16442 i + 0.016666 i i 0.49
(3.57)
(3.58)
where:
a = ac
2 2
R Tc
a c = 0.45724 -----------Pc
RT c
b = 0.077480 --------Pc
3-24
(3.59)
3-25
i = [ 1 + i ( 1 Tr ) ]
0.5
(3.60)
i = 0i + 1 ( 1 + T ri ) ( 0.7 T ri )
2
The adjustable 1 parameter allows for a much better fit of the pure
component vapour pressure curves. This parameter has been regressed
against the pure component vapour pressure for all library components.
For hypocomponents that have been generated to represent oil
fractions, the 1 term for each hypocomponent will be automatically
regressed against the Lee-Kesler vapour pressure curves. For individual
user-added hypothetical components, 1 terms can either be entered or
they will automatically be regressed against the Lee-Kesler, GomezThodos or Reidel correlations.
The second modification consists of a new set of mixing rules for
mixtures. To apply the PRSV EOS to mixtures, mixing rules are required
for the a and b terms in Equation (3.46). Refer to the Mixing Rules
section for the set of mixing rules applicable.
3-25
3-26
Equations of State
Property Methods
A quick reference of calculation methods is shown in the table below for
the PRSV EOS.
Calculation Method
Applicable Phase
Z Factor
COTHPRSVZFactor Class
Molar Volume
COTHPRSVVolume Class
Enthalpy
COTHPRSVEnthalpy Class
Entropy
COTHPRSVEntropy Class
COTHPRSVCp Class
Fugacity coefficient
calculation
COTHPRSVLnFugacityCoeff Class
Fugacity calculation
COTHPRSVLnFugacity Class
COTHPRSVCv Class
Mixing Rule 1
COTHPRSVab_1 Class
Mixing Rule 2
COTHPRSVab_2 Class
Mixing Rule 3
COTHPRSVab_3 Class
Mixing Rule 4
COTHPRSVab_4 Class
Mixing Rule 5
COTHPRSVab_5 Class
Mixing Rule 6
COTHPRSVab_6 Class
The calculation methods from the table are described in the following
sections.
PRSV Z Factor
The compressibility factor, Z, is calculated as the root for the following
equation:
3
Z ( 1 B )Z + Z ( A 3B 2B ) ( AB B B ) = 0
3-26
(3.61)
aP
A = ----------2 2
R T
(3.62)
bP
B = ------RT
(3.63)
3-27
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
(3.64)
Applicable Phase
COTHPRSVVolume Class
3-27
3-28
Equations of State
PRSV Enthalpy
The following relation calculates the enthalpy
HH
where:
IG
1
da
+ b(1 + 2)
= PV RT a ------ T ------------- ln V
dT 2 2b ---------------------------------V + b(1 2)
(3.65)
Applicable Phase
COTHPRSVEnthalpy Class
3-28
3-29
PRSV Entropy
The following relation calculates the entropy.
SS
where:
IG
Vb
1
V + b ( 1 + 2 ) da
= R ln ------------ ------------- ln ---------------------------------- ----- RT 2b 2 V + b ( 1 2 ) dT
(3.66)
Applicable Phase
COTHPRSVEntropy Class
P T
V
IG
Cp Cp
(3.67)
Applicable Phase
COTHPRSVCp Class
3-29
3-30
Equations of State
(3.68)
n a
a = -----------n
(3.69)
nb
b = --------n
(3.70)
Applicable Phase
COTHPRSVLnFugacityCoeff Class
PRSV Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
3-30
Applicable Phase
COTHPRSVLnFugacity Class
(3.71)
3-31
PRSV Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
(3.72)
Applicable Phase
COTHPRSVCv Class
Mixing Rules
The mixing rules available for the PRSV equation are shown below.
nc
a =
nc
( xi xj aij )
(3.73)
i =1 j = 1
nc
b =
bi xi
(3.74)
i =1
3-31
3-32
Equations of State
a ij = ( a ii a jj )
0.5
ij
(3.75)
0.5
i = ( 1 i ) ( 1 T ri )
2
(3.76)
0.45724R T ci
a i = --------------------------------P ci
(3.77)
0.07780RT ci
b i = ------------------------------P ci
(3.78)
0.5
i = i0+ i1 ( 1 + T ri )( 0.7 T ri )
2
(3.79)
(3.80)
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
where:
(3.81)
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
3-32
(3.82)
where:
3-33
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
(3.83)
3-33
3-34
Equations of State
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
(3.84)
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ij = 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where:
(3.85)
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
3-34
C ij
C ij
A + B T + ------ A + B ji T + -------
ij
ij
T ji
T
= 1 ----------------------------------------------------------------------------------------------------C
C ji
ij
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.86)
3-35
(3.87)
R Tc
a c = a -----------Pc
(3.88)
0.5
= 1 + S ( 1 Tr )
S = 0.480 + 1.574 0.176
To apply the SRK EOS to mixtures, mixing rules are required for the a
and b terms in Equation (3.270).
3-35
3-36
Equations of State
Property Methods
A quick reference of calculation methods is shown in the table below for
the SRK EOS.
Calculation Method
Applicable Phase
Z Factor
COTHSRKZFactor Class
Molar Volume
COTHSRKVolume Class
Enthalpy
COTHSRKEnthalpy Class
Entropy
COTHSRKEntropy Class
COTHSRKCp Class
COTHSRKLnFugacityCoeff
Class
Fugacity calculation
COTHSRKLnFugacity Class
COTHSRKCv Class
Mixing Rule 1
COTHSRKab_1 Class
Mixing Rule 2
COTHSRKab_2 Class
Mixing Rule 3
COTHSRKab_3 Class
Mixing Rule 4
COTHSRKab_4 Class
Mixing Rule 5
COTHSRKab_5 Class
Mixing Rule 6
COTHSRKab_6 Class
The calculation methods from the table are described in the following
sections.
SRK Z Factor
The compressibility factor is calculated as the root for the following
equation:
Z Z + Z ( A B B ) AB = 0
(3.89)
aP
A = ----------2 2
R T
(3.90)
bP
B = ------RT
(3.91)
3-37
It is considered that the smallest root is for the liquid phase and the
largest root is for the vapour phase. The third root has no physical
meaning.
(3.92)
Applicable Phase
COTHSRKVolume Class
SRK Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
a
V
= PV RT + --- a T ------ ln ------------b
T V + b
(3.93)
Applicable Phase
COTHSRKEnthalpy Class
3-37
3-38
Equations of State
SRK Entropy
The following relation calculates the entropy.
SS
where:
IG
V b 1 a
V+b
= R ln ------------ --- ------ ln -------------
RT b T V
(3.94)
Applicable Phase
COTHSRKEntropy Class
3-38
3-39
P T
2
IG
Cp Cp
(3.95)
Applicable Phase
COTHSRKCp Class
a b a
V+b
b
ln i = ln ( V b ) + ------------ + ---------- --- --- 1 ln -------------
V b RTb b a V
2
(3.96)
n a
a = -----------n
(3.97)
nb
b = --------n i
(3.98)
Applicable Phase
COTHSRKLnFugacityCoeff Class
3-39
3-40
Equations of State
SRK Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.99)
Applicable Phase
COTHSRKLnFugacity Class
SRK Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
3-40
Applicable Phase
COTHSRKCv Class
(3.100)
3-41
Mixing Rules
The mixing rules available for the SRK EOS state are shown below.
nc
a =
nc
( xi xj aij )
(3.101)
i =1 j =1
nc
b =
bi xi
(3.102)
i =1
a ij = ij a ci a cj i j
(3.103)
0.5
i = 1 ij ( 1 T ri )
2
(3.104)
0.42748R T ci
a ci = --------------------------------P ci
(3.105)
0.08664RT ci
b i = ------------------------------P ci
(3.106)
(3.107)
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
(3.108)
3-41
3-42
Equations of State
where:
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
where:
(3.109)
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
(3.110)
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
3-42
(3.111)
3-43
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
ij
where:
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
= 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
(3.112)
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
C ij
C ij
A + B T + ------ A ji + B ji T + -------
ij
ij
T
T
= 1 ----------------------------------------------------------------------------------------------------C ij
C ji
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.113)
3-43
3-44
Equations of State
(3.114)
a = 0.42748
b = 0.08664
2.5
2 Tc
a = a R --------Pc
Tc
b = b R ----Pc
3-44
(3.115)
3-45
when T r = 0.7
(3.116)
In this way, one may consider developing an equation of state using Tc,
Pc, and as correlating parameters.
To apply the RK EOS to mixtures, mixing rules are required for the a
and b terms in Equation (3.64). Refer to the Mixing Rules section for
the set of mixing rules applicable.
3-45
3-46
Equations of State
Property Methods
A quick reference of calculation methods is shown in the table below for
the RK EOS.
Calculation Method
Applicable Phase
Z Factor
COTHRKZFactor Class
Molar Volume
COTHRKVolume Class
Enthalpy
COTHRKEnthalpy Class
Entropy
COTHRKEntropy Class
COTHRKCp Class
COTHRKLnFugacityCoeff Class
Fugacity calculation
COTHRKLnFugacity Class
COTHRKCv Class
Mixing Rule 1
COTHRKab_1 Class
Mixing Rule 2
COTHRKab_2 Class
Mixing Rule 3
COTHRKab_3 Class
Mixing Rule 4
COTHRKab_4 Class
Mixing Rule 5
COTHRKab_5 Class
Mixing Rule 6
COTHRKab_6 Class
The calculation methods from the table are described in the following
sections.
RK Z Factor
The compressibility factor is calculated as the root for the following
equation:
Z Z + Z ( A B B ) AB = 0
(3.117)
aP
A = ----------2 2
R T
(3.118)
bP
B = ------RT
(3.119)
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
3-46
3-47
RK Molar Volume
The following relation calculates the molar volume for a specific phase.
ZRT
V = ----------P
(3.120)
Applicable Phase
COTHRKVolume Class
RK Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
a
V
= PV RT + --- a T ------ ln ------------b
T V + b
(3.121)
Applicable Phase
COTHRKEnthalpy Class
3-47
3-48
Equations of State
RK Entropy
The following relation calculates the entropy.
SS
where:
IG
V+b
V b 1 a
= R ln ------------ --- ------ ln -------------
RT b T V
(3.122)
Applicable Phase
COTHRKEntropy Class
RK Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
V 2
T ------
P
T P
= T --------2- dV + R + ------------------ T V
V
------
P T
V
IG
Cp Cp
3-48
Applicable Phase
COTHRKCp Class
(3.123)
3-49
RK Fugacity Coefficient
The following relation calculates the fugacity coefficient.
V+b
a b a
b
ln i = ln ( V b ) + ------------ + ---------- --- --- 1 ln -------------
V b RTb b a V
2
(3.124)
n a
a = -----------n
(3.125)
nb
b = --------n i
(3.126)
Applicable Phase
COTHRKLnFugacityCoeff Class
RK Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.127)
Applicable Phase
COTHRKLnFugacity Class
3-49
3-50
Equations of State
RK Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
(3.128)
Applicable Phase
COTHRKCv Class
Mixing Rules
The mixing rules available for the RK EOS state are shown below.
nc
a =
nc
( xi xj aij )
(3.129)
i =1 j =1
nc
b =
bi xi
(3.130)
i =1
a ij = ij a i a j
(3.131)
2
2.5
0.42748R T ci
a i = ----------------------------------P ci T
3-50
(3.132)
0.08664RT ci
b i = ------------------------------P ci
3-51
(3.133)
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
where:
(3.134)
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
where:
(3.135)
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
(3.136)
3-51
3-52
Equations of State
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
(3.137)
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ij = 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where:
(3.138)
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
3-52
C ij
C ij
A + B T + ------ A + B ji T + -------
ij
ij
T ji
T
= 1 ----------------------------------------------------------------------------------------------------C
C ji
ij
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.139)
3-53
(3.140)
To apply the ZJ EOS to mixtures, mixing rules are required for the a
and b terms in Equation (3.84). Refer to the Mixing Rules section for
the set of mixing rules applicable.
Property Methods
A quick reference of calculation methods is shown in the table below for
the ZJ EOS.
Calculation Method
Applicable Phase
Z Factor
COTHZJZFactor Class
Molar Volume
COTHZJVolume Class
Enthalpy
COTHZJEnthalpy Class
Entropy
COTHZJEntropy Class
COTHZJCp Class
COTHZJLnFugacityCoeff Class
Fugacity calculation
COTHZJLnFugacity Class
COTHZJCv Class
Mixing Rule 1
COTHZJab_1 Class
Mixing Rule 2
COTHZJab_2 Class
Mixing Rule 3
COTHZJab_3 Class
3-53
3-54
Equations of State
Calculation Method
Applicable Phase
Mixing Rule 4
COTHZJab_4 Class
Mixing Rule 5
COTHZJab_5 Class
Mixing Rule 6
COTHZJab_6 Class
The calculation methods from the table are described in the following
sections.
ZJ Z Factor
The compressibility factor is calculated as the root for the following
equation:
3
Z Z + Z ( A B B ) AB = 0
(3.141)
aP
A = ----------2 2
R T
(3.142)
bP
B = ------RT
(3.143)
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
ZJ Molar Volume
The following relation calculates the molar volume for a specific phase.
ZRT
V = ----------P
3-54
Applicable Phase
COTHZJVolume Class
(3.144)
3-55
ZJ Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
a
V
= PV RT + --- a T ------ ln -----------b
T V + b
(3.145)
Applicable Phase
COTHLeeKeslerEnthalpy Class
ZJ Entropy
The following relation calculates the entropy.
SS
where:
IG
V b 1 a
V+b
= R ln ------------ --- ------ ln -------------
RT b T V
(3.146)
3-55
3-56
Equations of State
Applicable Phase
COTHLeeKeslerEntropy Class
ZJ Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
V
T ------
T P
2 P
= T --------2- dV + R + ------------------ T V
V
------
P T
2
IG
Cp Cp
(3.147)
Applicable Phase
COTHLeeKeslerCp Class
ZJ Fugacity Coefficient
The following relation calculates the fugacity coefficient:
V+b
a b a
b
ln i = ln ( V b ) + ------------ + ---------- --- --- 1 ln -------------
V b RTb b a V
(3.148)
n a
a = -----------n
3-56
(3.149)
nb
b = --------n i
3-57
(3.150)
Applicable Phase
COTHZJLnFugacityCoeff Class
ZJ Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.151)
Applicable Phase
COTHZJLnFugacity Class
ZJ Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
(3.152)
3-57
3-58
Equations of State
Applicable Phase
COTHZJCv Class
Mixing Rules
The mixing rules available for the ZJ EOS state are shown below.
nc
nc
( xi xj aij )
a =
(3.153)
i =1 j = 1
nc
bi xi
b =
(3.154)
i =1
a ij = ij a i a j i j
i sub c ritical= 1 +
k=1
Pr
D k ln ----- ln 10
Tr
k+1
-----------2
sat
Pr = Pi
(3.155)
10
Pr
- ln 10
Dk ln ---Tr
k1
(3.156)
k=3
P ci
(3.157)
ln super critical = 2M 1 ( 1 T r
(3.158)
With M1 and M2 determined at 0.9Tc to match the value and slope of the
vapour pressure curve (14Mathias, 1983):
1 d
M 1 M 2 = --- --------
2 dTr 0.9T c
3-58
(3.159)
M1 1
M 2 = ---------------M1
2
3-59
(3.160)
0.42748R T ci
a ci = --------------------------------P ci
(3.161)
0.08664RT ci
b i = ------------------------------P ci
(3.162)
(3.163)
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
where:
(3.164)
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
where:
(3.165)
3-59
3-60
Equations of State
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
(3.166)
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
(3.167)
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ij = 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where:
3-60
(3.168)
3-61
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
C ij
C ij
A + B T + ------ A + B ji T + -------
ij
ij
T ji
T
= 1 ----------------------------------------------------------------------------------------------------C
C ji
ij
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.169)
(3.170)
3-61
3-62
Equations of State
The KD equation of state is similar to the SRK equation of state, with the
following modifications:
0.315
k iw = 0.3325 + 0.061667Watson
0.5
where:
(3.171)
3 T
b
Watson = ---------SG
(3.172)
f 1 SG + f 2 SG
(3.174)
f 1 = C 1 + C 2 ln T b ( R )
(3.175)
f 2 = C 3 + C 4 ln T b ( R )
(3.176)
SG = e
G 1.358
-------------------------- 426 1.358
3-62
(3.173)
a5
5 ( SG SG )
N gv + a 6 F
1
= ----- ln ---------------------------
a 4 N gv F
(3.177)
(3.178)
3-63
a4
1 + a6 e
N gv = ----------------------- a4
1e
(3.179)
a1
a1
1 + a3 e
1e
-------------------------F = -----------------------a1
a1
1 + a3 e
1e
(3.180)
T b 200.99 a2
= ----------------------------------
2000 200.99
(3.181)
Coefficients
a1 = 0.405040
a6 = -0.958481
a2 = 1.99638
c1 = -0.178530
a3 = 34.9349
c2 = 1.41110
a4 = 0.507059
c3 = 0.237806
a5 = 1.2589
c4 = -1.97726
12
Tb
= 1 ----Tc
T b 13
Tb
3
7 2
10 3
-------- = 0.533272 + 0.191017 10 T b + 0.779681 10 T b 0.284376 10 T b + 95.9468 ---------
100
Tc
(3.182)
(3.183)
(3.184)
To apply the KD EOS to mixtures, mixing rules are required for the a
and b terms in Equation (3.170). Refer to the Mixing Rules section for
the applicable set of mixing rules.
