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Table of Contents
Technical Support.................................................... iii
Online Technical Support Center ............................iv
Phone and Email ................................................. v
iii
4.4 Viscosity ........................................................414
4.5 Thermal Conductivity.......................................418
4.6 Surface Tension ..............................................421
4.7 Insoluble Solids ..............................................422
8 Utilities................................................................. 81
8.1 Introduction .................................................... 82
8.2 Envelope Utility................................................ 82
Index.................................................................... I1
iv
v
vi
Introducing COMThermo 11
1 Introducing
COMThermo
1.1 Introduction................................................................................... 2
11
12 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.
12
Introducing COMThermo 13
13
14 Introduction
14
Thermodynamic Principles 21
2 Thermodynamic
Principles
2.1 Introduction................................................................................... 3
21
22
22
Thermodynamic Principles
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.
( dU ) S, = 0 (2.2)
V
π π π nc
j j j j j j
dU = ∑T dS – ∑P dV + ∑ ∑ µi dn i (2.3)
j=1 j=1 j=1i=1
j ∂U
µi = (2.4)
∂ni S, V, n j
k≠1
23
24 Introduction
π
j
dS = ∑ dS = 0 (2.5)
j=1
π
j
dV = ∑ dV = 0 (2.6)
j=1
π
j
∑ dni = 0 i = 1, ..., nc (2.7)
j=1
π
1 j
dS = – ∑ dS (2.8)
j=2
π
1 j
dV = – ∑ dV (2.9)
j=2
π
1 j
dn i = ∑ dni (2.10)
j=2
24
Thermodynamic Principles
π π π nc
j 1 j j 1 j j 1 j
dU = ∑(T –T ) dS – ∑( P – P ) dV + ∑ ∑ ( µi – µi )dni (2.11)
j >1 j >1 j > 1 i= 1
∂U ∂U ∂U ∂2U (2.12)
 = 0  = 0  = 0  = 0
∂S ∂V ∂n i ∂S 2
Therefore:
1
T = T
j
j = 2, ..., π (2.13)
25
26 Chemical Potential & Fugacity
26
Thermodynamic Principles
nc
dG = – SdT + VdP + ∑ µi dni (2.17)
i=1
where:
∂G
µi = (2.18)
∂ n i T, P, n k ≠ 1
dG i = – S i dT + V i dP (2.19)
where:
∂G
G i =  (2.20)
∂n i T, P, n k ≠ 1
dµi = dG i = V i dP (2.21)
27
28 Chemical Potential & Fugacity for a Real
µi = C i + RT ln f i (2.22)
1 2 π (2.23)
fi = fi = … = fi
Vi
∂ ( ln f ) =  (2.24)

∂P i
T RT
28
Thermodynamic Principles
RTd ln P = V
ideal
dP (2.26)
P ideal
ln f = V
 V dP
P ∫ RT – 
RT
(2.28)
0
P
(
Z – 1 )
ln f = ∫ dP (2.29)
P P
0
29
210 Fugacity & Activity Coefficients
The ratio f/P measures the deviation of a real gas from ideal gas
behaviour, and is called the fugacity coefficient:
f (2.30)
φ = 
P
P
fi ( Zi – 1 ) (2.31)
ln 
Px i
 = ∫  dP
P
0
∂Z P ∂V PV
Zi = =  = i (2.32)
∂n i T, j
P, n k ≠ i RT ∂n i T, j
P, n k ≠ i RT
P
fi 1
 =  ∫ V i – RT
ln   dP (2.33)
Px i RT P
0
fi
φi = 
 (2.34)
Px i
210
Thermodynamic Principles
V
fi = yi fi
V, pure (2.35)
L
fi = xi fi
L, pure (2.36)
L
fi
γ i = 
 (2.37)
L, pure
fi xi
211
212 Henry’s Law
L
fi
 = lim γ i = 1
lim  (2.38)
x i →1 f L, purex x i →1
i i
L
fi
 = lim γ i∗ = 1
lim  (2.39)
ref
x i →0 f x x i →0
i i
212
Thermodynamic Principles
L
ref f
fi = lim i = H ij (2.40)
x i →0 x i
∞ sat
Pj
Sat
A ij 2 Vi ( P – Pj )
ln H ij = ln H ij +  ( x j – 1 ) + 
 (2.41)
RT RT
213
214 Henry’s Law
2.6.1 NonCondensable
Components
Noncondensable components are treated using Henry’s
constants as defined by Equation (2.40). The temperature
dependency of the Henry’s law for a binary pair ij is represented
by an Antoinetype of equation with four parameters per binary
pair:
B (2.42)
ln H ij = A ij + ij + C ij ln T + D ij T
T
The Henry’s constant of A mixing rule for the Henry’s constant of a noncondensable
component i in a multi component in a mixture of condensable components must be
component mixture is
estimated neglecting the defined. There are several alternatives, but the following
solventsolvent formulation works reasonably well:
interactions.
nc 2