3-63
3-64
Equations of State
Property Methods
A quick reference of calculation methods is shown in the table below for
the KD EOS.
Calculation Method
Applicable Phase
Z Factor
COTHKDZFactor Class
Molar Volume
COTHKDVolume Class
Enthalpy
COTHKDEnthalpy Class
Entropy
COTHKDEntropy Class
COTHKDCp Class
COTHKDLnFugacityCoeff Class
Fugacity calculation
COTHKDLnFugacity Class
COTHKDCv Class
Mixing Rule 1
COTHKDab_1 Class
Mixing Rule 2
COTHKDab_2 Class
Mixing Rule 3
COTHKDab_3 Class
Mixing Rule 4
COTHKDab_4 Class
Mixing Rule 5
COTHKDab_5 Class
Mixing Rule 6
COTHKDab_6 Class
The calculation methods from the table are described in the following
sections.
KD Z Factor
The compressibility factor is calculated as the root for the following
equation:
Z Z + Z ( A B B ) AB = 0
(3.185)
aP
A = ----------2 2
R T
(3.186)
bP
B = ------RT
(3.187)
3-64
3-65
There are three roots for the above equation. It is considered that the
smallest root is for the liquid phase and the largest root is for the vapour
phase. The third root has no physical meaning.
KD Molar Volume
The following relation calculates the molar volume for a specific phase.
ZRT
V = ----------P
(3.188)
Applicable Phase
COTHKDVolume Class
3-65
3-66
Equations of State
KD Enthalpy
The following relation calculates the enthalpy.
HH
where:
IG
1
a
V
= PV RT + --- a T ------ ln -----------b
T V + b
(3.189)
Applicable Phase
COTHKDEnthalpy Class
KD Entropy
The following relation calculates the entropy.
SS
where:
IG
V b 1 a
V+b
= R ln ------------ --- ------ ln -------------
RT b T V
(3.190)
Applicable Phase
COTHKDEntropy Class
3-66
3-67
KD Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
V 2
T ------
T P
P
= T --------2- dV + R + ------------------ T V
V
------
P T
V
IG
Cp Cp
(3.191)
Applicable Phase
COTHKDCp Class
KD Fugacity Coefficient
The following relation calculates the Fugacity Coefficient:
V+b
a b a
b
ln i = ln ( V b ) + ------------ + ---------- --- --- 1 ln -------------
V b RTb b a V
(3.192)
n a
a = -----------n
(3.193)
nb
b = --------n i
(3.194)
3-67
3-68
Equations of State
Applicable Phase
COTHKDLnFugacityCoeff Class
KD Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.195)
Applicable Phase
COTHKDLnFugacity Class
KD Cv (isochoric)
The following relation calculates the isochoric heat capacity.
P 2
T ------
T V
C v = C p + --------------------- P
------
V T
3-68
Applicable Phase
COTHKDCv Class
(3.196)
3-69
Mixing Rules
The mixing rules available for the KD EOS state are shown below.
nc
a =
nc
nc
( xi xj aij ) + ( xi xw ai)
2
i =1 j = 1
(3.197)
i =1
nc
b =
bi xi
(3.198)
i =1
a ij = ij a i a j i j
0.5
( 1 + i ) ( 1 T ri )
i =
0.8
1 + 0.662 ( 1 T rw
)
(3.199)
iw
(3.200)
i =w
0.42747R T ci
a i = --------------------------------P ci
(3.201)
0.08664RT ci
b i = ------------------------------P ci
(3.202)
G 1 T rw
a i = i
0.0
T < T cw
T T cw
(3.203)
(3.204)
3-69
3-70
Equations of State
Mixing Rule 1
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 A ij + B ij T + C ij T
where:
(3.205)
Mixing Rule 2
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ij
ij = 1 A ij + B ij T + ------T
where:
(3.206)
Mixing Rule 3
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij = 1 x i ( A ij + B ij + C ij T ) x j ( A ji + B ji T + C ji T )
3-70
(3.207)
3-71
Mixing Rule 4
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
C ji
C ij
ij = 1 x i A ij + B ij T + ------- x j A ji + B ji + -------
T
T
where:
(3.208)
Mixing Rule 5
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ij = 1 --------------------------------------------------------------------------------------------------------------2
2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where:
(3.209)
Mixing Rule 6
The definition of terms a and b are the same for all Mixing Rules. The
only difference between the mixing rules is the temperature dependent
binary interaction parameter, ij, which is defined as:
ij
where:
C ij
C ij
A + B T + ------ A + B ji T + -------
ij
ij
T ji
T
= 1 ----------------------------------------------------------------------------------------------------C
C ji
ij
x i A ij + B ij T + ------- + x j A ji + B ji T + -------
T
T
(3.210)
3-71
3-72
Equations of State
where:
(3.211)
Z = 1 + B + C + D +
(3.212)
and pressure:
Z = 1 + BP + CP + DP +
(3.213)
(3.214)
Z = B + 2C + 3D 2 +
T
(3.215)
3-72
(3.216)
3-73
3Z
D = lim 3
0
T
(3.217)
(3.218)
B = B
where:
(0)
+ B
(1)
(3.219)
3-73
3-74
Equations of State
B = B
where:
(0)
+ B
(1)
+B
(2)
(3.220)
10 P c
R = --------------------- 0.9869
Tc
where:
(3.221)
B ij = B ij + B ij
F
(3.222)
BijF, non-polar = Second virial coefficient contribution from the nonpolar part due to physical interactions
BijF, polar = Second virial coefficient contribution from the polar part
due to physical interactions
BijD, metastable = Second virial coefficient contribution due to the
formation of metastable compounds due to the "chemical"
(dimerization) reaction
BijD, bound = Second virial coefficient contribution due to the
formation of chemical bonds
BijD, chemical = Second virial coefficient contribution due to the
chemical reaction
3-74
3-75
T ij
T ij
T ij
(3.223)
F
0 *
3.0 2.1 2.1
B ij, polar = b ij ij 0.74 ------ + -------- + --------
*
*2
*3
T ij T ij
T ij
(3.224)
H ij
D
D
0
( B ij , metastable ) + ( B ij , bound ) = b ij A ij exp -----------
T ij
(3.225)
1500 ij
D
0
( B ij , chemical ) = b ij E ij 1 exp -------------------
(3.226)
3-75
3-76
Equations of State
where:
1
1
-----*- = -----*- 1.6 ij
T ij
T ij
*
T
T ij = ----------------( ij k )
0
b ij = 1.26184 ij ( cm gmol )
*
ij = ij
ij = 0
*
if ij < 0.04
ij = ij 0.25
if ij 0.25
*
A ij = 0.3 0.05 ij
*2
H ij = 1.99 + 0.2 ij
7243.8 i j
*
ij = -------------------------- -----ij 3
k ij
E ij
650
= exp ij -------------------------- 4.27
ij
+ 300
----k
42800
E ij = exp ij -------------------------------- 4.27
ij + 22400
----k
if ij < 4.5
if ij 4.5
k
k
2
i = i' ( 1 + C 2 )
13
i
----i = T 0.748 + 0.91 0.4 -------------------c, i
i
k
2 + 20 i
3-76
(3.227)
3-77
and
T c, i 1 3
i = ( 2.44 i ) 1.0133 ---------
P c, i
= 0
if i < 1.45
(3.228)
or
7 4
1.7941 10 i
= -----------------------------------------------------------------------------------
1.882 i
i
6
- T ' ----
2.882 --------------------0.03 + i c, i i k
if i 1.45
16 + 400 i
3
C 1 = --------------------------- and C 2 = --------------------------10 + 400 i
10 + 400 i
(3.229)
jj
-----ij = 0.7 -----ii ---- k
k k
1
--2
(3.230)
0.6
+ ------------------------------------1
1
------------ + ----------- ii k jj k
1
---
ij = ( ii jj ) 2
23
2 jj
4
u i ----- jj
k
= --------------------------------- -----ij 6
k ij
2 ii
4
u ----- ii
k
= -------------------------- -----ij 6
k ij
if i 2 and j = 0
(3.231)
if j 2 and i = 0
3-77
3-78
Equations of State
16 + 400 ij
3
C 1 = ----------------------------- and C 2 = ----------------------------10 + 400 ij
10 + 400 ij
(3.232)
Mixing Rules
For a multi-component mixture, it can be shown that Bmix is rigorously
calculated by:
B mix =
i j yi yj Bij
(3.233)
P
ln i = 2 yi B ij B mix ------ j
RT
3-78
(3.234)
3-79
(3.235)
f ij
Z ij ij
k ij = ------ = -------------------------fi fj Z Z # # P
j
i j i
where:
(3.236)
3-79
3-80
Equations of State
i Zi = i yi
where:
i Zi
i = ---------yi
or
(3.237)
Bi P
#
ln i = ---------RT
where:
(3.238)
(3.239)
and finally:
k ij
F P
exp B ij -------
RT
Z ij 1
= ---------- --- -----------------------------------------------------------Zi Zj P
F P
F P
exp B ii ------- exp B jj -------
RT
RT
(3.240)
B ij ( 2 ij )
k ij = -----------------------------RT
ij
where:
3-80
0
=
1
(3.241)
ij
i=j
3-81
Therefore:
k ij
F P
exp B ij -------
RT
Z ij 1
= ---------- --- -----------------------------------------------------------Zi Zj P
F P
F P
exp B ii ------- exp B jj -------
RT
RT
(3.242)
B ij ( 2 ij )
= -----------------------------RT
critical temperature
critical pressure
dipole moment
mean radius of gyration
association parameter
association parameter for each binary pair
3-81
3-82
Equations of State
T
P --2
yi Pc
i
i=1
-------------------m
yi Tc
(3.243)
i=1
Property Methods
A quick reference of calculation methods is shown in the table below for
the Virial EOS.
Calculation Method
Applicable Phase
Molar Volume
Vapour
COTHVirial_Volume Class
Enthalpy
Vapour
COTHVirial_Enthalpy Class
Entropy
Vapour
COTHVirial_Entropy Class
Vapour
COTHVirial_Cp Class
Fugacity coefficient
calculation
Vapour
COTHVirial_LnFugacityCoeff Class
Fugacity calculation
Vapour
COTHVirial_LnFugacity Class
Density
Vapour
COTHVirial_Density Class
Vapour
COTHVirial_Cv Class
Gibbs Energy
Vapour
COTHVirial_GibbsEnergy Class
Helmholtz Energy
Vapour
COTHVirial_HelmholtzEnergy Class
Z Factor
Vapour
COTHVirial_ZFactor Class
The calculation methods from the table are described in the following
sections.
3-82
3-83
(3.244)
Applicable Phase
COTHVirial_Volume Class
Vapour
Virial Enthalpy
The following relation calculates the enthalpy.
H H = A A + T ( S S ) + RT ( Z 1 )
(3.245)
Applicable Phase
COTHVirial_Enthalpy Class
Vapour
Virial Entropy
The following relation calculates the entropy.
( dB dT )
o
V
V
S S = RT ---------------------- R ln ------------- + R ln -----VB
VB
Vo
(3.246)
3-83
3-84
Equations of State
Applicable Phase
COTHVirial_Entropy Class
Vapour
T T
2
Cp Cp
(3.247)
Applicable Phase
COTHVirial_Cp Class
Vapour
P
ln i = 2 yi B ij B mix ------ j
RT
3-84
Applicable Phase
COTHVirial_LnFugacityCoeff Class
Vapour
(3.248)
3-85
Virial Fugacity
The following relation calculates the fugacity for a specific phase.
fi = i yi P
(3.249)
Applicable Phase
COTHVirial_LnFugacity Class
Virial Density
The following relation calculates the molar density for a specific phase.
P
= ----------ZRT
(3.250)
Applicable Phase
COTHVirial_Density Class
Virial Cv (isochoric)
The following relation calculates the isochoric heat capacity.
V
P
C v C v = T 2 dV
T
(3.251)
3-85
3-86
Equations of State
Applicable Phase
COTHVirial_Cv Class
(3.252)
Applicable Phase
COTHVirial_GibbsEnergy Class
Vapour
3-86
Applicable Phase
COTHVirial_HelmholtzEnergy Class
Vapour
(3.253)
3-87
Virial Z Factor
The following relation calculates the Z Factor.
B
Z = 1 + --V
(3.254)
Applicable Phase
COTHVirial_ZFactor Class
Vapour
Z = Z + ------r ( Z r Z )
where:
(3.255)
They chose the reduced form of the BWR EOS to represent both Z o and
Z r:
D
B C D
------2
V r
(3.256)
3-87
3-88
Equations of State
where:
VP c
V r = --------RT c
b2 b3 b4
B = b 1 ----- -----2 -----4
Tr T T
r
r
c2 c3
C = c 1 ----- + -----3
Tr Tr
d2
D = d 1 + ----Tr
Property Methods
A quick reference of calculation methods is shown in the table below for
the LK EOS.
Calculation Method
Applicable Phase
Enthalpy
COTHLeeKeslerEnthalpy Class
Entropy
COTHLeeKeslerEntropy Class
COTHLeeKeslerCp Class
The calculation methods from the table are described in the following
sections.
LK Enthalpy
The following relation calculates the enthalpy departure.
b3
b4
c3
d2
Tr
Tr
Tr
HH
-------------------- = T r Z 1 ------------------------------------- ------------------- --------------5- + 3E
2
RT c
Tr Vr
2T r V r
5T r V r
IG
3-88
(3.257)
3-89
where:
T
T r = ----Tc
(3.258)
V
V r = ----Vc
(3.259)
Applicable Phase
COTHLeeKeslerEnthalpy Class
LK Entropy
The following relation calculates the entropy departure.
b4
b3
c3
b 1 + -----2 + 2 -----3 c 1 3 -----2
S S
Tr
Tr
Tr d1
P
------------------- = ln Z ln ------ -------------------------------- ------------------- ---------2 + 2E
2
P
R
Vr
5V r
2V r
IG
(3.260)
where:
T
T r = ----Tc
(3.261)
V
V r = ----Vc
(3.262)
3-89
3-90
Equations of State
Applicable Phase
COTHLeeKeslerEntropy Class
LK Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
V 2
T ------
T P
2 P
= T --------2- dV + R + ------------------ T V
V
------
P T
V
IG
Cp Cp
3-90
Applicable Phase
COTHLeeKeslerCp Class
(3.263)
3-91
Mixing Rules
For mixtures, the Critical properties for the LK EOS state are defined as
follows.
N
xi i
i=1
z c = 0.2905 0.0851 i
i
Z c RT c
i
i
V c = ----------------i
Pc
i
1
V c = --8
i=1 j=1
1
T c = --------8V c
i=1 j=1
1 3
---
--33
x i x j V c + V c
j
i
1 3
---
--30.5
3
x i x j V c + V c ( T c T c )
j
i
j
i
RT c
P c = ( 0.2905 0.085 ) --------Vc
3.1.11 Lee-Kesler-Plcker
The Lee-Kesler-Plcker
equation does not use the
COSTALD correlation in
computing liquid density. This
may result in differences when
comparing results between
equation of states.
The Lee-Kesler-Plcker equation is an accurate general method for nonpolar substances and mixtures. 3Plcker et al, applied the Lee-Kesler
equation to mixtures, which itself was modified from the BWR equation.
z = z
(o)
(r) (o)
+ --------(z z )
(r)
(3.264)
(3.265)
C4
B C D
- + ----- exp ----2z = 1 + ---- + ----2- + ----5- + ---------3 2
2
vr vr vr Tr vr
vr
vr
(3.266)
3-91
3-92
Equations of State
where:
pc v
v r = --------RT c
b2 b3 b4
B = b 1 ----- -----2 -----3
Tr Tr Tr
c2 c3
C = c 1 ----- + -----2
Tr Tr
(o)
d
D = d 1 ----2Tr
= 0
(r)
= 0.3978
(3.267)
where:
Tc = ( Tc Tc )
ij
vc =
m
12
xi xj vc
i
Tc = Tc
ii
ij
Tc = Tc
jj
1 13
13 3
v c = --- ( v c + v c )
ij
j
8 i
RT c
v c = z c ----------i
i
i p
c
z c = 0.2905 0.085 i
RT c
p c = z c -----------mm
m v
c
z c = 0.2905 0.085 m
m =
xi i
i
3-92
3-93
(3.268)
3-93
3-94
Activity Models
Although for ideal solutions the activity coefficient is unity, for most
chemical (non-ideal) systems this approximation is incorrect.
Dissimilar chemicals normally exhibit not only large deviations from an
ideal solution, but the deviation is also found to be a strong function of
the composition. To account for this non-ideality, activity models were
developed to predict the activity coefficients of the components in the
liquid phase. The derived correlations were based on the excess Gibbs
energy function, which is defined as the observed Gibbs energy of a
mixture in excess of what it would be if the solution behaved ideally, at
the same temperature and pressure.
For a multi-component mixture consisting of ni moles of component i,
the total excess Gibbs free energy is represented by the following
expression:
where:
= RT ( n i ln i )
(3.269)
The individual activity coefficients for any system can be obtained from
a derived expression for excess Gibbs energy function coupled with the
Gibbs-Duhem equation. The early models (Margules, van Laar) provide
an empirical representation of the excess function that limits their
application. The newer models such as Wilson, NRTL and UNIQUAC
use the local composition concept and provide an improvement in their
general application and reliability. All of these models involve the
concept of binary interaction parameters and require that they be fitted
to experimental data.
Since the Margules and van Laar models are less complex than the
Wilson, NRTL and UNIQUAC models, they require less CPU time for
solving flash calculations. However, these are older and more
empirically based models and generally give poorer results for strongly
non-ideal mixtures such as alcohol-hydrocarbon systems, particularly
for dilute regions.
3-94
3-95
Margules
van Laar
Wilson
NRTL
UNIQUAC
Binary Systems
multi-component Systems
LA
LA
Azeotropic Systems
Liquid-Liquid Equilibria
N/A
Dilute Systems
Self-Associating Systems
Polymers
N/A
N/A
N/A
N/A
Extrapolation
Vapour phase non-ideality can be taken into account for each activity
model by selecting the Redlich-Kwong, Peng-Robinson or SRK
equations of state as the vapour phase model. When one of the
equations of state is used for the vapour phase, the standard form of the
Poynting correction factor is always used for liquid phase correction.
The binary parameters required for the activity models have been
regressed based on the VLE data collected from DECHEMA, Chemistry
Data Series. There are over 16,000 fitted binary pairs in the library. The
structures of all library components applicable for the UNIFAC VLE
estimation have been stored. The Poynting correction for the liquid
phase is ignored if ideal solution behaviour is assumed.
All of the binary parameters stored in the properties library have been
regressed using an ideal gas model for the vapour phase.
If you are using the built-in binary parameters, the ideal gas model
should be used. All activity models, with the exception of the Wilson
equation, automatically calculate three phases given the correct set of
energy parameters. The vapour pressures used in the calculation of the
standard state fugacity are based on the pure component library
coefficients using the modified form of the Antoine equation.
The internally stored binary parameters have NOT been regressed
against three-phase equilibrium data.
3-95
3-96
Activity Models
Property Methods
A quick reference of calculation methods is shown in the table below for
the Ideal Solution model.
Calculation Method
Applicable Phase
Activity coefficient
Liquid
COTHIdealSolLnActivityCoeff Class
Fugacity coefficient
Liquid
COTHIdealSolLnFugacityCoeff Class
Fugacity
Liquid
COTHIdealSolLnFugacity Class
Activity coefficient
differential wrt
temperature
Liquid
COTHIdealSolLnActivityCoeffDT Class
Enthalpy
Liquid
COTHIdealSolEnthalpy Class
Gibbs energy
Liquid
COTHIdealSolGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
3-96
(3.270)
3-97
Applicable Phase
COTHIdealSolLnActivityCoeff Class
Liquid
f i
ln i = ln --------
P
where:
(3.271)
i = 1
P = pressure
fi = standard state fugacity
Applicable Phase
COTHIdealSolLnFugacityCoeff Class
Liquid
For the standard fugacity, fi std, refer to Section 5.4 - Standard State
Fugacity.
3-97
3-98
Activity Models
(3.272)
ln f i = ln ( x i f i )
where:
i = 1
fi std = standard state fugacity
xi = mole fraction of component i
Applicable Phase
COTHIdealSolLnFugacity Class
Liquid
For the standard fugacity, fi std, refer to Section 5.4 - Standard State
Fugacity.
3-98
(3.273)
3-99
Applicable Phase
COTHIdealSolLnActivityCoeffDT Class
Liquid
G =
xi Gi + RT xi ln xi
i
where:
(3.274)
Applicable Phase
COTHIdealSolGibbsEnergy Class
Liquid
H =
xi Hi
(3.275)
where:
3-99
3-100
Activity Models
Applicable Phase
COTHIdealSolEnthalpy Class
Liquid
Property Methods
A quick reference of calculation methods is shown in the table below for
the Regular Solution activity model.
Calculation Method
Applicable
Phase
Fugacity coefficient
Liquid
COTHRegSolLnFugacityCoeff Class
Activity coefficient
Liquid
COTHRegSolLnActivityCoeff Class
Fugacity
Liquid
COTHRegSolLnFugacity Class
Activity coefficient
differential wrt temperature
Liquid
COTHRegSolLnActivityCoeffDT Class
Standard Fugacity
Liquid
COTHIdealStdFug Class
Liquid
COTHRegSolExcessGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
3-100
3-101
(3.276)
xj Vj
j = ----------------- xk Vk
(3.277)
where:
Applicable Phase
COTHRegSolLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
(3.278)
3-101
3-102
Activity Models
Applicable Phase
COTHRegSolLnFugacityCoeff Class
Liquid
(3.279)
ln f i = ln ( i x i f i )
where:
Applicable Phase
COTHRegSolLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
Regular Solution Ln Activity Coefficient. For the standard fugacity, fi std,
refer to Section 5.4 - Standard State Fugacity.
3-102
3-103
(3.280)
Applicable Phase
COTHVanLaarLnActivityCoeffDT Class
Liquid
= RT x i ln i
(3.281)
where:
3-103
3-104
Activity Models
Applicable Phase
COTHRegSolLnActivityCoeffDT Class
Liquid
= U + PV TS
(3.282)
simplifies to:
E
G = H = U
To calculate the Gibbs free energy of mixing, the simple Van Laar
thermodynamic cycle is shown below:
Figure 3.2
Pressure
Ideal Gas
Mix Ideal Cases
Vapourize each liquid
dropping system P to
a very low value
(Ideal Gas)
Compress
Vapour
Mixture
Pure
Liquid
3-104
Liquid
Mixture
(3.283)
3-105
= U I + U II + U III
(3.284)
The expression
(3.285)
U = T P P
V T
T V
P = V P P
T V
T P V T
P = V V
T P P T
T V
(3.286)
Therefore:
V
T P
U = P + T --------------
V T
P T
(3.287)
(3.288)
3-105
3-106
Activity Models
id
x 1 ( U U )1 =
a1 x1
- dV
---------2
V
L
V1
a1 x1
= ---------L
V1
(3.289)
a1 x1
a2 x2
id
- dV = ---------x 2 ( U U ) 2 = ---------2
L
V
V
1
L
V2
thus:
id
id
U I = x 1 ( U U ) 1 + x 2 ( U U ) 2
(3.290)
a1 x1 a2 x2
U I = ---------- + ---------L
L
V2
V1
(3.291)
and:
(3.292)
P
and for a real fluid well below its critical point, V T should be a large
negative number (since liquids exhibit low compressibility) and
consequently:
V b 0 or V b
(3.293)
a1 x1 a2 x2
U I = ----------- + ----------b1
b2
(3.294)
Therefore,
3-106
3-107
It follows that:
U II = 0
(3.295)
a mix
U III = ---------b mix
(3.296)
a mix =
xi xj
(3.297)
= x1 b1 + x2 b2
(3.298)
a i a j = x 1 a 1 + x 2 a 2 + 2x 1 x 2 a 1 a 2
nc
b mix =
xi bi
i =1
x1 x2 b1 b2 a1
a 2
= ---------------------------- --------- ---------
x1 b1 + x2 b2 b1
b2
(3.299)
and:
A
ln 1 = --------------------------2Ax
1 + --- ----1B x2
B
ln 2 = --------------------------2Bx
1 + --- ----2A x1
(3.300)
3-107
3-108
Activity Models
where:
b1 a1
a 2
A = ------- --------- ---------
RT b 1
b2
(3.301)
b2 a1
a 2
B = ------- --------- ---------
RT b 1
b2
Ethanol:
Tc=513.9 K
Pc=6147 kPa
a=1252.5 l2/gmol2
b=0.087 l2/gmol2
Water:
Tc=647.3 K
Pc=22120 kPa
a=552.2 l2/gmol2
b=0.030 l2/gmol2
System:
T = 25 C
Two important features that are evident from the activity coefficient
equations are that the log of the activity coefficient is proportional to the
inverse of the absolute temperature, and that the activity coefficient of a
component in a mixture is always greater than one. The quantitative
agreement of the van Laar equation is not good, mainly due to the use of
the van der Waals equation to represent the behaviour of the condensed
phase, and the poor mixing rules for the mixture.
If one uses the van Laar equation to correlate experimental data
(regarding the A and B parameters as purely empirical), good results are
obtained even for highly non-ideal systems. One well-known exception
is when one uses the van Laar equation to correlate data for selfassociating mixtures like alcohol-hydrocarbon.
Aij = 4.976
Aij = 1.716
3-108
3-109
Property Methods
A quick reference of calculation methods is shown in the table below for
the van Laar model.
Applicable
Phase
Activity coefficient
Liquid
COTHVanLaarLnActivityCoeff Class
Fugacity coefficient
Liquid
COTHVanLaarLnFugacityCoeff Class
Fugacity
Liquid
COTHVanLaarLnFugacity Class
Activity coefficient
differential wrt temperature
Liquid
COTHVanLaarLnActivityCoeffDT Class
Excess Gibbs
Liquid
COTHVanLaarExcessGibbsEnergy Class
Excess enthalpy
Liquid
COTHVanLaarExcessEnthalpy Class
Enthalpy
Liquid
COTHVanLaarEnthalpy Class
Gibbs energy
Liquid
COTHVanLaarGibbsEnergy Class
Calculation Method
The calculation methods from the table are described in the following
sections.
ln i = A i [ 1.0 z i ] ( 1.0 + E i z i )
where:
(3.302)
Ai =
j =1
Bi =
j =1
( a ij + b ij T )
x j --------------------------( 1.0 x i )
(3.303)
( a ji + b ji T )
x j --------------------------( 1.0 x i )
(3.304)
3-109
3-110
Activity Models
Ai xi
z i = ------------------------------------------------[ A i x i + B i ( 1.0 x i ) ]
where:
(3.305)
T = temperature (K)
n = total number of components
Applicable Phase
COTHVanLaarLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
3-110
(3.306)
3-111
Applicable Phase
COTHVanLaarLnFugacityCoeff Class
Liquid
(3.307)
ln f i = ln ( i x i f i )
where:
Applicable Phase
COTHVanLaarLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
van Laar Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
3-111
3-112
Activity Models
x j b ji
-----------1 xi
j=1
dB i
dA i
x i ( 1 x i ) -------- B i -------- A i
dZ i
dT
dT
-------- = -------------------------------------------------------------2
dT
[ Ai xi + Bi ( 1 xi ) ]
dA i
-------- =
dT
x j b ij
-----------1 xi
j=1
3-112
Applicable Phase
COTHVanLaarLnActivityCoeffDT Class
Liquid
(3.308)
3-113
= RT x i ln i
(3.309)
where:
Applicable Phase
COTHVanLaarExcessGibbsEnergy Class
Liquid
G =
xi Gi + RT xi ln xi + G
i
where:
n
E
(3.310)
3-113
3-114
Activity Models
Applicable Phase
COTHVanLaarGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
van Laar Excess Gibbs Energy.
= RT
d ln i
xi -----------dT
(3.311)
where:
Applicable Phase
COTHVanLaarExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the van Laar Activity Coefficient Differential wrt Temperature.
3-114
3-115
H =
xi Hi + H
(3.312)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
Applicable Phase
COTHVanLaarEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
van Laar Ln Activity Coefficient.
The Margules equation was the first Gibbs excess energy representation
developed. The equation does not have any theoretical basis, but is
useful for quick estimates and data interpolation. The software has an
extended multi-component Margules equation with up to four
adjustable parameters per binary.
The four adjustable parameters for the Margules equation are the aij
and aji (temperature independent) and the bij and bji terms
(temperature dependent). The equation will use stored parameter
values or any user-supplied value for further fitting the equation to a
given set of data.
3-115
3-116
Activity Models
Property Methods
A quick reference of calculation methods is shown in the table below for
the Margules property model.
Calculation Method
Applicable
Phase
Activity Coefficient
Liquid
COTHMargulesLnActivityCoeff Class
Fugacity coefficient
calculation
Liquid
COTHMargulesLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHMargulesLnFugacity Class
COTHMargulesLnActivityCoeffDT Class
Excess Gibbs
Liquid
COTHMargulesExcessGibbsEnergy
Class
Excess enthalpy
Liquid
COTHMargulesExcessEnthalpy Class
Enthalpy
Liquid
COTHMargulesEnthalpy Class
Gibbs energy
Liquid
COTHMargulesGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
ln i = [ 1.0 x i ] [ A i + 2x i ( B i A i ) ]
where:
(3.313)
Ai =
j =1
3-116
( a ij + b ij T )
x j --------------------------( 1.0 x i )
(3.314)
Bi =
j =1
where:
( a ji + b ji T )
x j --------------------------( 1.0 x i )
3-117
(3.315)
T = temperature (K)
n = total number of components
aij = non-temperature-dependent energy parameter between
components i and j
bij = temperature-dependent energy parameter between components i
and j [1/K]
aji = non-temperature-dependent energy parameter between
components j and i
bji = temperature-dependent energy parameter between components j
and i [1/K]
Applicable Phase
COTHMargulesLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
(3.316)
3-117
3-118
Activity Models
Applicable Phase
COTHMargulesLnFugacityCoeff Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
Margules Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
Margules Fugacity
This method calculates the fugacity logarithm of components using
Margules activity model. The fugacity of component i, fi, is calculated
from the following relation.
std
ln f i = ln ( i x i f i )
where:
(3.317)
Applicable Phase
COTHMargulesLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
Margules Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
3-118
3-119
(3.318)
Applicable Phase
COTHMargulesLnActivityCoeffDT Class
Liquid
= RT x i ln i
(3.319)
where:
3-119
3-120
Activity Models
Applicable Phase
COTHMargulesExcessGibbsEnergy Class
Liquid
G =
where:
xi Gi + RT xi ln xi + G
(3.320)
Applicable Phase
COTHMargulesGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
Margules Excess Gibbs Energy.
3-120
3-121
= RT
d ln i
xi -----------dT
(3.321)
where:
Applicable Phase
COTHMargulesExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the Margules Activity Coefficient Differential wrt Temperature.
Margules Enthalpy
This method calculates the enthalpy using the Margules activity model
from the following relation.
n
H =
xi Hi + H
(3.322)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
3-121
3-122
Activity Models
Applicable Phase
COTHMargulesEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
Margules Excess Enthalpy.