3
∑ ln H ij x j V c, j
j =1 , j ≠ i
ln H i, mixture =  (2.43)
nc 2

3
∑ x j V c, j
j =1 , j ≠ i
214
Thermodynamic Principles
∆g = ∆g + ∆g
I II (2.44)
L, pure
I fi
∆g = RT ln  (2.45)
G
fi
II (2.46)
∆g = RT ln γ i x i
G
fi = γ i xi fi
L, pure (2.47)
and therefore:
∆g = 0 (2.48)
L
RT ln γ i = ν i ( δj – δi ) φj
2 2 (2.49)
215
216 GibbsDuhem Equation
G L 2 2
fi ν i ( δj – δi ) φj
H ij
L,
 = fi
= 
pure
exp  (2.50)
xi RT
G L 2
fi ν i ( δi – δj )
H ij = 
L,
 = fi
pure
exp  (2.51)
xi RT
2.7 GibbsDuhem
Equation
At constant temperature and pressure, the GibbsDuhem
equation states that:
nc
∑ xi d ln γ i = 0 (2.52)
i=1
216
Thermodynamic Principles
ref
ref P V
= γ i exp ∫  dP
P P i
γi (2.53)
RT
P
ref P V
exp ∫  dP
L P ref L P ref i
fi = γ i xi fi or fi = γi xi fi (2.54)
RT
ref
P
P ref
ref vap sat Vi
fi = P i φi exp ∫  dP (2.55)
RT
P vap
i
217
218 GibbsDuhem Equation
ref
P
L vap sat V V
fi = P i φi exp ∫vap
i + i dP
RT RT
(2.56)
Pi
Ideal Gas
When ideal gas behaviour is assumed, this usually implies that
the Poynting correction is dropped. Also, since the gas is ideal,
φisat = 1:
L vap (2.57)
fi = γ i xi Pi
218
Thermodynamic Principles
P
L vap sat Vi

fi = γ i x i P i φi exp ∫ RT
 dP (2.59)
vap
Pi
P
L vap sat Vi

fi = γ i x i P i φi exp ∫ RT
 dP (2.60)
vap
Pi
vap
Vi ( P – Pi )
L
fi = γ i xi Pi
vap sat
φi exp  (2.61)
RT
vap
ref vap sat Vi ( P – Pi )
fi = Pi φi exp  (2.62)
RT
219
220 Association in Vapour Phase  Ideal Gas
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
fi = γ i xi Pi φi (2.63)
2A ↔ A 2 (2.65)
[ A2 ]
K = 

2
(2.66)
[A]
220
Thermodynamic Principles
Assuming that the species in the vapour phase behave like ideal
gases:
[ Pd ]
K = 

2
(2.67)
[ Pm ]
2 –2 e (2.68)
y m = 
2–e
e 
y d =  (2.69)
2–e
vap
P PA yd e ( 2 – e )  = 
e( 2 – e) 
K = d = 
 =  (2.70)
2 vap 2 2 vap vap 2
Pm ( PA ym ) ( 2 – 2e ) P A 4P A ( 1 – e )
1
e = 
 (2.71)
vap
1 + 4KP A
221
222 Association in Vapour Phase  Ideal Gas
vap 2
PA ° + Pd = Pm
= Pm ° + K [ Pm
° ] (2.72)
vap
1 + 4KP A – 1 (2.73)
°
Pm = 

2K
Pm = γ A xA Pm
° (2.74)
w A = n m M m + 2n d M m (2.75)
Dividing by Mm:
n A = n m + 2n d (2.76)
222
Thermodynamic Principles
x m + 2x d + x 2 = 1 (2.77)
P A = P m + 2P d + P 2 (2.78)
Knowing that:
P = Pm + Pd + P2 (2.79)
You have:
P m + 2P d P m + 2P d
y A =  = 
 (2.80)
P m + 2P d + P 2 P + Pd
vap
P2 P2 γ 2 x2 P2
y 2 =  = 
 = 
 (2.81)
P m + 2P d + P 2 P + Pd P + Pd
P
f dimerizing =  P m° ( 1 + 2KP m )
L
(2.82)
P + Pd
223
224 Equilibrium Calculations
P
f non – d imerizing =  Pnon – dimerizing
L vap
(2.83)
P + Pd
2.9 Equilibrium
Calculations
When performing flash calculations, Kvalues are usually
calculated. Kvalues are defined as follows:
y
K i = i (2.84)
xi
224
Thermodynamic Principles
V V
f i = φi y i P (2.85)
L L
f i = φi x i P (2.86)
and therefore:
L
φ
K i = i (2.87)
V
φi
L L ref (2.88)
f i = φ i x i P = γ i x i fi
and therefore:
ref
L γ i fi (2.89)
φi = 

P
225
226 Basic Models for VLE & LLE
226
Thermodynamic Principles
227
228 Basic Models for VLE & LLE
Temperature
Method Pressure, psia
,F
PR > 456 (271 < 15,000 (100,000
C) kPa)
SRK > 225 (143 < 5,000 (35,000
C) kPa)
228
Thermodynamic Principles
229
230 Basic Models for VLE & LLE
Recommended Property
Type of System
Method
TEG Dehydration PR
Cryogenic Gas Processing PR, PRSV
Air Separation PR, PRSV
Reservoir Systems PR, PR Options
Highly Polar and nonhydrocarbon Activity Models, PRSV
systems
Hydrocarbon systems where H2O Kabadi Danner
solubility in HC is important
Enthalpy/Entropy
Property Method VLE Calculation
Calculation
Equations of State
PR PR PR
SRK SRK SRK
Equation of State Options
PRSV PRSV PRSV
Kabadi Danner Kabadi Danner SRK
RKZudekevitchJoffee RKZudekevitchJoffee RKZudekevitchJoffee
Activity Models
Liquid
Margules Margules Cavett
Van Laar Van Laar Cavett
Wilson Wilson Cavett
NRTL NRTL Cavett
UNIQUAC UNIQUAC Cavett
Chien Null Chien Null Cavett
Vapour
Ideal Gas Ideal Gas Ideal Gas
230
Thermodynamic Principles
Enthalpy/Entropy
Property Method VLE Calculation
Calculation
Ideal Gas/Dimer Ideal Gas/Dimer Ideal Gas
RK RK RK
Peng Robinson Peng Robinson Peng Robinson
Virial Virial Virial
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.
Henry’s Law
For systems containing noncondensable components, you can
supply Henry’s law information via the extended Henry’s law
equations.
231
232 Basic Models for VLE & LLE
ln H ij = A + B
 + C ln ( T ) + DT (2.90)
T
T = temperature in degrees K
232
Thermodynamic Principles
Mathematically:
I II III
fi = fi = fi … (2.91)
233
234 Phase Stability
nc fi
E ID
G = G–G = RT ∑ xi ln γ i = RT ∑x i ln 
ref
(2.92)
i=1 xi fi
np nc
E P P, E
G = ∑ ∑xi Gi (2.93)
j =1 i
is smaller than:
np – 1 nc
E P P, E
G = ∑ ∑xi Gi (2.94)
j =1 i
234
Thermodynamic Principles
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
Figure 2.2
G1
1 dG1
dx
0 0.5
0.5 xi xi
235
236 Phase Stability
I 2 I
xi – xi G – G
β =  and β =  (2.95)
II I II I
xi – xi G –G
Therefore, (G2, xi), (GI, xiI) and (GII, xiII) are colinear points
and you can calculate G2 = βGI + (1β)GII.
where:
I I I I II II II II
G = G ( x i , x j , P, T ) G = G ( x i , x j , P, T ) (2.96)
2
∂G 1 ∂ G 1
= 0 and 2 = 0 (2.97)
∂ x i T, P ∂x i T, P
If you use
nc
E ID
G = G–G = RT ∑ xi ln γ i (2.98)
i=1
236
Thermodynamic Principles
ID E ID
G = G +G = G + Ax i x j
ID
(2.99)
G = ∑xi Gi + RTxi ln xi + RTxj ln xj
and
G = ∑xi Gi + RT ( xi ln xi + xj ln xj ) + Axi xj
∂G x
∂x i T, = A – 2Axi + RT ln i + G i – G j
P xj (2.100)
2
∂ G T
= – 2A + R 
∂ x i T, P
xj xi
2
∂ G RT
= – 2A +  < 0 (2.101)
∂ x i T, P
xj xi
RT