(3.323)
The parameters a21 and a11 are related to the potential energies of the 11 and 1-2 pairs of molecules. Similarly, to see what is happening in the
region of a specific molecule of type 2, you have:
a 12
x 1 exp -------
x 12
RT
------- = -------------------------------x 22
a 22
x 2 exp -------
RT
3-122
(3.324)
3-123
Wilson defined the local volume fractions based on the two equations
above, using the pure component molar volumes as weights:
V 1 x 11
1 = ---------------------------------V 1 x 11 + V 2 x 21
i is the volume fraction of
component i.
G
------- =
RT
V 2 x 22
2 = ---------------------------------V 1 x 12 + V 2 x 22
(3.325)
When the above relations for are substituted into the Flory-Huggins
equation:
i
xi ln ---x-i
G
------- = x 1 ln ( x 1 + 12 x 2 ) x 2 ln ( x 2 + 21 x 1 )
RT
(3.326)
where:
V2
12
12 = ------ exp --------
RT
V1
21
V1
21
= ------ exp --------
RT
V2
(3.327)
and:
12
21
ln 1 = ln ( x 1 + 12 x 2 ) + x 2 -------------------------- -------------------------x 1 + 12 x 2 x 2 + 21 x 1
21
12
ln 2 = ln ( x 2 + 21 x 1 ) + x 1 -------------------------- -------------------------x 1 + 12 x 2 x 2 + 21 x 1
(3.328)
3-123
3-124
Activity Models
(3.329)
(3.330)
3-124
3-125
Although the Wilson equation is more complex and requires more CPU
time than either the van Laar or Margules equations, it can represent
almost all non-ideal liquid solutions satisfactorily, except electrolytes
and solutions exhibiting limited miscibility (LLE or VLLE). It provides an
excellent prediction of ternary equilibrium using parameters regressed
from binary data only. The Wilson equation will give similar results as
the Margules and van Laar equations for weak non-ideal systems, but
consistently outperforms them for increasingly non-ideal systems.
Setting all four parameters to zero does not reduce the binary to an ideal
solution, but maintains a small effect due to molecular size differences
represented by the ratio of molar volumes.
Property Methods
A quick reference of calculation methods is shown in the table below for
the Wilson property model.
Calculation Method
Activity Coefficient
Liquid
COTHWilsonLnActivityCoeff Class
Fugacity coefficient
calculation
Liquid
COTHWilsonLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHWilsonLnFugacity Class
Activity coefficient
differential wrt
temperature
Liquid
COTHWilsonLnActivityCoeffDT Class
Excess Gibbs
Liquid
COTHWilsonExcessGibbsEnergy Class
Excess enthalpy
Liquid
COTHWilsonExcessEnthalpy Class
Enthalpy
Liquid
COTHWilsonEnthalpy Class
Gibbs energy
Liquid
COTHWilsonGibbsEnergy Class
3-125
3-126
Activity Models
The calculation methods from the table are described in the following
sections.
ln i = 1.0 ln
xj ij
j=1
k =1
xk ki
----------------------n
xk kj
(3.331)
j=1
where:
3-126
3-127
Applicable Phase
COTHWilsonLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
(3.332)
Applicable Phase
COTHWilsonLnFugacityCoeff Class
Liquid
3-127
3-128
Activity Models
Wilson Fugacity
This method calculates the fugacity of components using the Wilson
activity model. The fugacity of component i, fi, is calculated from the
following relation.
std
ln f i = ln ( i x i f i )
where:
(3.333)
Applicable Phase
COTHWilsonLnFugacity Class
Liquid
n d
d ki
x j d ij
kj
x k ----------- x j kj x k ij x j -----------
-------------
n
dT
dT
dT
j = 1
j = 1
d ln i
=1
------------ = j------------------------ ----------------------------------------------------------------------------------------------n
2
n
dT
k=1
x
xj ij
j kj
j = 1
j=1
n
3-128
(3.334)
3-129
Applicable Phase
COTHWilsonLnActivityCoeffDT Class
Liquid
= RT x i ln i
(3.335)
where:
Applicable Phase
COTHWilsonExcessGibbsEnergy Class
Liquid
3-129
3-130
Activity Models
G =
xi Gi + RT xi ln xi + G
i
where:
n
E
(3.336)
Applicable Phase
COTHWilsonGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
Wilson Excess Gibbs Energy.
3-130
3-131
= RT
d ln i
xi -----------dT
(3.337)
where:
Applicable Phase
COTHWilsonExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the Wilson Activity Coefficient Differential wrt Temperature.
Wilson Enthalpy
This method calculates the enthalpy using the Wilson activity model
from the following relation.
n
H =
xi Hi + H
(3.338)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
3-131
3-132
Activity Models
Applicable Phase
COTHWilsonEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
Wilson Excess Enthalpy.
where:
12 g 21-
x 2 exp ------------------x 21
RT
------- = ----- ----------------------------------x1
x 11
12 g 11
exp --------------------
RT
(3.339)
12 g 12-
x 1 exp ------------------x 21
RT
------- = ----- ----------------------------------x2
x 22
12 g 22
exp --------------------
RT
(3.340)
3-132
3-133
21
12
------x12 + x22 = 1 and x21 + x11 = 1. If the ratios -----x 11 and x 22 are multiplied:
x 21 x 12
( 2g 12 g 11 g 22 )
------- ------- = exp 12 -------------------------------------------
RT
x 11 x 22
(3.341)
RT
(3.342)
Pressure
Ideal Gas
Mix Ideal Cases
Vapourize each liquid
dropping system P to
a very low value
(Ideal Gas)
Compress
Vapour
Mixture
Pure
Liquid
Liquid
Mixture
RT
where:
(3.343)
3-134
Activity Models
x 21
( g 21 g 11 )
x 2 exp 12 -------------------------RT
= ----------------------------------------------------------------------( g 21 g 11 )
x 1 + x 2 exp 12 -------------------------RT
(3.344)
x 12
( g 12 g 22 )
x 1 exp 12 -------------------------RT
= ----------------------------------------------------------------------( g 12 g 22 )
x 1 + x 2 exp 12 -------------------------RT
(3.345)
and
Renon and Prausnitz used the above equations in the two-liquid theory
of Scott. Scott assumed that a liquid mixture can be idealized as a set of
cells, in which there are cells with molecules of type 1 and type 2 in the
centre. "For cells with molecules of type 1 in the centre, the residual
Gibbs free energy (the Gibbs free energy when compared with that of an
ideal gas at the same temperature, pressure and composition) is the
sum of all the residual Gibbs free energies for two body interactions
experienced by centre molecule of type 1" (22Renon and Prausnitz,
1968). Thus:
(1)
= x 11 g 11 + x 21 g 21
(1)
g pure = g 11
3-134
(3.346)
3-135
(2)
= x 22 g 22 + x 12 g 12
(3.347)
(2)
g pure = g 22
The Gibbs excess energy is the sum of the changes where molecules of
type 1 from a cell of pure component 1 are transferred into the centre of
a cell of liquid 2; the same reasoning applies for molecule 2.
Consequently:
= x1 ( g
(1)
(1)
g pure ) + x 2 ( g
(2)
(2)
g pure )
(3.348)
= x 1 x 21 ( g 21 g 11 ) + x 2 x 12 ( g 12 g 22 )
(3.349)
where:
2
ln 1 = x 2 21 ----------------------------------------------------------2 + 12 ----------------------------------------------------------2
[ x 1 + x 2 exp ( 12 21 ) ]
[ x 2 + x 1 exp ( 12 12 ) ]
(3.350)
exp ( 2 12 12 )
exp ( 2 12 21 )
2
ln 2 = x 1 12 ----------------------------------------------------------2 + 21 ----------------------------------------------------------2
[ x 2 + x 1 exp ( 12 12 ) ]
[ x 1 + x 2 exp ( 12 21 ) ]
(3.351)
3-135
3-136
Activity Models
where:
g 12 g 22
12 = --------------------RT
g 21 g 11
21 = --------------------RT
(3.352)
g 12 = exp ( 12 12 )
g 21 = exp ( 12 21 )
The NRTL equation offers little advantage over Wilson for systems that
are completely miscible. On the other hand, the NRTL equation can be
used for systems that will phase split. When the gij - gji parameters are
temperature dependent, the NRTL equation is very flexible and can be
used to model a wide variety of chemical systems. Although the ij term
has a physical meaning and 22Renon and Prausnitz (1968) suggested a
series of rules to fix its value depending on the mixture type, it is better
treated as an empirical parameter to be determined through regression
of experimental data. That is, if there is enough data to justify the use of
3 parameters.
The NRTL equation is an extension of the original Wilson equation. It
uses statistical mechanics and the liquid cell theory to represent the
liquid structure. These concepts, combined with Wilsons local
composition model, produce an equation capable of representing VLE,
LLE and VLLE phase behaviour. Like the Wilson equation, the NRTL is
thermodynamically consistent and can be applied to ternary and higher
order systems using parameters regressed from binary equilibrium data.
It has an accuracy comparable to the Wilson equation for VLE systems.
The NRTL combines the advantages of the Wilson and van Laar
equations, and, like the van Laar equation, it is not extremely CPU
intensive and can represent LLE quite well. It is important to note that
because of the mathematical structure of the NRTL equation, it can
produce erroneous multiple miscibility gaps. Unlike the van Laar
equation, NRTL can be used for dilute systems and hydrocarbonalcohol mixtures, although it may not be as good for alcoholhydrocarbon systems as the Wilson equation.
3-136
3-137
Property Methods
A quick reference of calculation methods is shown in the table below for
the NRTL property model.
Calculation Method
Applicable
Phase
Activity Coefficient
Liquid
COTHNRTLLnActivityCoeff Class
Liquid
COTHNRTLLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHNRTLLnFugacity Class
Liquid
COTHNRTLLnActivityCoeffDT Class
Liquid
COTHNRTLTempDep Class
Excess Gibbs
Liquid
COTHNRTLExcessGibbsEnergy Class
Excess enthalpy
Liquid
COTHNRTLExcessEnthalpy Class
Enthalpy
Liquid
COTHNRTLEnthalpy Class
Gibbs energy
Liquid
COTHNRTLGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
x
G
mi m mi
n
x j G ij
j=1
m=1
ln i = ---------------------------- + ------------- ij ------------------------------------
n
x k G kj
n
x k G kj
xk Gki j = 1
=
k
1
k=1
ji x j G ji
where:
(3.353)
3-137
3-138
Activity Models
Applicable Phase
COTHNRTLLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
(3.354)
Applicable Phase
COTHNRTLLnFugacityCoeff Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
NRTL Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
3-138
3-139
NRTL Fugacity
This method calculates the fugacity of components using the NRTL
activity model. The fugacity of component, fi, is calculated from the
following relation.
std
ln f i = ln ( i x i f i )
where:
(3.355)
Applicable Phase
COTHNRTLLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
NRTL Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
(3.356)
3-139
3-140
Activity Models
Applicable Phase
COTHNRTLLnActivityCoeffDT Class
Liquid
ij = a ij + ------ + c ij ln T + d ij T + -----2
T
(3.357)
G ij = EXP ( ij )
(3.358)
where:
= 0 + 1 T
a ij = 0 ; b ij = 0 ; c ij = 0 ; d ij = 0 ; e ij = 0
ij = 0
where:
3-140
Applicable Phase
COTHNRTLTempDep Class
Liquid
3-141
= RT x i ln i
(3.359)
where:
Applicable Phase
COTHNRTLExcessGibbsEnergy Class
Liquid
G =
xi Gi + RT xi ln xi + G
i
where:
n
E
(3.360)
3-141
3-142
Activity Models
Applicable Phase
COTHNRTLGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
NRTL Gibbs Energy.
= RT
d ln i
xi -----------dT
(3.361)
where:
Applicable Phase
COTHNRTLExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the NRTL Activity Coefficient Differential wrt Temperature.
3-142
3-143
NRTL Enthalpy
This method calculates the enthalpy using the NRTL activity model
from the following relation.
n
H =
xi Hi + H
(3.362)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
Applicable Phase
COTHNRTLEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
NRTL Excess Enthalpy.
3-143
3-144
Activity Models
(3.363)
a ij + b ij T
ij = ---------------------RT
(3.364)
3-144
3-145
Property Methods
A quick reference of calculation methods is shown in the table below for
the HYPNRTL property model.
Calculation Method
Applicable Phase
Activity Coefficient
Liquid
COTHHYPNRTLLnActivityCoeff Class
Fugacity coefficient
calculation
Liquid
COTHHYPNRTLLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHHYPNRTLLnFugacity Class
Activity coefficient
differential wrt
temperature
Liquid
COTHHYPNRTLLnActivityCoeffDT
Class
Excess Gibbs
Liquid
COTHHYPNRTLExcessGibbsEnergy
Class
Excess enthalpy
Liquid
COTHHYPNRTLExcessEnthalpy Class
Enthalpy
Liquid
COTHHYPNRTLEnthalpy Class
Gibbs energy
Liquid
COTHHYPNRTLGibbsEnergy Class
3-145
3-146
Activity Models
With the General NRTL model, you can specify the format for the
equations of ij and aij to be any of the following:
ij and ij Options
B ij C ij
ij = A ij + ------ + ------2- + F ij T + G ij ln ( T )
T
T
ij = Alp1 ij + Alp2 ij T
ij
B ij
A ij + -----T
= -------------------RT
ij = Alp1 ij
B ij
ij = A ij + ------ + F ij T + G ij ln ( T )
T
ij = Alp1 ij + Alp2 ij T
C ij
ij = A ij + B ij t + ------T
ij = Alp1 ij + Alp2 ij T
where: T is in K and t is C
B ij
ij = A ij + -----T
ij = Alp1 ij
Depending on the form of the equations that you choose, you can
specify values for the different component energy parameters. The
General NRTL model provides radio buttons on the Binary Coeffs tab
which access the matrices for the Aij, Bij, Cij, Fij, Gij, Alp1ij and Alp2ij
energy parameters.
3-146
3-147
Description
HYSIMStdLiquidVolume
Equation
nc
V =
MW i
-x
-------------i i
i=1
HYSIMLiqDensity
Density
HYSIMLiqVolume
Volume
NRTLActCoeff
Activity Coefficient
std
f
i
= ---------
i
i P
x
G
ji x j G ji
n
mi m mi
xG
j ij
=1
m=1
--------------- -------------------------------------------+
-
ln = j-------------------------------i
n
n
x k G kj ij
j=1
x k G ki
x k G kj
k=1
k=1
ActivityLiquid1Fugacity
Fugacity
f = xf
i
i ii
CavettEnthalpy
Enthalpy
l
H = x
steam67
H
+
water water
std
xi H i + Hi
Cavett
CavettEntropy
Entropy
l
S = x
steam67
S
+
water water
xi S + Si
Cavett
CavettGibbs
CavettHelmholtz
Helmholtz Energy
CavettInternal
Internal Energy
CavettCp
Cp
G = G + ( A A ) + RT ( Z 1 )
A = A + ( H H ) + T ( S S ) RT ( Z 1 )
U = U + (A A) + T(S S)
steam67
Cp l = x water Cp water +
xi Cp i + Cpi
Cavett
CavettCv
Cv
C = C R
v
p
3-147
3-148
Activity Models
Method
Description
Equation
NRTLGe
nc
G
= RT
xi ln i
i=1
MRTLHe
Excess enthalpy
H
HYSIMLiquidViscosity*
Viscosity
G E
E
= G T
HYSIMVapourThermalK*
Thermal Conductivity
HYSIMSurfaceTension
Surface Tension
Abrams and Prausnitz (1975) derived an equation with a semitheoretical basis like NRTL, but using only two adjustable parameters
per binary pair. Their approach is heavily dependent on some statistical
mechanics concepts which are outside the scope of this guide. Only a
few highlights from their work will be presented here.
"Guggenheim proposed that a liquid mixture can be seen as a set of tridimensional lattice sites, the volume in the immediate vicinity of a site is
called a cell. Each molecule in the liquid is divided in segments such
that each segment occupies one cell" (23Abrams and Prausnitz, 1975).
Using the configurational partition function, it can be shown that:
g a
where:
A
= ----------------- RT ( x 1 ln x 1 + x 2 ln x 2 )
n1 + n2
A = Helmholtz function
n = number of moles
x = mole fraction
3-148
(3.365)
3-149
= G combinational + G resdiual
(3.366)
and:
Combinational refers to the
non-ideality caused by
differences in size and shape
(entropic effects).