The minimum of x j x i is at xi = xj = 0.5 and is equal to 4RT. Thus,
the minimum value of A for which phase splitting occurs is
A
 > 2 . A similar analysis can be performed for the other activity
RT
coefficient models for the binary case. The multicomponent
problem is more complex and useful discussions can be found in
the book by 3Modell and Reid (1983) and in the works of
4
Michelsen (1982) and 5Seider (1979).
237
238 Enthalpy/Cp Departure Functions
2.12 Enthalpy/Cp
Departure Functions
Let Prop be any thermodynamic property. If you define the
difference of PropPropo to be the residual of that property (its
value minus the value it would have at a reference state) and
call this reference state the ideal gas at the system temperature
and composition, you have:
P° V° = RT or V° = RT
 (2.102)
P°
Figure 2.3
1 2
erm erm
Isoth Isoth
A
Isobar 2
Pressure
Isobar 1
B
Ideal Gas
Enthalpy C D
238
Thermodynamic Principles
V
A – A° = – ∫ P dV (2.103)
V°
V ∞
A – A° = – ∫ P dV – ∫ P dV (2.104)
∞ V°
∞ ∞
RT
P = RT
 and ∫ P dV = ∫  dV (2.105)
V V
V° V°
It is interesting to note that AAo for an ideal gas is not zero. The
AAo
V
RT
term can be rearranged by adding and subtracting∫  dVand the
∞ V
final result is:
A – A° = – ∫ P – RT V
 dV – RT ln  (2.106)
V V°
∞
239
240 Enthalpy/Cp Departure Functions
V
∂ ∂P – R V
S – S° = –
∂T
( A – A° ) V = ∫ ∂T V V dV + R ln 
V° (2.107)
∞
H – H° = ( A – A° ) + T ( S – S° ) + RT ( Z – 1 )
2
∂H
Cp = and ∂C p = – T ∂ V
∂T P ∂P T ∂T 2 P
(2.108)
2
∂ V
dC p = – T 2 dP
∂T P
P 2
∂ V
C p – C p ° = – T ∫ 2 dP
∂T P
P°
or (2.109)
∂P 2
V 2 T 
∂ P ∂T V
C p – C p ° = T ∫ 2 dV –  – R
∂T V ∂
P
∞ ∂T T
nc
mix
I = ∑ xi Ii (2.110)
i=1
240
Thermodynamic Principles
T nc
L L L L
Hi = ∫ Cp i dT and H = ∑ xi Hi + ∆Hmix (2.111)
T, ref i=1
V L V V
H mix = H mix + ∆H + ∆H P + ∆H mix
V (2.112)
It is assumed that HiL at where: ∆HV is the enthalpy of vapourization of the mixture at the
the reference temperature
system pressure
is zero.
V
Usually the ∆H mix term is ignored (although it can be computed
in a fairly straight forward way for systems where association in
the vapour phase is important (2Prausnitz et al., (1980)).
V
The term ∆H P is the contribution to the enthalpy due to
compression or expansion, and is zero for an ideal gas. The
calculation of this term depends on what model was selected for
the vapour phase—Ideal Gas, Redlich Kwong or Virial.
241
242 Enthalpy/Cp Departure Functions
Figure 2.4
as)
deal G
0 (I
P =
A
re
ressu
Molar Enthalpy H
D
pressure to
compress the
liquid
T Tc
Absolute Temperature T Critical Temperature
242
Thermodynamic Calculation Models 31
3 Thermodynamic
Calculation Models
31
32 Equations of State
32
Thermodynamic Calculation Models
PV = RT (3.1)
Figure 3.1
33
34 Equations of State
Property Methods
systems without
association at low
Applicable
Calculation Method Property Class Name
Phase
Molar Volume Vapour COTHIGVolume Class
Enthalpy Vapour COTHIGEnthalpy Class
Entropy Vapour COTHIGEntropy Class
Isobaric heat capacity Vapour COTHIGCp Class
Fugacity coefficient Vapour COTHIGLnFugacityCoeff
calculation Class
Fugacity calculation Vapour COTHIGLnFugacity Class
IG Molar Volume
The following relation calculates the Molar Volume for a specific
phase.
V = RT
 (3.2)
P
34
Thermodynamic Calculation Models
IG Enthalpy
The following relation calculates enthalpy.
IG
H = ∑xi Hi (3.3)
IG Entropy
The following relation calculates entropy.
IG
S = ∑xi Si – R ∑x i ln x i (3.4)
35
36 Equations of State
IG Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
IG
Cp = ∑xi Cp i
(3.5)
IG Fugacity Coefficient
The following relation calculates the fugacity coefficient.
ln φi = 0 (3.6)
36
Thermodynamic Calculation Models
IG Fugacity
The following relation calculates the fugacity for a specific
phase.
fi = yi P (3.7)
RT  – 
a
P =   (3.8)
V – b V( V + b) + b( V – b )
37
38 Equations of State
where:
a = ac α
2 2
R Tc
a c = 0.45724  (3.9)
Pc
RT c
b = 0.077480 
Pc
Equations of state in
general  attractive and The functional dependency of the “a” term is shown in the
repulsion parts following relation.
Simplest cubic EOS  van
der Waals
Principle of corresponding 0.5
α = 1 + κ ( 1 – Tr )
states (3.10)
2
First successful κ = 0.37464 + 1.5422ω – 0.26992ω
modification for
engineering  RK
The property that is usually The accuracy of the PR and SRK equations of state are
required for engineering approximately the same. However, the PR EOS represents the
calculations is vapour
pressure. density of the liquid phase more accurately due to the lower
The SRK and RK EOS critical compressibility factor.
propose modifications
which improve the vapour These equations were originally developed for pure components.
pressure calculations for
relatively simple gases and To apply the PR EOS to mixtures, mixing rules are required for
hydrocarbons. 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.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and COTHPRZFactor Class
Liquid
Molar Volume Vapour and COTHPRVolume Class
Liquid
Enthalpy Vapour and COTHPREnthalpy Class
Liquid
Entropy Vapour and COTHPREntropy Class
Liquid
38
Thermodynamic Calculation Models
Applicable
Calculation Method Property Class Name
Phase
Isobaric heat capacity Vapour and COTHPRCp Class
Liquid
Fugacity coefficient Vapour and COTHPRLnFugacityCoeff
calculation Liquid Class
Fugacity calculation Vapour and COTHPRLnFugacity Class
Liquid
Isochoric heat capacity Vapour and COTHPRCv Class
Liquid
Mixing Rule 1 Vapour and COTHPRab_1 Class
Liquid
Mixing Rule 2 Vapour and COTHPRab_2 Class
Liquid
Mixing Rule 3 Vapour and COTHPRab_3 Class
Liquid
Mixing Rule 4 Vapour and COTHPRab_4 Class
Liquid
Mixing Rule 5 Vapour and COTHPRab_5 Class
Liquid
Mixing Rule 6 Vapour and COTHPRab_6 Class
Liquid
PR Z Factor
The compressibility factor, Z, is calculated as the root for the
following equation:
3 2 2 2 3
Z – ( 1 – B )Z + Z ( A – 3B – 2B ) – ( AB – B – B ) = 0 (3.11)
aP
A = 
 (3.12)
2 2
R T
bP (3.13)
B = 
RT
39
310 Equations of State
PR Molar Volume
The following relation calculates the molar volume for a specific
phase.
V = ZRT
 (3.14)
P
PR Enthalpy
The following relation calculates the enthalpy.
da 1 V + b( 1 + 2)
= PV – RT – a –  T  ln 
IG (3.15)
H–H dT 2 2b V + b ( 1 – 2 )
310
Thermodynamic Calculation Models
PR Entropy
The following relation calculates the entropy.
V–b 1 V + b ( 1 + 2 ) da
= R ln  –  ln  
IG
S–S (3.16)
RT 2b 2 V + b ( 1 – 2 ) dT
311
312 Equations of State
PR Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
∂V 2
V
2 T 
IG ∂ P ∂T
Cp – Cp = – T ∫ 2 dV + R + P (3.17)
∂T V ∂V

∞ ∂P T
312
Thermodynamic Calculation Models
PR Fugacity Coefficient
The following relation calculates the fugacity coefficient.
a
b  +  V + b(1 + 2)
ln φi = – ln ( V – b ) +  ln  – 1 + a + b (3.18)
V – b 2 2b V + b ( 1 – 2 ) a b
2
a = ∂n
a (3.19)
∂n
b = ∂nb
 (3.20)
∂n
PR Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.21)
313
314 Equations of State
PR Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.22)
∂P

∂V T
Mixing Rules
The mixing rules available for the PR EOS state are shown
below.
nc nc
a = ∑ ∑ ( xi xj aij ) (3.23)
i =1 j =1
nc
b = ∑ bi xi (3.24)
i =1
a ij = ξ ij a ci a cj αi αj (3.25)
0.5 (3.26)
αi = ( 1 – κ i ) ( 1 – T ri )
314
Thermodynamic Calculation Models
2 2
0.45724R T ci (3.27)
a ci = 

P ci
0.07780RT ci
b i = 
 (3.28)
P ci
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, ξ ij, which is
defined as:
2
ξ ij = 1 – A ij + B ij T + C ij T (3.30)
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
C (3.31)
ξ ij = 1 – A ij + B ij T + ij
T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
315
316 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, ξ ij, which is
defined as
2 2 (3.32)
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T )
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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.33)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
 (3.34)
2 2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
316
Thermodynamic Calculation Models
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.35)
C C
x i A ij + B ij T + ij + x j A ji + B ji T + ji
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
RT  – 
a (3.36)
P =  
V – b V( V + b) + b( V – b )
where:
a = ac α
2 2
R Tc
a c = 0.45724  (3.37)
Pc
RT c
b = 0.077480 
Pc
317
318 Equations of State
0.5
α = 1 + S ( 1 – Tr )
(3.38)
2
S = 0.37464 + 1.5422ω – 0.26992ω
Property Methods
A quick reference of calculation methods is shown in the table
below for the HysysPR EOS.
Calculation Applicable
Property Class Name
Method Phase
Z Factor Vapour and COTH_HYSYS_ZFactor Class
Liquid
Molar Volume Vapour and COTH_HYSYS_Volume Class
Liquid
Enthalpy Vapour and COTH_HYSYS_PREnthalpy Class
Liquid
Entropy Vapour and COTH_HYSYS_Entropy Class
Liquid
Isobaric heat Vapour and COTH_HYSYS_Cp Class
capacity Liquid
Fugacity coefficient Vapour and COTH_HYSYS_LnFugacityCoeff
calculation Liquid Class
Fugacity calculation Vapour and COTH_HYSYS_LnFugacity Class
Liquid
Isochoric heat Vapour and COTH_HYSYS_Cv Class
capacity Liquid
HysysPR Z Factor
The compressibility factor, Z, is calculated as the root for the
following equation:
3 2 2 2 3
Z – ( 1 – B )Z + Z ( A – 3B – 2B ) – ( AB – B – B ) = 0 (3.39)
318
Thermodynamic Calculation Models
aP 
A = 
2 2
(3.40)
R T
bP (3.41)
B = 
RT
V = ZRT
 (3.42)
P
319
320 Equations of State
HysysPR Enthalpy
The following relation calculates the enthalpy.
da 1 + b( 1 + 2)
= PV – RT – a –  T  ln V
IG (3.43)
H–H 
dT 2 2b V + b ( 1 – 2 )
320
Thermodynamic Calculation Models
HysysPR Entropy
The following relation calculates the entropy.
V–b 1 V + b ( 1 + 2 ) da
= R ln  –  ln  
IG
S–S (3.44)
RT 2b 2 V + b ( 1 – 2 ) dT
∂V 2
V
2 T 
IG ∂ P ∂T
Cp – Cp = – T ∫ 2 dV + R + P (3.45)
∂T V ∂V

∞ ∂P T
321
322 Equations of State
a
b  +  V + b(1 + 2)
ln φi = – ln ( V – b ) +  ln  – 1 + a + b (3.46)
V – b 2 2b V + b ( 1 – 2 ) a b
2
a = ∂n
a (3.47)
∂n
b = ∂nb
 (3.48)
∂n
HysysPR Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.49)
322
Thermodynamic Calculation Models
HysysPR Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.50)
∂P

∂V T
Mixing Rules
The mixing rules available for the HysysPR EOS state are shown
below.
nc nc
a = ∑ ∑ ( 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 αi αj (3.53)
323
324 Equations of State
0.5 (3.54)
αi = ( 1 – κ i ) ( 1 – T ri )
2 2
0.45724R T ci (3.55)
a ci = 