1
2
1
2
Z
E
G combinational = x 1 ln ----- + x 2 ln ----- + --- q 1 x 1 ln ----- + q 2 x 2 ln -----
x 1
x2 2
1
2
G resdiual = q 1 x 1 ln ( 1 + 2 21 ) q 2 x 2 ln ( 2 + 1 12 )
u 21 u 11
21 = exp ---------------------
RT
12
(3.367)
(3.368)
(3.369)
u 12 u 22
= exp ---------------------
RT
where:
q1 x1
1 = ---------------------------q1 x1 + q2 x2
q2 x2
2 = ---------------------------q1 x1 + q2 x2
r1 x1
1 = --------------------------r1 x1 + r2 x2
r2 x2
2 = --------------------------r1 x1 + r2 x2
(3.370)
3-149
3-150
Activity Models
x 1 2
1
r2
(3.371)
Z
l 1 = --- ( r 1 q 1 ) ( r 1 1 )
2
Application of UNIQUAC
The UNIQUAC (UNIversal QUASI-Chemical) equation uses statistical
mechanics and the quasi-chemical theory of Guggenhiem to represent
the liquid structure. The equation is capable of representing LLE, VLE
and VLLE with accuracy comparable to the NRTL equation, but without
the need for a non-randomness factor. The UNIQUAC equation is
significantly more detailed and sophisticated than any of the other
activity models. Its main advantage is that a good representation of both
VLE and LLE can be obtained for a large range of non-electrolyte
mixtures using only two adjustable parameters per binary. The fitted
parameters usually exhibit a smaller temperature dependence which
makes them more valid for extrapolation purposes.
3-150
3-151
Property Methods
A quick reference of calculation methods is shown in the table below for
the UNIQUAC property model.
Calculation Method
Applicable
Phase
Activity Coefficient
Liquid
COTHUNIQUACLnActivityCoeff Class
Fugacity coefficient
calculation
Liquid
COTHUNIQUACLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHUNIQUACLnFugacity Class
COTHUNIQUACLnActivityCoeffDT Class
Excess Gibbs
Liquid
COTHUNIQUACExcessGibbsEnergy
Class
Excess enthalpy
Liquid
COTHUNIQUACExcessEnthalpy Class
Enthalpy
Liquid
COTHUNIQUACEnthalpy Class
Gibbs energy
Liquid
COTHUNIQUACGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
3-151
3-152
Activity Models
i
i
ln i = ln ------ + 0.5Zq i ln ------
xi
i
n
n
i
j ji
xi
j=1
j=1
j = 1
k kj
(3.372)
k=1
where:
(3.373)
(3.374)
(3.375)
3-152
3-153
Applicable Phase
COTHUNIQUACLnActivityCoeff Class
Liquid
fi
ln i = ln i --------
P
where:
(3.376)
Applicable Phase
COTHUNIQUACLnFugacityCoeff Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
UNIQUAC Ln Activity Coefficient. For the standard fugacity, fi std, refer
to Section 5.4 - Standard State Fugacity.
3-153
3-154
Activity Models
UNIQUAC Fugacity
This method calculates the fugacity of components using the UNIQUAC
activity model. The fugacity of component i, fi, is calculated from the
following relation.
std
ln f i = ln ( i x i f i )
where:
(3.377)
Applicable Phase
COTHUNIQUACLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
UNIQUAC Ln Activity Coefficient. For the standard fugacity, fi std, refer
to Section 5.4 - Standard State Fugacity.
3-154
(3.378)
3-155
Applicable Phase
COTHUNIQUACLnActivityCoeffDT Class
Liquid
= RT x i ln i
(3.379)
where:
Applicable Phase
COTHUNIQUACExcessGibbsEnergy Class
Liquid
3-155
3-156
Activity Models
G =
xi Gi + RT xi ln xi + G
i
where:
(3.380)
Applicable Phase
COTHUNIQUACGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
UNIQUAC Excess Gibbs Energy.
= RT
d ln i
xi -----------dT
i
where:
3-156
(3.381)
3-157
Applicable Phase
COTHUNIQUACExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the UNIQUAC Activity Coefficient Differential wrt Temperature.
UNIQUAC Enthalpy
This method calculates the enthalpy using the UNIQUAC activity model
from the following relation.
n
H =
xi Hi + H
(3.382)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
Applicable Phase
COTHUNIQUACEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
UNIQUAC Excess Enthalpy.
3-157
3-158
Activity Models
ethanol
ethanol
CH2
OH
CH3
CH2
H2O
H2O
OH
H2O
CH3
H2O
Classical
View
Solution of
Groups
Point
of View
3-158
3-159
The original UNIFAC method also has several shortcomings that stem
from the assumptions used to make it a useful engineering tool. Perhaps
the most important one is that the group activity concept is not correct,
since the group area and volume should be a function of the position in
the molecule, as well as the other groups present in the molecule. Also,
35
Sandler suggested that the original choice of groups might not be
optimal (1991a, 361991b) and sometimes wrong results are predicted.
Also, the original UNIFAC VLE produces wrong LLE predictions (which
is not surprising). This was remedied by 31Magnussen (1981) with the
publication of interaction parameter tables for LLE calculations. This
area has received considerably less attention than the VLE, and
hopefully new revisions for the LLE interaction parameter matrix will
appear.
One more interesting point is that the amk interaction parameter term is
not, in reality, temperature independent. Thus, serious errors can be
expected when predicting excess enthalpies. There is work being done
to extend the applicability and reliability of the UNIFAC method,
especially in Denmark (1984) and Germany (1987).
3-159
3-160
Activity Models
( 0 ) a mk
(2)
a mk = a mk + --------- + a mk ln T
T
(3.383)
These refinements will probably continue for several years and UNIFAC
will be continuously updated.
For more complex mixtures, 26Wilson and Deal (1962), and 27Derr and
Deal (1969), proposed a group contribution method in which the
mixture was treated as a solution of atomic groups instead of a solution
of molecules. The concept of atomic group activity, although not new in
chemical engineering (28Le Bas, 1915), was shown to be applicable to the
prediction of mixture behaviour, thus increasing its utility many times.
The Wilson, Deal and Derr approach was based on the athermal FloryHuggins equation and it found acceptance, especially in Japan where it
modified to a computer method called ASOG (Analytical Solution of
Groups) by 29Kojima and Toguichi (1979).
Figure 3.5
ethanol
ethanol
CH2
OH
CH3
CH2
3-160
H2O
H2O
OH
H2O
CH3
H2O
Classical
View
Solution of
Groups
Point
of View
3-161
Property Methods
A quick reference of calculation methods is shown in the table below for
the UNIFAC property model.
Calculation Method
Applicable Phase
Activity Coefficient
(VLE)
Liquid
COTHUNIFAC1_VLELnActivityCoeff
Class
Fugacity coefficient
calculation (VLE)
Liquid
COTHUNIFAC1_VLELnFugacityCoeff
Class
Fugacity calculation
(VLE)
Liquid
COTHUNIFAC1_VLELnFugacity Class
Activity coefficient
differential wrt
temperature (VLE)
Liquid
COTHUNIFAC1_VLELnActivityCoeffDT
Class
Enthalpy (VLE)
Liquid
COTHUNIFAC1_VLEEnthalpy Class
Liquid
COTHUNIFAC1_VLEGibbsEnergy Class
Activity Coefficient
(LLE)
Liquid
COTHUNIFAC1_LLELnActivityCoeff
Class
Fugacity coefficient
calculation (LLE)
Liquid
COTHUNIFAC1_LLELnFugacityCoeff
Class
Fugacity calculation
(LLE)
Liquid
COTHUNIFAC1_LLELnFugacity Class
Activity coefficient
differential wrt
temperature (LLE)
Liquid
COTHUNIFAC1_LLELnActivityCoeffDT
Class
Enthalpy (LLE)
Liquid
COTHUNIFAC1_LLEEnthalpy Class
Liquid
COTHUNIFAC1_LLEGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
3-161
3-162
Activity Models
ln i = ln i + ln i
(3.384)
ln i =
(i)
vk
(i)
ln ( k ln k )
(3.385)
where:
The summation is extended over all the groups present in the mixture.
k is calculated in a similar manner as iR in the UNIQUAC equation:
m mk
ln k = Q k 1 ln m mk ----------------------
m n nm
n
3-162
(3.386)
where:
3-163
(3.387)
where:
xm Qm
j
(3.388)
x m = --------------------- n nm
n
where:
vm xj
mk = --------------------------(j)
vm xj
j
(3.389)
In which amk = 0 when m = k. Also, the area and volume for the
molecules are computed by:
ri =
(i)
vk
k
where:
Rk
qi =
(i)
vk
Qk
(3.390)
3-163
3-164
Activity Models
Applicable Phase
COTHUNIFAC1_VLELnActivityCoeff Class
Liquid
COTHUNIFAC1_LLELnActivityCoeff Class
Liquid
The UNIFAC VLE model uses the interaction parameters which have
been calculated from the experimental VLE data, whereas, the UNIFAC
LLE uses the interaction parameters calculated from LLE experimental
data.
fi
ln i = ln i --------
P
where:
3-164
(3.391)
3-165
Applicable Phase
COTHUNIFAC1_VLELnFugacityCoeff Class
Liquid
COTHUNIFAC1_LLELnFugacityCoeff Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
UNIFAC Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
The UNIFAC VLE model uses the interaction parameters which have
been calculated from the experimental VLE data, whereas, the UNIFAC
LLE uses the interaction parameters calculated from LLE experimental
data.
UNIFAC Fugacity
This method calculates the fugacity of components using the UNIFAC
activity model. The fugacity of component i, fi, is calculated from the
following relation.
std
ln f i = ln ( i x i f i )
where:
(3.392)
3-165
3-166
Activity Models
Applicable Phase
COTHUNIFAC1_VLELnFugacity Class
Liquid
COTHUNIFAC1_LLELnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
UNIFAC Ln Activity Coefficient. For the standard fugacity, fi std, refer to
Section 5.4 - Standard State Fugacity.
The UNIFAC VLE model uses the interaction parameters which have
been calculated from the experimental VLE data, whereas, the UNIFAC
LLE uses the interaction parameters calculated from LLE experimental
data.
(3.393)
Applicable Phase
COTHUNIFAC1_VLELnActivityCoeffDT Class
Liquid
COTHUNIFA1_LLECLnActivityCoeffDT Class
Liquid
The UNIFAC VLE model uses the interaction parameters which have
been calculated from the experimental VLE data, whereas, the UNIFAC
LLE uses the interaction parameters calculated from LLE experimental
data.
3-166
3-167
G =
xi Gi + RT xi ln xi + G
i
where:
n
E
(3.394)
Applicable Phase
COTHUNIFAC1_VLEGibbsEnergy Class
Liquid
COTHUNIFAC1_LLEGibbsEnergy Class
Liquid
3-167
3-168
Activity Models
UNIFAC Enthalpy
This method calculates the enthalpy using the UNIFAC activity model
from the following relation.
n
H =
xi Hi + H
(3.395)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
Applicable Phase
COTHUNIFAC1_VLEEnthalpy Class
Liquid
COTHUNIFAC1_LLEEnthalpy Class
Liquid
3-168
3-169
Chien-Null Form
The Chien-Null generalized multi-component equation can be
expressed as:
2 ln i
A j, k x j R j, k x j
A j, i x j R j, i x j
j
j
j
j
= -------------------------------------------------------- + x k -------------------------------------------------------------
k
S j, k x j V j, i x j
S j, i x j V j, i x j
(3.396)
A i, k
R i, k
S i, k
V i, k
----------------------- + ----------------------- ---------------------- ---------------------- A j, k x j R j, k x j S j, k x j V j, k x j
j
Each of the parameters in this equation are defined specifically for each
of the applicable activity methods.
3-169
3-170
Activity Models
Description of Terms
The Regular Solution equation uses the following:
L
vi ( i j )
A i, j = ---------------------------RT
A i, j
R i, j = -------A j, i
V i, j = R i, j
(3.397)
S i, j = R i, j
v i = v , i ( 5.7 + 3T r, i )
(3.398)
The van Laar, Margules and Scatchard Hamer use the following:
Model
Ai,j
Ri,j
van Laar
ln i, j
2 ln i, j
------------------------------
ln i, j
---------------1+
ln j
,i
Margules
Scatchard Hamer
2 ln i, j
------------------------------
ln i, j
1 + ---------------
ln j
,i
Si,j
Vi,j
A i, j
-------A j, i
R i, j
R i, j
A i, j
-------A j, i
A i, j
-------A j, i
vi
----
vj
vi
----
vj
ln i, j = a i, j + -------- + c ij T
T
where:
(3.399)
T must be in K
This equation is of a different form than the original van Laar and
Margules equations in HYSY S, which used an a + bT relationship.
However, since HYSYS only contains aij values, the difference should
not cause problems.
3-170
3-171
A i, j = 2 i, j V i, j
R i, j = 1
V i, j = exp ( c i, j i, j )
S i, j = 1
b i, j
i, j = a i, j + -----------T(K)
(3.400)
The expression for the term under the Chien-Null incorporates the R
term of NRTL into the values for aij and bij. As such, the values initialized
for NRTL under Chien-Null will not be the same as for the regular NRTL.
When you select NRTL for a binary pair, aij will be empty (essentially
equivalent to the regular NRTL bij term), bij will be initialized and cij will
be the term for the original NRTL, and will be assumed to be
symmetric.
The General Chien-Null equation is:
b i, j
A i, j = a i, j + -----------T(K)
A i, j
R i, j = -------A j, i
V i, j = C i, j
S i, j = C i, j
(3.401)
In all cases:
A i, i = 0
R i, i = S i, i = V i, i = 1
(3.402)
With the exception of the Regular Solution option, all models can use six
constants, ai,j, aj,i, bi,j, bj,i, ci,j and cj,i for each component pair. For all
models, if the constants are unknown they can be estimated from the
UNIFAC VLE or LLE methods, the Insoluble option, or using Henrys
Law coefficients for appropriate components. For the general ChienNull model, the cij values are assumed to be 1.
3-171
3-172
Activity Models
Property Methods
A quick reference of calculation methods is shown in the table below for
the Chien-Null (CN) property model.
Calculation Method
Activity Coefficient
Liquid
COTHCNLnActivityCoeff Class
Fugacity coefficient
calculation
Liquid
COTHCNLnFugacityCoeff Class
Fugacity calculation
Liquid
COTHCNLnFugacity Class
COTHCNLnActivityCoeffDT Class
NRTL temperature
dependent properties
Liquid
COTHNRTLTempDep Class
Excess Gibbs
Liquid
COTHCNExcessGibbsEnergy Class
Excess enthalpy
Liquid
COTHCNExcessEnthalpy Class
Enthalpy
Liquid
COTHCNEnthalpy Class
Gibbs energy
Liquid
COTHCNGibbsEnergy Class
The calculation methods from the table are described in the following
sections.
3-172
Applicable Phase
COTHCNLnActivityCoeff Class
Liquid
3-173
fi
ln i = ln i --------
P
where:
(3.403)
Applicable Phase
COTHCNLnFugacityCoeff Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
Chien-Null Ln Activity Coefficient. For the standard fugacity, fi std, refer
to Section 5.4 - Standard State Fugacity.
Chien-Null Fugacity
This method calculates the fugacity of components using the UNIFAC
activity model. The fugacity of component i, fi, is calculated from the
following relation.
std
ln f i = ln ( i x i f i )
where:
(3.404)
3-173
3-174
Activity Models
Applicable Phase
COTHCNLnFugacity Class
Liquid
The term, lni, in the above equation is exclusively calculated using the
Chien-Null Ln Activity Coefficient. For the standard fugacity, fi std, refer
to Section 5.4 - Standard State Fugacity.
(3.405)
3-174
Applicable Phase
COTHCNLnActivityCoeffDT Class
Liquid
3-175
= RT x i ln i
(3.406)
where:
Applicable Phase
COTHCNExcessGibbsEnergy Class
Liquid
G =
xi Gi + RT xi ln xi + G
i
where:
n
E
(3.407)
3-175
3-176
Activity Models
Applicable Phase
COTHCNGibbsEnergy Class
Liquid
The term, GE, in the above equation is exclusively calculated using the
Chien-Null Excess Gibbs Energy.
= RT
d ln i
xi -----------dT
(3.408)
where:
Applicable Phase
COTHCNExcessEnthalpy Class
Liquid
d ln i
-----------The term, dT , in the above equation is exclusively calculated using
the Chien-Null Activity Coefficient Differential wrt Temperature.