P ci
0.07780RT ci
b i = 
 (3.56)
P ci
2
0.37464 + 1.54226ωi – 0.26992ωi ωi < 0.49
κi = (3.57)
0.37964 + 1.48503ωi – 0.16442ω2i + 0.016666ω3i ωi ≥ 0.49
RT  – 
a (3.58)
P =  
V – b V( V + b) + b( V – b)
324
Thermodynamic Calculation Models
where:
a = ac α
2 2
R Tc
a c = 0.45724  (3.59)
Pc
RT c
b = 0.077480 
Pc
325
326 Equations of State
0.5 2
αi = [ 1 + κ i ( 1 – T r ) ]
0.5
κ i = κ 0i + κ 1 ( 1 + T ri ) ( 0.7 – T ri ) (3.60)
2 3
κ 0i = 0.378893 + 1.4897153ωi – 0.17131848ωi + 0.0196554ωi
ωi = Acentric factor
326
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the PRSV EOS.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and COTHPRSVZFactor Class
Liquid
Molar Volume Vapour and COTHPRSVVolume Class
Liquid
Enthalpy Vapour and COTHPRSVEnthalpy Class
Liquid
Entropy Vapour and COTHPRSVEntropy Class
Liquid
Isobaric heat capacity Vapour and COTHPRSVCp Class
Liquid
Fugacity coefficient Vapour and COTHPRSVLnFugacityCoeff
calculation Liquid Class
Fugacity calculation Vapour and COTHPRSVLnFugacity Class
Liquid
Isochoric heat capacity Vapour and COTHPRSVCv Class
Liquid
Mixing Rule 1 Vapour and COTHPRSVab_1 Class
Liquid
Mixing Rule 2 Vapour and COTHPRSVab_2 Class
Liquid
Mixing Rule 3 Vapour and COTHPRSVab_3 Class
Liquid
Mixing Rule 4 Vapour and COTHPRSVab_4 Class
Liquid
Mixing Rule 5 Vapour and COTHPRSVab_5 Class
Liquid
Mixing Rule 6 Vapour and COTHPRSVab_6 Class
Liquid
PRSV Z Factor
The compressibility factor, Z, is calculated as the root for the
327
328 Equations of State
following equation:
3 2 2 2 3
Z – ( 1 – B )Z + Z ( A – 3B – 2B ) – ( AB – B – B ) = 0 (3.61)
aP 
A = 
2 2
(3.62)
R T
bP (3.63)
B = 
RT
328
Thermodynamic Calculation Models
V = ZRT
 (3.64)
P
329
330 Equations of State
PRSV Enthalpy
The following relation calculates the enthalpy
da 1 + b( 1 + 2)
= PV – RT – a –  T  ln V
IG
H–H  (3.65)
dT 2 2b V + b ( 1 – 2 )
330
Thermodynamic Calculation Models
PRSV Entropy
The following relation calculates the entropy.
V–b 1 V + b ( 1 + 2 ) da
= R ln  –  ln  
IG
S–S (3.66)
RT 2b 2 V + b ( 1 – 2 ) dT
∂V 2
V T 
IG ∂2 P ∂T
Cp – Cp = – T ∫ 2 dV + R + P (3.67)
∂T V ∂V

∞ ∂P T
331
332 Equations of State
a
b  +  V + b(1 + 2)
ln φi = – ln ( V – b ) +  ln  – 1 + a + b (3.68)
V – b 2 2b V + b ( 1 – 2 ) a b
2
a = ∂n
a (3.69)
∂n
b = ∂nb
 (3.70)
∂n
PRSV Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.71)
332
Thermodynamic Calculation Models
PRSV Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.72)
∂P

∂V T
Mixing Rules
The mixing rules available for the PRSV equation are shown
below.
nc nc
a = ∑ ∑ ( xi xj aij ) (3.73)
i =1 j = 1
nc
b = ∑ bi xi (3.74)
i =1
0.5 (3.75)
a ij = ( a ii a jj ) ξ ij
333
334 Equations of State
αi = ( 1 – κ i ) ( 1 – T ri )
0.5 (3.76)
2 2
0.45724R T (3.77)
a i = ci
P ci
0.07780RT ci
b i = 
 (3.78)
P ci
0.5
κ i = κ i0+ κ i1( 1 + T ri )( 0.7 – T ri ) (3.79)
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, ξ ij, which is
defined as:
2 (3.81)
ξ ij = 1 – A ij + B ij T + C ij T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
C
ξ ij = 1 – A ij + B ij T + ij (3.82)
T
334
Thermodynamic Calculation Models
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T ) (3.83)
335
336 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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.84)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
 (3.85)
2 2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.86)
C C
x i A ij + B ij T + ij + x j A ji + B ji T + ji
T T
336
Thermodynamic Calculation Models
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
3.1.5 SoaveRedlichKwong
Equation of State
Wilson (1965, 1966) noted that the main drawback of the RK
equation of state was its inability of accurately reproducing the
vapour pressures of pure component constituents of a given
mixture. He proposed a modification to the RK equation of state
using the acentricity as a correlating parameter, but this
approach was widely ignored until 1972, when 11Soave (1972)
proposed a modification of the RK equation of this form:
RT a ( T, Tc , ω) (3.87)
P =  – 

V–b V( V + b)
ac α
RT  – 
P = 
V – b V( V + b)
2 2
R Tc
a c = Ωa  (3.88)
Pc
0.5
α = 1 + S ( 1 – Tr )
2
S = 0.480 + 1.574ω – 0.176ω
337
338 Equations of State
Refer to the Mixing To apply the SRK EOS to mixtures, mixing rules are required for
Rules section for the
applicable set of mixing
the “a” and “b” terms in Equation (3.270).
Property Methods
A quick reference of calculation methods is shown in the table
below for the SRK EOS.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and COTHSRKZFactor Class
Liquid
Molar Volume Vapour and COTHSRKVolume Class
Liquid
Enthalpy Vapour and COTHSRKEnthalpy Class
Liquid
Entropy Vapour and COTHSRKEntropy Class
Liquid
Isobaric heat capacity Vapour and COTHSRKCp Class
Liquid
Fugacity coefficient Vapour and COTHSRKLnFugacityCoeff
calculation Liquid Class
Fugacity calculation Vapour and COTHSRKLnFugacity Class
Liquid
Isochoric heat capacity Vapour and COTHSRKCv Class
Liquid
Mixing Rule 1 Vapour and COTHSRKab_1 Class
Liquid
Mixing Rule 2 Vapour and COTHSRKab_2 Class
Liquid
Mixing Rule 3 Vapour and COTHSRKab_3 Class
Liquid
Mixing Rule 4 Vapour and COTHSRKab_4 Class
Liquid
Mixing Rule 5 Vapour and COTHSRKab_5 Class
Liquid
Mixing Rule 6 Vapour and COTHSRKab_6 Class
Liquid
338
Thermodynamic Calculation Models
SRK Z Factor
The compressibility factor is calculated as the root for the
following equation:
3 2 2
Z – Z + Z ( A – B – B ) – AB = 0 (3.89)
aP
A = 
 (3.90)
2 2
R T
bP (3.91)
B = 
RT
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.
ZRT (3.92)
V = 
P
339
340 Equations of State
SRK Enthalpy
The following relation calculates the enthalpy.
1 ∂a V 
= PV – RT +  a – T  ln 
IG (3.93)
H–H
b ∂T V + b
SRK Entropy
The following relation calculates the entropy.
V – b 1 ∂a V+b
= R ln  –   ln 
IG (3.94)
S–S
RT b ∂T V
340
Thermodynamic Calculation Models
341
342 Equations of State
∂V 2
V T 
IG ∂2 P ∂T P
Cp – Cp = – T ∫ 2 dV + R +  (3.95)
∂T V ∂V

∞ ∂P T
a b a V
b  +  +b (3.96)
ln φi = ln ( V – b ) +   –  – 1 ln 
V – b RTb b a V
2
a = ∂n
a (3.97)
∂n
b = ∂nb
 (3.98)
∂n i
342
Thermodynamic Calculation Models
SRK Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.99)
SRK Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.100)
∂P

∂V T
343
344 Equations of State
Mixing Rules
The mixing rules available for the SRK EOS state are shown
below.
nc nc
a = ∑ ∑ ( xi xj aij ) (3.101)
i =1 j = 1
nc
b = ∑ bi xi (3.102)
i =1
a ij = ξ ij a ci a cj αi αj (3.103)
0.5 (3.104)
αi = 1 – κ ij ( 1 – T ri )
2 2
0.42748R T ci
a ci = 
 (3.105)
P ci
0.08664RT ci
b i = 
 (3.106)
P ci
2 (3.107)
κ i = 0.48 + 1.574ωi – 0.176ωi
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, ξ ij, which is
defined as:
ξ ij = 1 – A ij + B ij T + C ij T
2 (3.108)
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
344
Thermodynamic Calculation Models
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, ξ ij, which is
defined as:
C
ξ ij = 1 – A ij + B ij T + ij (3.109)
T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T )
2 (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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.111)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
345
346 Equations of State
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
 (3.112)
2 2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.113)
C C
x i A ij + B ij T + ij + x j A ji + B ji T + ji
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
346
Thermodynamic Calculation Models
a
RT  –  1
P =   (3.114)
V – b V( V + b) T
347
348 Equations of State
3T r 9Ωa
P r = 
 – 

V r – 3Ωb T V ( V + 3Ω ) 0.5
r r r b
Ωa = 0.42748
Ωb = 0.08664
(3.115)
2.5
2 Tc
a = Ωa R 
Pc
Tc
b = Ωb R 
Pc
Pitzer's definition is based Although simple systems approximately obey the corresponding
on an empirical study in states law as expressed by the RK equation, further
which it was verified that
noble gases have a improvements were required, especially when using the
reduced pressure of about equation to predict the vapour pressure of pure substances. It
0.1 at Tr = 0.7.
was noted by several researchers, notably Pitzer, that the
corresponding states principle could be extended by the use of a
third corresponding state parameter, in addition to Tc and Pc.
The two most widely used third parameters are the critical
compressibility (Zc) and the acentric factor (ω). The acentric
factor has a special appeal for equations of state based on the
van der Waals ideas, since it is related to the lack of sphericity of
a given substance. Pitzer defined the acentric factor as:
348
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the RK EOS.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and COTHRKZFactor Class
Liquid
Molar Volume Vapour and COTHRKVolume Class
Liquid
Enthalpy Vapour and COTHRKEnthalpy Class
Liquid
Entropy Vapour and COTHRKEntropy Class
Liquid
Isobaric heat capacity Vapour and COTHRKCp Class
Liquid
Fugacity coefficient Vapour and COTHRKLnFugacityCoeff
calculation Liquid Class
Fugacity calculation Vapour and COTHRKLnFugacity Class
Liquid
Isochoric heat capacity Vapour and COTHRKCv Class
Liquid
Mixing Rule 1 Vapour and COTHRKab_1 Class
Liquid
Mixing Rule 2 Vapour and COTHRKab_2 Class
Liquid
Mixing Rule 3 Vapour and COTHRKab_3 Class
Liquid
Mixing Rule 4 Vapour and COTHRKab_4 Class
Liquid
Mixing Rule 5 Vapour and COTHRKab_5 Class
Liquid
Mixing Rule 6 Vapour and COTHRKab_6 Class
Liquid
RK Z Factor
The compressibility factor is calculated as the root for the
349
350 Equations of State
following equation:
3 2 2
Z – Z + Z ( A – B – B ) – AB = 0 (3.117)
aP 
A = 
2 2
(3.118)
R T
bP (3.119)
B = 
RT
RK Molar Volume
The following relation calculates the molar volume for a specific
phase.
V = ZRT
 (3.120)
P
350
Thermodynamic Calculation Models
RK Enthalpy
The following relation calculates the enthalpy.
1 ∂a V
= PV – RT +  a – T  ln 
IG
H–H (3.121)
b ∂T V + b
351
352 Equations of State
RK Entropy
The following relation calculates the entropy.
V – b 1 ∂a V+b (3.122)
= R ln  –   ln 
IG
S–S
RT b ∂T V
RK Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
∂V 2
V
2 T 
IG ∂ P ∂T
Cp – Cp = – T ∫ 2 dV + R + P (3.123)
∂T V ∂V