3-176
3-177
Chien-Null Enthalpy
This method calculates the enthalpy using the CN activity model from
the following relation.
n
H =
xi Hi + H
(3.409)
where:
= excess enthalpy
xi = mole fraction of component i
Hi = enthalpy of component i
Applicable Phase
COTHCNEnthalpy Class
Liquid
The term, HE, in the above equation is exclusively calculated using the
Chien-Null Excess Enthalpy.
3-177
3-178
Chao-Seader Model
Description
Chao-Seader
Applicable Phase
COTHChaoSeaderLnFugacityCoeff Class
Liquid
COTHChaoSeaderLnFugacity Class
Liquid
Temp. (C)
Temp. (C)
Press. (psia)
Press. (kPa)
CS
0 to 500
18 to 260
< 1,500
< 10,000
Conditions of Applicability
For all hydrocarbons (except
CH4):
If CH4 or H2 is present:
3-178
Aromatic Mixtures
3-179
Description
Grayson-Streed
Applicable Phase
COTHGraysonStreedLnFugacityCoeff Class
Liquid
COTHGraysonStreedLnFugacity Class
Liquid
Temp. (C)
Temp. (C)
Press. (psia)
Press. (kPa)
GS
0 to 800
18 to 425
< 3,000
< 20,000
Conditions of Applicability
For all hydrocarbons (except
CH4):
If CH4 or H2 is present:
Aromatic Mixtures
3-179
3-180
Grayson-Streed Model
3-180
4-1
4 Physical Property
Calculation Methods
4.1 Cavett Method ..................................................................................2
4.2 Rackett Method ................................................................................8
4.3 COSTALD Method..........................................................................11
4.4 Viscosity .........................................................................................14
4.5 Thermal Conductivity ....................................................................18
4.6 Surface Tension .............................................................................20
4.7 Insoluble Solids .............................................................................21
4-1
4-2
Cavett Method
Property Methods
A quick reference of calculation methods is shown in the table below for
the Cavett method.
Calculation Method
Phase
Applicable
Enthalpy
Liquid
COTHCavettEnthalpy Class
Entropy
Liquid
COTHCavettEntropy Class
Liquid
COTHNCavettCp Class
Helmholtz energy
Liquid
COTHCavettHelmholtz Class
Gibbs energy
Liquid
COTHCavettGibbs Class
Internal energy
Liquid
COTHCavettInternalEnergy Class
The calculation methods from the table are described in the following
sections.
4-2
4-3
Cavett Enthalpy
This method calculates the liquid enthalpy using the Cavett model from
the following relation.
steam67
H = x water H water
+ x i ( H i + H i
Cavett
(4.1)
where:
cavett
H non aqueous =
cavett
min ( H i
)x i
(4.2)
i = 1; i 1
e1
(4.3)
(4.4)
(4.5)
H i = T c, i ( a1 + a2 ( 1 T r, i ) )
a1 = b1 + b2 i + b3 i + b4 i
a2 = b5 + b6 i + b7 i + b8 i
2
(4.6)
e1 = 1 a3 ( T r, i 0.1 )
(4.7)
where:
(4.8)
i = non-aqueous components
xi = mole fraction of component i
H i
cavett
= H i
(4.9)
4-3
4-4
Cavett Method
H i
cavett
(4.10)
= min ( H i , H i )
H i
cavett
= H i
(4.11)
Phase Applicable
COTHCavettEnthalpy Class
Liquid
Cavett Entropy
This method calculates the liquid entropy using the Cavett model from
the following relation:
steam67
S = x water S water
+ x i ( S i + S i
Cavett
(4.12)
S i
cavett
H i
= -----------T
(4.13)
S i
4-4
cavett
min ( H i , H i )
= -----------------------------------------T
(4.14)
4-5
S i
where:
cavett
H i
= -----------T
(4.15)
i = non-aqueous components
xi = mole fraction of component i
T = Temperature (K)
Phase Applicable
COTHCavettEntropy Class
Liquid
Cavett Cp (Isobaric)
This method calculates the liquid isobaric heat capacity using the Cavett
model from the following relation.
steam67
Cp = x water Cp water
+ x i ( Cp i + Cp i
Cavett
(4.16)
where:
i = non-aqueous components
cavett
(4.17)
Cp i
cavett
H i
e1
T
1
T r, i
c, i
(4.18)
4-5
4-6
Cavett Method
For supercritical components with Hi2 equal to zero, the change in heat
capacity is:
Cp i
cavett
(4.19)
= 0
For supercritical components with Hi2 different than zero, the change
in heat capacity is:
Cp i
cavett
= T r, i ( 2 ( c 2 + c 5 P r, i ) + T r, i ( 3c 3 + T r, i ( 4c 4 ) ) )
(4.20)
where:
b1 = -67.022001
b7 = -23612.5670
c1 = 10.273695
b2 = 644.81654
b8 = 34152.870
c2 = -1.5594238
b3 = -1613.1584
b9 = 8.9994977
c3 = 0.019399
b4 = 844.13728
b10 = -78.472151
c4 = -0.03060833
b5 = -270.43935
b11 = 212.61128
c5 = -0.168872
b6 = 4944.9795
b12 = -143.59393
Phase Applicable
COTHCavettCp Class
Liquid
The term, Hi1, in the above equation is exclusively calculated using the
Cavett Enthalpy.
4-6
4-7
A = G PV
Phase Applicable
COTHCavettHelmholtz Class
Liquid
(4.22)
H = Cavett enthalpy
S = Cavett entropy
4-7
4-8
Rackett Method
Phase Applicable
COTHCavettGibbs Class
Liquid
U = H PV
Phase Applicable
COTHCavettInternal Class
Liquid
4-8
4-9
The Rackett Equation has been found to produce slightly more accurate
estimations for chemical groups such as acetylenes, cycloparaffins,
aromatics, flurocarbons, cryogenic liquids, and sulfides.
Property Methods
A quick reference of liquid density and volume calculations are shown in
the table below for the Rackett method.
Calculation Method
Phase Applicable
Liquid Volume
Liquid
COTHRackettVolume Class
Liquid Density
Liquid
COTHRackettDensity Class
The calculation methods from the table are described in the following
sections.
RT c 1 + ( 1 Tr ) 7
V s = ---------Z RA
Pc
where:
(4.24)
4-9
4-10
Rackett Method
Phase Applicable
COTHRackettVolume Class
Liquid
RT c
1 + ( 1 Tr )
s = 1 --------- Z RA
Pc
where:
2
--7
4-10
Phase Applicable
COTHRackettDensity Class
Liquid
(4.25)
4-11
4-11
4-12
COSTALD Method
Property Methods
A quick reference of liquid density and volume calculations are shown in
the table below for the Rackett method.
Calculation Method
Phase Applicable
Liquid Volume
Liquid
COTHCOSTALDVolume Class
Liquid Density
Liquid
COTHCOSTALDDensity Class
The calculation methods from the table are described in the following
sections.
()
V s V = V r [ 1 SRK V r ]
4
(o)
Vr
= 1+
Ak ( 1 Tr )
k3
k=1
()
Vr
Bk Tr
k=0
4-12
( T r 1.00001 )
(4.26)
4-13
T cm = x i x j V ij T c V m
ij
2
1
----3
3
V m = 1 4 x i V i + 3 x i V i x i V i
i
i
(4.27)
1
---
2
V ij T c = ( V i T c V j T c )
ij
SRK =
m
xi SRK
where:
Phase Applicable
COTHCOSTALDVolume Class
Liquid
4-13
4-14
Viscosity
(4.28)
Phase Applicable
COTHCOSTALDDensity Class
Liquid
The saturated liquid volume, Vs, is calculated from Equations (4.26) and
(4.27).
4.4 Viscosity
This method will automatically select the model best suited for
predicting the phase viscosities of the system under study. The model
selected will be from one of the three available in this method: a
modification of the NBS method (39Ely and Hanley), Twus model, or a
modification of the Letsou-Stiel correlation. This method will select the
appropriate model using the following criteria:
Chemical System
4-14
Vapour Phase
Liquid Phase
Twu
Non-Ideal Chemicals
Mod Letsou-Stiel
4-15
All of the models are based on corresponding states principles and have
been modified for more reliable application. Internal validation showed
that these models yielded the most reliable results for the chemical
systems shown. Viscosity predictions for light hydrocarbon liquid
phases and vapour phases were found to be handled more reliably by an
in-house modification of the original Ely and Hanley model, heavier
hydrocarbon liquids were more effectively handled by Twus model, and
chemical systems were more accurately handled by an in-house
modification of the original Letsou-Stiel model.
A complete description of the original corresponding states (NBS)
model used for viscosity predictions is presented by Ely and Hanley in
their NBS publication. The original model has been modified to
eliminate the iterative procedure for calculating the system shape
factors. The generalized Leech-Leland shape factor models have been
replaced by component specific models. This method constructs a PVT
map for each component using the COSTALD for the liquid region. The
shape factors are adjusted such that the PVT map can be reproduced
using the reference fluid.
The shape factors for all the library components have already been
regressed and are included in the Pure Component Library.
Hypocomponent shape factors are regressed using estimated
viscosities. These viscosity estimations are functions of the
hypocomponent Base Properties and Critical Properties.
Hypocomponents generated in the Oil Characterization Environment
have the additional ability of having their shape factors regressed to
match kinematic or dynamic viscosity assays.
The general model employs CH4 as a reference fluid and is applicable to
the entire range of non-polar fluid mixtures in the hydrocarbon
industry. Accuracy for highly aromatic or naphthenic crudes will be
increased by supplying viscosity curves when available, since the pure
component property generators were developed for average crude oils.
The model also handles H2O and acid gases as well as quantum gases.
4-15
4-16
Viscosity
Although the modified NBS model handles these systems very well, the
Twu method was found to do a better job of predicting the viscosities of
heavier hydrocarbon liquids. The Twu model is also based on
corresponding states principles, but has implemented a viscosity
correlation for n-alkanes as its reference fluid instead of CH4. A
complete description of this model is given in the paper entitled
"42Internally Consistent Correlation for Predicting Liquid Viscosities of
Petroleum Fractions".
For chemical systems, the modified NBS model of Ely and Hanley is
used for predicting vapour phase viscosities, whereas a modified form of
the Letsou-Stiel model is used for predicting the liquid viscosities. This
method is also based on corresponding states principles and was found
to perform satisfactorily for the components tested.
The shape factors contained within this methods Pure Component
Library have been fit to match experimental viscosity data over a broad
operating range.
4-16
Phase Applicable
COTHViscosity Class
4-17
3.6 ( 1 oil )
(4.29)
where:
If the volume fraction of the hydrocarbon phase is less than 0.33, the
oil + 0.4 H2 O
- H O
eff = 1 + 2.5 oil ----------------------------------2
oil + H2 O
(4.30)
where:
xi MWi
1
= ----------------xi
---
(molecular weight)
(mixture density)
(4.31)
Cp
eff
xi Cp
4-17
4-18
Thermal Conductivity
4-18
Phase Applicable
COTHThermCond Class
4-19
where:
mix
= 1 L + 2 1 2 12 + 2 L
1
(4.32)
2
i j kij
i
x1 V1
------------------2
xi Vi
i=1
2 =
x2 V2
------------------2
xi Vi
i=1
4-19
4-20
Surface Tension
Phase Applicable
COTHSurfaceTension Class
= Pc
where:
TR ) b
(4.33)
4-20
4-21
Property Methods
A quick reference of calculation methods for insoluble solids is shown in
the table below.
Calculation Method
Phase Applicable
MolarDensity
xptInsolubleSolid
COTHSolidDensity Class
MolarVolume
xptInsolubleSolid
COTHSolidVolume Class
Enthalpy
xptInsolubleSolid
COTHSolidEnthalpy Class
Entropy
xptInsolubleSolid
COTHSolidEntropy Class
Cp
xptInsolubleSolid
COTHSolidCp Class
The calculation methods from the table are described in the following
sections.
Phase Applicable
COTHSolidDensity Class
xptInsolubleSolid
Phase Applicable
COTHSolidVolume Class
xptInsolubleSolid
4-21
4-22
Insoluble Solids
Phase Applicable
COTHSolidEnthalpy Class
xptInsolubleSolid
Phase Applicable
COTHSolidEnthalpy Class
xptInsolubleSolid
Insoluble Solid Cp
Property Class Name and Phases Applicable
4-22
Phase Applicable
COTHSolidCp Class
xptInsolubleSolid
5-1
5-1
5-2
Property Methods
The enthalpy reference state calculation methods are shown in the table
below.
Calculation Method
Phase Applicable
COTHOffsetIGH Class
Enthalpy Offset
COTHOffsetH Class
ig
H i + offset H i
Phase Applicable
COTHOffsetIGH Class
5-2
(5.1)
5-3
Offset H i = H i
fig ( 25 C )
+ Hi
(5.2)
Phase Applicable
COTHOffsetH Class
Property Methods
The entropy reference state calculation methods are shown in the table
below.
Calculation Method
Phase Applicable
COTHOffsetIGS Class
Entropy Offset
COTHOffsetS Class
5-3
5-4
ig
S i + offset S i
(5.3)
Phase Applicable
COTHOffsetIGS Class
Offset S = 0
5-4
Phase Applicable
COTHOffsetS Class
(5.4)
5-5
fi = i xi fi
where:
(5.5)
sat sat
f i = P i i exp
Vi
------- dP
RT
(5.6)
sat
Pi
where:
5-5
5-6
The Poynting factor accounts for the effect of pressure on liquid fugacity
and is represented by the exponential term in the above equation. The
correction factor generally is neglected if the pressure does not exceed a
few atmospheres. The liquid volume has little effect on pressure and the
above equation simplifies to:
std
sat sat
sat
f i = P i i exp [ ( P P i )V i ( RT ) ]
(5.7)
The vapour phase fugacity can be calculated by any method when liquid
activity coeffiecients are used.
Property Methods
The standard state fugacity calculation methods are shown in the
following table.
Calculation Method Phase Applicable
LnStdFugacity
Liquid
COTHIdealStdFug Class
LnStdFugacity
Liquid
COTHPoyntingStdFug Class
LnStdFugacity
Liquid
COTHPhiStdFug Class
LnStdFugacity
Liquid
COTHPoyntingPhiStdFug Class
sat
fi = Pi
5-6
(5.8)
5-7
Phase Applicable
COTHIdealStdFug Class
Liquid
Notes
For non-condensible components in the presence of any condensible
components, Henrys law is used as shown below.
std
f i = H i, j
(5.9)
sat
fi = Pi
(5.10)
sat
sat
f i = P i exp [ ( P P i )V i ( RT ) ]
(5.11)
5-7
5-8
Phase Applicable
COTHPoyntingStdFug Class
Liquid
Notes
For non-condensible components in the presence of any condensible
components, Henrys law is used as shown below.
std
f i = H i, j
(5.12)
sat
sat
f i = P i exp [ ( P P i )V i ( RT ) ]
(5.13)
sat sat
fi = Pi i
5-8
(5.14)
5-9
Phase Applicable
COTHPhiStdFug Class
Liquid
Notes
For non-condensible components in the presence of any condensible
components, Henrys law is used as shown below.
std
sat
f i = H i, j exp [ ( P P i )V i ( RT ) ]
(5.15)
std
sat
sat
f i = P i exp [ ( P P i )V i ( RT ) ]
(5.16)
sat sat
sat
f i = P i i exp [ ( P P i )V i ( RT ) ]
(5.17)
5-9
5-10
Phase Applicable
COTHPoyntingPhiStdFug Class
Liquid
Notes
For non-condensible components in the presence of any condensible
components, Henrys law is used as shown below.
std
sat
f i = H i, j exp [ ( P P i )V i ( RT ) ]
(5.18)
std
sat
sat
f i = P i exp [ ( P P i )V i ( RT ) ]
(5.19)
5-10
Flash Calculations
6-1
6 Flash Calculations
6.1 Introduction......................................................................................2
6.2 T-P Flash Calculation ......................................................................3
6.3 Vapour Fraction Flash .....................................................................4
6.3.1 Dew Points ...............................................................................4
6.3.2 Bubble Points/Vapour Pressure ...............................................5
6.3.3 Quality Points ...........................................................................5
6.4 Flash Control Settings ....................................................................7
6-1
6-2
Introduction
6.1 Introduction
Specified variables can only
be re-specified by you or via
the Recycle Adjust, or
SpreadSheet operations. They
will not change through any
heat or material balance
calculations.
6-2
Flash Calculations
6-3
6-3
6-4
6-4
Flash Calculations
6-5
Enthalpy Flash
Given the enthalpy and either the temperature or pressure of a stream,
the property package will calculate the unknown dependent variables.
Although the enthalpy of a stream cannot be specified directly, it will
often occur as the second property variable as a result of energy
balances around unit operations such as valves, heat exchangers and
mixers.
If an error message appears, this may mean that an internally set
temperature or pressure bound has been encountered. Since these
bounds are set at quite large values, there is generally some erroneous
input that is directly or indirectly causing the problem, such as an
impossible heat exchange.
6-5
6-6
Entropy Flash
Given the entropy and either the temperature or pressure of a stream,
the flash will calculate the unknown dependent variables.
Solids
COMThermo flash does not check for solid phase formation of pure
components within the flash calculations.
Solids do not participate in vapour-liquid equilibrium (VLE)
calculations. Their vapour pressure is taken as zero. However, since
solids do have an enthalpy contribution, they will have an effect on heat
balance calculations. Thus, while the results of a temperature flash will
be the same whether or not such components are present, an Enthalpy
flash will be affected by the presence of solids.
6-6
Flash Calculations
6-7
Description
Fixed Control
Additional Control
Refer to the Flash Control Settings in the Flash XML File section in the
Programmers guide of the COMThermo development kit for more
information.
6-7
6-8
6-8
Property Packages
7-1
7 Property Packages
7.1 Introduction......................................................................................2
7.2 Vapour Phase Models......................................................................2
7.3 Liquid Phase Models .....................................................................13
7-1
7-2
Introduction
7.1 Introduction
A summary of the property packages used within the COMThermo
framework are grouped into the following sections:
Each section consists of tables which include the file name, description,
property names, and class names within COMThermo.
Ideal Gas
PV=nRT can be used to model the vapour phase but is only suggested for
ideal systems under moderate conditions.
7-2
Name
Description
Ideal_vapour
Ideal Gas
Property Name
Class Name
Description
Enthalpy
COTHIGEnthalpy
Entropy
COTHIGEntropy
Cp
COTHIGCp
LnFugacityCoeff
COTHIGLnFugacityCoeff
LnFugacity
COTHIGLnFugacity
MolarVolume
COTHIGVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHIGZFactor
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
Property Packages
Property Name
Class Name
Description
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-3
Peng-Robinson
This model is ideal for VLE calculations as well as calculating liquid
densities for hydrocarbon systems. However, in situations where highly
non-ideal systems are encountered, the use of Activity Models is
recommended.
XML File Name
Name
Description
pr_vapour
Peng-Robinson
Property Name
Class Name
Description
Enthalpy
COTHPREnthalpy
Peng-Robinson enthalpy.
Entropy
COTHPREntropy
Peng-Robinson entropy.
Cp
COTHPRCp
LnFugacityCoeff
COTHPRLnFugacityCoeff
Peng-Robinson fugacity
coefficient.
LnFugacity
COTHPRLnFugacity
Peng-Robinson fugacity.
MolarVolume
COTHPRVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHPRZFactor
Peng-Robinson compressibility
factor.
amix
COTHPRab_1
Peng-Robinson amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-3
7-4
HysysPR
The HysysPR EOS is similar to the PR EOS with several enhancements to
the original PR equation. It extends its range of applicability and better
represents the VLE of complex systems.
7-4
Name
Description
hysyspr_vapour
HysysPR
Property Name
Class Name
Description
Enthalpy
COTHPR_HYSYS_Enthalpy
Peng-Robinson enthalpy.
Entropy
COTHPR_HYSYS_Entropy
Peng-Robinson entropy.
Cp
COTHPR_HYSYS_Cp
LnFugacityCoeff
COTHPR_HYSYS_LnFuga
cityCoeff
Peng-Robinson fugacity
coefficient.
LnFugacity
COTHPR_HYSYS_LnFuga
city
Peng-Robinson fugacity.
MolarVolume
COTHPR_HYSYS_Volume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHPRZFactor
Peng-Robinson compressibility
factor.
amix
COTHPRab_1
Peng-Robinson amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
Property Packages
7-5
Peng-Robinson-Stryjek-Vera
This is a two-fold modification of the PR equation of state that extends
the application of the original PR method for moderately non-ideal
systems. It provides a better pure component vapour pressure
prediction as well as a more flexible mixing rule than Peng robinson.
XML File Name
Name
Description
prsv_vapour
PRSV
Property Name
Class Name
Description
Enthalpy
COTHPRSVEnthalpy
PRSV enthalpy.
Entropy
COTHPRSVEntropy
PRSV entropy.
Cp
COTHPRSVCp
LnFugacityCoeff
COTHPRSVLnFugacityCoeff
LnFugacity
COTHPRSVLnFugacity
PRSV fugacity.
MolarVolume
COTHPRSVVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHPRSVZFactor
amix
COTHPRSVab_1
PRSV amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-5
7-6
Soave-Redlich-Kwong
In many cases it provides comparable results to PR, but its range of
application is significantly more limited. This method is not as reliable
for non-ideal systems.
7-6
Name
Description
srk_vapour
SRK
Property Name
Class Name
Description
Enthalpy
COTHSRKEnthalpy
SRK enthalpy.
Entropy
COTHSRKEntropy
SRK entropy.
Cp
COTHSRKCp
LnFugacityCoeff
COTHSRKLnFugacityCoeff
LnFugacity
COTHSRKLnFugacity
SRK fugacity.
MolarVolume
COTHSRKVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHSRKZFactor
amix
COTHSRKab_1
SRK amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
Property Packages
7-7
Redlich-Kwong
The Redlich-Kwong equation generally provides results similar to PengRobinson. Several enhancements have been made to the PR as
described above which make it the preferred equation of state.
XML File Name
Name
Description
rk_vapour
Redlich-Kwong
Property Name
Class Name
Description
Enthalpy
COTHRKEnthalpy
RK enthalpy.
Entropy
COTHRKEntropy
RK entropy.
Cp
COTHRKCp
RK heat capacity.
LnFugacityCoeff
COTHRKLnFugacityCoeff
RK fugacity coefficient.
LnFugacity
COTHRKLnFugacity
RK fugacity.
MolarVolume
COTHRKVolume
RK molar volume.
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHRKZFactor
amix
COTHRKab_1
SRK amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-7
7-8
Zudkevitch-Joffee
This is a modification of the Redlich-Kwong equation of state, which
reproduces the pure component vapour pressures as predicted by the
Antoine vapour pressure equation. This model has been enhanced for
better prediction of vapour-liquid equilibrium for hydrocarbon systems,
and systems containing Hydrogen.
7-8
Name
Description
zj_vapour
Zudkevitch-Joffee
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHZJLnFugacityCoeff
ZJ fugacity coefficient.
LnFugacity
COTHZJLnFugacity
ZJ fugacity.
MolarVolume
COTHZJVolume
ZJ molar volume.
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHZJZFactor
ZJ compressibility factor.
amix
COTHZJab_1
ZJ amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
Property Packages
7-9
Kabadi-Danner
This model is a modification of the original SRK equation of state,
enhanced to improve the vapour-liquid-liquid equilibrium calculations
for water-hydrocarbon systems, particularly in dilute regions.
XML File Name
Name
Description
kd_vapour
Kabadi-Danner
Property Name
Class Name
Description
Enthalpy
COTHKDEnthalpy
KD enthalpy.
Entropy
COTHKDEntropy
KD entropy.
Cp
COTHKDCp
KD heat capacity.
LnFugacityCoeff
COTHKDLnFugacityCoeff
KD fugacity coefficient.
LnFugacity
COTHKDLnFugacity
KD fugacity.
MolarVolume
COTHKDVolume
KD molar volume.
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHKDZFactor
KD compressibility factor.
amix
COTHKDab_1
KD amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-9
7-10
Virial
This model enables you to better model vapour phase fugacities of
systems displaying strong vapour phase interactions. Typically this
occurs in systems containing carboxylic acids, or compounds that have
the tendency to form stable hydrogen bonds in the vapour phase. In
these cases, the fugacity coefficient shows large deviations from ideality,
even at low or moderate pressures.
7-10
Name
Description
virial_vapour
Virial
Property Name
Class Name
Description
Enthalpy
COTHVirial_Enthalpy
Virial enthalpy.
Entropy
COTHVirial_Entropy
Virial entropy.
Cp
COTHVirial_Cp
LnFugacityCoeff
COTHVirial_LnFugacityCoeff
LnFugacity
COTHVirial_LnFugacity
Virial fugacity.
MolarVolume
COTHVirial_Volume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
ZFactor
COTHVirial_ZFactor
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
Property Packages
7-11
Lee-Kesler-Plcker
This model is the most accurate general method for non-polar
substances and mixtures.
XML File Name
Name
Description
lkp_vapour
Lee-Kesler-Plcker
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEnthalpy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHLKPLnFugacityCoeff
LnFugacity
COTHLKPLnFugacity
LKP fugacity.
MolarVolume
COTHLKPMolarVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
ZFactor
COTHLKPZFactor
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-11
7-12
Braun K10
This model is strictly applicable to heavy hydrocarbon systems at low
pressures. The model employs the Braun convergence pressure method,
where, given the normal boiling point of a component, the K-value is
calculated at system temperature and 10 psia (68.95 kPa).
7-12
Name
Description
braunk10_vapour
Braun K10
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHBraunK10LnFugacityCoeff
LnFugacity
COTHBraunK10LnFugacity
MolarVolume
COTHBraunK10Volume
MolarDensity
COTHCOSTALDDensity
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
Property Packages
7-13
Ideal Solution
Assumes the volume change due to mixing is zero. This model is more
commonly used for solutions comprised of molecules not too different
in size and of the same chemical nature.
XML File Name
Name
Description
idealsol_liquid
Ideal Solution
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHIdealSolLnFugacityCoeff
LnFugacity
COTHIdealSolLnFugacity
LnActivity Coeff
COTHIdealSolLnActivityCoeff
LnStdFugacity
COTHIdealStdFug
LnActivityCoeffDT
COTHIdealSolLnActivityCoeffDT
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHIdealSolGibbsEnergy
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
7-13
7-14
Property Name
Class Name
Description
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Regular Solution
This model eliminates the excess entropy when a solution is mixed at
constant temperature and volume. The model is recommended for nonpolar components where the molecules do not differ greatly in size. By
the attraction of intermolecular forces, the excess Gibbs energy may be
determined.
7-14
Name
Description
regsol_liquid
Regular Solution
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHRegSolLnFugacityCoeff
LnFugacity
COTHRegSolLnFugacity
LnActivity Coeff
COTHRegSolLnActivityCoeff
LnStdFugacity
COTHIdealStdFug
LnActivityCoeffDT
COTHRegSolLnActivityCoeffDT
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
Property Packages
Property Name
Class Name
Description
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-15
van Laar
This equation fits many systems quite well, particularly for LLE
component distributions. It can be used for systems that exhibit positive
or negative deviations from Raoults Law; however, it cannot predict
maxima or minima in the activity coefficient. Therefore it generally
performs poorly for systems with halogenated hydrocarbons and
alcohols.
XML File Name
Name
Description
vanlaar_liquid
van Laar
Two-parameter temperature
dependent van Laar Model
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHVanLaarLnFugacityCoeff
LnFugacity
COTHVanLaarLnFugacity
7-15
7-16
7-16
Property Name
Class Name
Description
LnActivity Coeff
COTHVanLaarLnActivityCoeff
LnStdFugacity
COTHVanLaarStdFug
LnActivityCoeffDT
COTHVanLaarLnActivityCoeffDT
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-17
Margules
This was the first Gibbs excess energy representation developed. The
equation does not have any theoretical basis, but is useful for quick
estimates and data interpolation.
XML File Name
Name
Description
margules_liquid
Margules
Two-parameter temperature
dependent Margules Model
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHMargulesLnFugacityCoeff
Margules fugacity
coefficient.
LnFugacity
COTHMargulesLnFugacity
Margules fugacity.
LnActivity Coeff
COTHMargulesLnActivityCoeff
Margules activity
coefficient.
LnStdFugacity
COTHMargulesStdFug
LnActivityCoeffDT
COTHMargulesLnActivityCoeffDT
Margules activity
coefficient wrt
temperature.
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
7-17
7-18
Property Name
Class Name
Description
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Wilson
First activity coefficient equation to use the local composition model to
derive the Gibbs Excess energy expression. It offers a
thermodynamically consistent approach to predicting multicomponent behaviour from regressed binary equilibrium data. However
the Wilson model cannot be used for systems with two liquid phases.
7-18
Name
Description
wilson_liquid
Wilson
Two-parameter temperature
dependent Wilson Model
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHWilsonLnFugacityCoeff
LnFugacity
COTHWilsonLnFugacity
Wilson fugacity.
LnActivity Coeff
COTHWilsonLnActivityCoeff
LnStdFugacity
COTHWilsonStdFug
LnActivityCoeffDT
COTHWilsonLnActivityCoeffDT
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
Property Packages
Property Name
Class Name
Description
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-19
General NRTL
This variation of the NRTL model uses five parameters and is more
flexible than the NRTL model. Apply this model to systems with a wide
boiling point range between components, where you require
simultaneous solution of VLE and LLE, and where there exists a wide
boiling point or concentration range between components.
XML File Name
Name
Description
nrtl_liquid
General NRTL
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
ActTempDep
COTHNRTLTempDep
LnFugacityCoeff
COTHNRTLLnFugacityCoeff
LnFugacity
COTHNRTLLnFugacity
NRTL fugacity.
LnActivity Coeff
COTHNRTLLnActivityCoeff
LnStdFugacity
COTHNRTLStdFug
LnActivityCoeffDT
COTHNRTLLnActivityCoeffDT
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
7-19
7-20
Property Name
Class Name
Description
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
UNIQUAC
This model uses statistical mechanics and the quasi-chemical theory of
Guggenheim to represent the liquid structure. The equation is capable
of representing LLE, VLE, and VLLE with accuracy comparable to the
NRTL equation, but without the need for a non-randomness factor.
7-20
Name
Description
uniquac_liquid
UNIQUAC
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHUNIQUACLnFugacityCoeff
UNIQUAC fugacity
coefficient.
LnFugacity
COTHUNIQUACLnFugacity
UNIQUAC fugacity.
LnActivity Coeff
COTHUNIQUACLnActivityCoeff
UNIQUAC activity
coefficient.
Property Packages
7-21
Property Name
Class Name
Description
LnStdFugacity
COTHIdeallStdFug
LnActivityCoeffDT
COTHUNIQUACLnActivityCoeffDT
UNIQUAC activity
coefficient wrt
temperature.
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-21
7-22
Chien-Null
This model provides consistent framework for applying existing Activity
Models on a binary by binary basis. It allows you to select the best
Activity Model for each pair in your case.
7-22
Name
Description
cn_liquid
Chien-Null
Three-parameter temperature
dependent Chien-Null Model.
Property Name
Class Name
Description
Enthalpy
COTHCavettEnthalpy
Cavett enthalpy.
Entropy
COTHCavettEntropy
Cavett entropy.
Cp
COTHCavettCp
LnFugacityCoeff
COTHCNLnFugacityCoeff
CN fugacity coefficient.
LnFugacity
COTHCNLnFugacity
CN fugacity.
LnActivity Coeff
COTHCNLnActivityCoeff
CN activity coefficient.
LnActivityCoeffDT
COTHCNLnActivityCoeffDT
LnStdFugacity
COTHIdealStdFug
ActTempDep
COTHCNTempDep
HYSYS CN temperature
dependent properties.
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
Viscosity.
ThermalConductivity
COTHThermCond
Thermal conductivity.
SurfaceTension
COTHSurfaceTension
Surface Tension.
Helmholtz
COTHCavettHelmholtz
InternalEnergy
COTHCavettInternalEnergy
GibbsEnergy
COTHCavettGibbs
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Property Packages
Property Name
Class Name
Description
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-23
Antoine
This model is applicable for low pressure systems that behave ideally.
XML File Name
Name
Description
antoine_liquid
Antoine
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHAntoineLnFugacityCoeff
LnFugacity
COTHAntoineLnFugacity
Antoine fugacity.
LnActivity Coeff
COTHAntoineLnActivityCoeff
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
HYSYS Viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
Surface Tension.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-23
7-24
Braun K10
This model is strictly applicable to heavy hydrocarbon systems at low
pressures. The model employs the Braun convergence pressure method,
where, given the normal boiling point of a component, the K-value is
calculated at system temperature and 10 psia (68.95 kPa).
7-24
Name
Description
braunk10_liquid
Braun K10
Property Name
Class Name
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHBraunK10LnFugacityCoeff
LnFugacity
COTHBraunK10LnFugacity
LnActivity Coeff
COTHBraunK10LnActivityCoeff
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
HYSYS thermal
conductivity.
Description
SurfaceTension
COTHSurfaceTension
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-25
Esso Tabular
This model is strictly applicable to hydrocarbon systems at low
pressures. The model employs a modification of the Maxwell-Bonnel
vapour pressure model.
XML File Name
Name
Description
essotabular_liquid
Esso Tabular
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHEssoLnFugacityCoeff
LnFugacity
COTHEssoLnFugacity
Esso fugacity.
LnActivity Coeff
COTHEssoLnActivityCoeff
MolarDensity
COTHCOSTALDDensity
MolarVolume
COTHCOSTALDVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-25
7-26
Chao-Seader
This method for heavy hydrocarbons, where the pressure is less than
10342 kPa (1500 psia), and temperatures range between -17.78 and
260C (0-500F).
7-26
Name
Description
cs_liquid
Chao-Seader
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
Lee-Kesler heat
capacity.
LnFugacityCoeff
COTHChaoSeaderLnFugacityCoeff
Chao-Seader fugacity
coefficient.
LnFugacity
COTHChaoSeaderLnFugacity
Chao-Seader fugacity.
MolarVolume
COTHRKVolume
Redlich-Kwong molar
volume.
ZFactor
COTHRKZFactor
Redlich-Kwong
compressibility factor.
amix
COTHRKab_1
Redlich-Kwong EOS
amix.
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
HYSYS thermal
conductivity.
SurfaceTension
COTHSurfaceTension
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-27
Grayson-Streed
This model is recommended for simulating heavy hydrocarbon systems
with a high hydrogen content.
XML File Name
Name
Description
gs_liquid
Grayson-Streed
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHGraysonStreedLnFugacity
Coeff
Grayson-Streed fugacity
coefficient.
LnFugacity
COTHGraysonStreedLnFugacity
Grayson-Streed fugacity.
MolarVolume
COTHRKVolume
Redlich-Kwong molar
volume.
ZFactor
COTHRKZFactor
Redlich-Kwong
compressibility factor.
amix
COTHRKab_1
Redlich-Kwong EOS
amix.
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
HYSYS thermal
conductivity.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-27
7-28
HysysPR
The HysysPR EOS is similar to the PR EOS with several enhancements to
the original PR equation. It extends the range of applicability and better
represents the VLE of complex systems.
7-28
Name
Description
hysyspr_liquid
HysysPR
Property Name
Class Name
Description
Enthalpy
COTHPR_HYSYS_Enthalpy
Peng-Robinson
enthalpy.
Entropy
COTHPR_HYSYS_Entropy
Peng-Robinson entropy.
Cp
COTHPR_HYSYS_Cp
Peng-Robinson heat
capacity.
LnFugacityCoeff
COTHPR_HYSYS_LnFugacityCoeff
Peng-Robinson fugacity
coefficient.
LnFugacity
COTHPR_HYSYS_LnFugacity
Peng-Robinson
fugacity.
MolarVolume
COTHPR_HYSYS_Volume
Peng-Robinson molar
volume.
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
HYSYS thermal
conductivity.
ZFactor
COTHPRZFactor
Peng-Robinson
compressibility factor.
amix
COTHPRab_1
Peng-Robinson amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-29
Kabadi-Danner
This model is a modification of the original SRK equation of state,
enhanced to improve the vapour-liquid-liquid equilibrium calculations
for water-hydrocarbon systems, particularly in dilute regions.
XML File Name
Name
Description
kd_liquid
Kabadi-Danner
Property Name
Class Name
Description
Enthalpy
COTHKDEnthalpy
Kabadi-Danner enthalpy.
Entropy
COTHKDEntropy
Kabadi-Danner entropy.
Cp
COTHKDCp
LnFugacityCoeff
COTHKDLnFugacityCoeff
Kabadi-Danner fugacity
coefficient.
LnFugacity
COTHKDLnFugacity
Kabadi-Danner fugacity.
MolarVolume
COTHKDVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHKDZFactor
Kabadi-Danner compressibility
factor.
amix
COTHKDab_1
Kabadi-Danner amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-29
7-30
Peng-Robinson
This model is ideal for VLE calculations as well as calculating liquid
densities for hydrocarbon systems. However, in situations where highly
non-ideal systems are encountered, the use of Activity Models is
recommended.
7-30
Name
Description
pr_liquid
Peng-Robinson
Property Name
Class Name
Description
Enthalpy
COTHPREnthalpy
Peng-Robinson enthalpy.
Entropy
COTHPREntropy
Peng-Robinson entropy.
Cp
COTHPRCp
LnFugacityCoeff
COTHPRLnFugacityCoeff
Peng-Robinson fugacity
coefficient.
LnFugacity
COTHPRLnFugacity
Peng-Robinson fugacity.
MolarVolume
COTHPRVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHPRZFactor
Peng-Robinson compressibility
factor.
amix
COTHPRab_1
Peng-Robinson amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-31
Peng-Robinson-Stryjek-Vera
This is a two-fold modification of the PR equation of state that extends
the application of the original PR method for moderately non-ideal
systems. It provides a better pure component vapour pressure
prediction as well as a more flexible Mixing Rule than Peng robinson.
XML File Name
Name
Description
prsv_liquid
PRSV
Peng-Robinson-Stryjek-Vera EOS
using Mixing Rule 1 for all properties.
Property Name
Class Name
Description
Enthalpy
COTHPRSVEnthalpy
PRSV enthalpy.
Entropy
COTHPRSVEntropy
PRSV entropy.
Cp
COTHPRSVCp
LnFugacityCoeff
COTHPRSVLnFugacityCoeff
LnFugacity
COTHPRSVLnFugacity
PRSV fugacity.
MolarVolume
COTHPRSVVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHPRSVZFactor
amix
COTHPRSVab_1
PRSV amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-31
7-32
Soave-Redlich-Kwong
In many cases it provides comparable results to PR, but its range of
application is significantly more limited. This method is not as reliable
for non-ideal systems.
7-32
Name
Description
srk_liquid
SRK
Property Name
Class Name
Description
Enthalpy
COTHSRKEnthalpy
SRK enthalpy.
Entropy
COTHSRKEntropy
SRK entropy.
Cp
COTHSRKCp
LnFugacityCoeff
COTHSRKLnFugacityCoeff
LnFugacity
COTHSRKLnFugacity
SRK fugacity.
MolarVolume
COTHSRKVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHSRKZFactor
amix
COTHSRKab_1
SRK amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-33
Virial
This model enables you to better model vapour phase fugacities of
systems displaying strong vapour phase interactions. Typically this
occurs in systems containing carboxylic acids, or compounds that have
the tendency to form stable hydrogen bonds in the vapour phase. In
these cases, the fugacity coefficient shows large deviations from ideality,
even at low or moderate pressures.
XML File Name
Name
Description
virial_liquid
Virial
Property Name
Class Name
Description
LnFugacityCoeff
COTHPR_LnFugacityCoeff
Peng-Robinson fugacity
coefficient.
LnFugacity
COTHPR_LnFugacity
Peng-Robinson fugacity.
LnStdFugacity
COTHIdealStdFug
MolarVolume
COTHSolidVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHPR_ZFactor
Peng-Robinson compressibility
factor.
Enthalpy
COTHPR_Enthalpy
Peng-Robinson enthalpy.
Enthalpy
COTHSolidEnthalpy
Entropy
COTHPR_Entropy
Peng-Robinson entropy.
Entropy
COTHSolidEntropy
Cp
COTHPR_Cp
Cp
COTHSolidCp
amix
COTHPRab_1
Peng-Robinson amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
7-33
7-34
Zudkevitch-Joffee
This is a modification of the Redlich-Kwong equation of state, which
reproduces the pure component vapour pressures as predicted by the
Antoine vapour pressure equation. This model has been enhanced for
better prediction of vapour-liquid equilibrium for hydrocarbon systems,
and systems containing Hydrogen.
7-34
Name
Description
zj_liquid
Zudkevitch-Joffee
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEntropy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHZJLnFugacityCoeff
Zudkevitch-Joffee fugacity
coefficient.
LnFugacity
COTHZJLnFugacity
Zudkevitch-Joffee fugacity.
MolarVolume
COTHZJVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHZJZFactor
Zudkevitch-Joffee compressibility
factor.
amix
COTHZJab_1
Zudkevitch-Joffee amix.
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
Property Packages
7-35
Lee-Kesler-Plcker
This model is the most accurate general method for non-polar
substances and mixtures.
XML File Name
Name
Description
lkp_liquid
Lee-Kesler-Plcker
Property Name
Class Name
Description
Enthalpy
COTHLeeKeslerEnthalpy
Lee-Kesler enthalpy.
Entropy
COTHLeeKeslerEnthalpy
Lee-Kesler entropy.
Cp
COTHLeeKeslerCp
LnFugacityCoeff
COTHLKPLnFugacityCoeff
LnFugacity
COTHLKPLnFugacity
LKP fugacity.
MolarVolume
COTHLKPMolarVolume
Viscosity
COTHViscosity
HYSYS viscosity.
ThermalConductivity
COTHThermCond
SurfaceTension
COTHSurfaceTension
ZFactor
COTHLKPZFactor
IGCp
COTHIdealGasCp
OffsetIGH
COTHOffsetIGH
OffsetH
COTHOffsetH
OffsetIGS
COTHOffsetIGS
OffsetS
COTHOffsetS
Offset entropy.
MolarDensity
COTHSolidDensity
MolarVolume
COTHMolarVolume
Enthalpy
COTHSolidEnthalpy
Solid enthalpy.
Entropy
COTHSolidEntropy
Solid entropy.
Cp
COTHSolidCp
7-35
7-36
7-36
References
8-1
8 References
1
Prausnitz, J.M.; Anderson, T.; Grens, E.; Eckert, C.; Hsieh, R.; and O'Connell,
J.P. Computer Calculations for Multi-Component Vapour-Liquid and
Liquid-Liquid Equilibria Prentice-Hall Inc. (1980).
Modell, M. and Reid, R.D., Thermodynamics and its Applications, 2nd Ed.,
Prentice-Hall, Inc. (1983).
Michelsen, M.L., The Isothermal Flash Problem. Part I. Stability, Part II. Phase
Split Calculation, Fluid Phase Equilibria, 9 1-19; 21-40. (1982).
Reid, J.C.; Prausnitz, J.M. and Poling, B.E. The Properties of Gases and Liquid
McGraw-Hill Inc. (1987).
Feynman, R.P., Leighton, R.B., and Sands, M., The Feyman Lectures on
Physics Addison-Wesley Publishing Company. (1966).
Peng, D.Y. and Robinson, D.B. A New Two Constant Equation of State Ind.
Eng. Chem. Fundamen. 15, 59-64. (1976).
10
11
12 Graboski,
13
8-1
8-2
14
15 Mathias,
16
Kabadi, V.N.; Danner, R.P., A Modified Soave Redlich Kwong Equation of State
for Water-Hydrocarbon Phase Equilibria, Ind. Eng. Chem. process Des.
Dev., 24, 537-541. (1985).
17
18
19 Hayden,
20
Wilson, G.M. Vapour-Liquid Equilibrium XI: A New Expression for the Excess
Free Energy of Mixing J. Am. Chem Soc. 86, 127-130. (1964).
21
24
25 Fredenslund,
26 Wilson,
27
Derr, E.L. and Deal, C.H., Instn. Chem. Eng. Symp. Ser. No. 32, Inst. Chem.
Engr. London 3, 40-51. (1969).
28
29 Kojima,
30
8-2
Orye, R.V. and Prausnitz, J.M. Multi-Component Equilibria with the Wilson
Equation Ind. Eng. Chem. 57, 18-26. (1965).
References
31
8-3
32 Jensen,
T.; Fredenslund, A. and Rasmussen, Pure Component VapourPressures using UNIFAC Group Contribution Ind. Eng. Chem. Fundamen.
20, 239-246. (1981).
33
34
35
W.H., H.S. and S.I. Sandler, Use of ab Initio Quantum Mechanics Calculations
in Group Contribution Methods. 1. Theory and the Basis for Group
Identifications Ind. Eng. Chem. Res. 30, 881-889. (1991).
36 W.H.,
37
McClintock, R.B.; Silvestri, G.J., Formulations and Iterative Procedures for the
Calculation of Properties of Steam, The American Society of Mechanical
Engineers, New York. (1967).
38
Hankinson, R.W. and Thompson, G.H., AIChE J., 25, 653. (1979).
39 Ely,
40
Hildebrand, J.H., Prausnitz, J.M. and Scott, R.L Regular and Related
Solutions, Van Nostrand Reinhold Co., New York. (1970).
41
42
Twu, C.H., I.E.C. Proc. Des. & Dev. 24, 1287. (1985).
43 Twu,
44
45
8-3
8-4
46
Soave, G. Improvement of the van der Waals Equation of State Chem. Eng.
Sci 39, 2, 357-369. (1984).
47 Chao,
48
49
Pierotti, G.J.; Deal, C.H. and Derr, E.L. Ind. Eng. Chem. 51, 95. (1959).
50 Lee,
51
52
53
Perry, R.H. and Green, D.W. Perrys Chemical Engineers Handbook (Seventh
Edition) McGraw-Hill. (1997).
54 Reid,
C.R., Prausnitz, J.M. and Sherwood, T.K., The Properties of Gases and
Liquids, McGraw-Hill Book Company. (1977).
8-4
Index
A
Activity Coefficient Models
vapour phase options 2-29
Activity Coefficients 2-9
See individual activity models
Activity Models 3-93
See individual Activity models
Asymmetric Phase Representation 2-24
B
Bubble Point 6-5
BWR Equation 3-91
C
carboxylic acid 2-22
Cavett Method 4-2
Chao Seader 3-178
semi-empirical method 3-178
Chao-Seader Model 3-178
Chemical Potential
ideal gas 2-6
real gas 2-8
Chien-Null Model 3-169
property classes 3-172
property methods 3-172
COSTALD Method 4-11
Cp 2-35
D
Departure Functions
Enthalpy 2-35
Dew Point 6-4
Dimerization 2-20
E
Enthalpy Flash 6-5
Enthalpy Reference States 5-2
Entropy Flash 6-6
Entropy Reference States 5-3
Equations of State
See also individual equations of state
Equilibrium Calculations 2-23
Equilibrium calculations 2-23
F
Flash
T-P Flash 6-3
vapour fraction 6-36-4
Flash Calculations
temperature-pressure (TP) 6-2
Flash calculations 2-23
Fugacity 2-8
ideal gas 2-17
simplifications 2-17
G
General NRTL Model 3-145
Gibbs Free Energy 2-31
Gibbs-Duhem Equation 2-15
Grayson Streed 3-179
semi-empirical method 3-179
Grayson-Streed Model 3-179
H
Henrys Law 2-11, 2-29
estimation of constants 2-13
HypNRTL Model 3-144
HysysPR Equation of State 3-16
mixing rules 3-23
property classes 3-17
property methods 3-17
I
Ideal Gas Cp 5-5
Ideal Gas Equation of State 3-3
property classes 3-4
property methods 3-4
Ideal Gas Law 2-29
Ideal Solution Activity Model 3-96
property classes 3-96
property methods 3-96
Insoluble Solids 4-21
Interaction Parameters 2-25
Internal Energy 2-3
K
Kabadi-Danner Equation of State 3-61
mixing rules 3-69
property classes 3-64
property methods 3-64
K-values 2-23
L
Lee-Kesler Equation of State 3-87
mixing rules 3-91
property classes 3-88
I-1
Index
I-2
I-2
Index
I-3
Z
Zudkevitch-Joffee Equation of State 3-53
mixing rules 3-58
property classes 3-53
property methods 3-53
I-3
I-4
I-4
Index