∞ ∂P T
352
Thermodynamic Calculation Models
RK Fugacity Coefficient
The following relation calculates the fugacity coefficient.
a b a V + b
b  
ln φi = ln ( V – b ) +  +   –  – 1 ln  (3.124)
V – b RTb b a V
2
∂n a (3.125)
a = 
∂n
b = ∂nb
 (3.126)
∂n i
RK Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.127)
353
354 Equations of State
RK Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.128)
∂P

∂V T
Mixing Rules
The mixing rules available for the RK EOS state are shown
below.
nc nc
a = ∑ ∑ ( xi xj aij ) (3.129)
i =1 j =1
nc
b = ∑ bi xi (3.130)
i =1
a ij = ξ ij a i a j (3.131)
2 2.5
0.42748R T ci
a i =  (3.132)
P ci T
0.08664RT ci
b i = 
 (3.133)
P ci
354
Thermodynamic Calculation Models
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, ξ ij, which is
defined as:
2
ξ ij = 1 – A ij + B ij T + C ij T (3.134)
where: Aij, Bij, and Cij are asymmetric binary interaction parameters.
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, ξ ij, which is
defined as:
C
ξ ij = 1 – A ij + B ij T + ij (3.135)
T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T ) (3.136)
355
356 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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.137)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
 (3.138)
2 2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.139)
C C
x i A ij + B ij T +  + x j A ji + B ji T + ji
ij
T T
356
Thermodynamic Calculation Models
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
357
358 Equations of State
3.1.7 ZudkevitchJoffee
Equation of State
The 13ZudkevitchJoffee (ZJ, 1970) model is a modification of the
Redlich Kwong equation of state. This model has been
enhanced for better prediction of vapourliquid equilibria for
hydrocarbon systems, and systems containing Hydrogen. The
major advantage of this model over previous versions of the RK
equation is the improved capability of predicting pure compound
vapour pressure and the simplification of the method for
determining the required coefficients for the equation.
RT  – 
a (3.140)
P = 
V – b V(V + b)
Property Methods
A quick reference of calculation methods is shown in the table
below for the ZJ EOS.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and Liquid COTHZJZFactor Class
Molar Volume Vapour and Liquid COTHZJVolume Class
Enthalpy Vapour and Liquid COTHZJEnthalpy Class
Entropy Vapour and Liquid COTHZJEntropy Class
Isobaric heat capacity Vapour and Liquid COTHZJCp Class
Fugacity coefficient Vapour and Liquid COTHZJLnFugacityCoeff
calculation Class
358
Thermodynamic Calculation Models
Applicable
Calculation Method Property Class Name
Phase
Fugacity calculation Vapour and Liquid COTHZJLnFugacity Class
Isochoric heat capacity Vapour and Liquid COTHZJCv Class
Mixing Rule 1 Vapour and Liquid COTHZJab_1 Class
Mixing Rule 2 Vapour and Liquid COTHZJab_2 Class
Mixing Rule 3 Vapour and Liquid COTHZJab_3 Class
Mixing Rule 4 Vapour and Liquid COTHZJab_4 Class
Mixing Rule 5 Vapour and Liquid COTHZJab_5 Class
Mixing Rule 6 Vapour and Liquid COTHZJab_6 Class
ZJ Z Factor
The compressibility factor is calculated as the root for the
following equation:
3 2 2
Z – Z + Z ( A – B – B ) – AB = 0 (3.141)
aP 
A =  (3.142)
2 2
R T
bP (3.143)
B = 
RT
ZJ Molar Volume
The following relation calculates the molar volume for a specific
phase.
ZRT (3.144)
V = 
P
359
360 Equations of State
ZJ Enthalpy
The following relation calculates the enthalpy.
1 ∂a V 
= PV – RT +  a – T  ln 
IG
H–H (3.145)
b ∂T V + b
360
Thermodynamic Calculation Models
ZJ Entropy
The following relation calculates the entropy.
V – b 1 ∂a V+b
= R ln  –   ln 
IG
S–S (3.146)
RT b ∂T V
361
362 Equations of State
ZJ Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
∂V 2
V T 
IG ∂2 P ∂T P
Cp – Cp = – T ∫ 2 dV + R +  (3.147)
∂T V ∂V

∞ ∂P T
ZJ Fugacity Coefficient
The following relation calculates the fugacity coefficient:
a  b a V + b
b   (3.148)
ln φi = ln ( V – b ) +  +  –  – 1 ln 
V – b RTb b a V
2
a = ∂n
a (3.149)
∂n
362
Thermodynamic Calculation Models
b = ∂nb
 (3.150)
∂n i
ZJ Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.151)
ZJ Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.152)
∂P

∂V T
363
364 Equations of State
Mixing Rules
The mixing rules available for the ZJ EOS state are shown below.
nc nc
a = ∑ ∑ ( xi xj aij ) (3.153)
i =1 j = 1
nc
b = ∑ bi xi (3.154)
i =1
a ij = ξ ij a i a j αi αj (3.155)
k + 1
2  10 k–1
P 2 Pr
αi sub –c ritical= 1 + ∑ D k – ln r – ln 10 + ∑Dk – ln 
 – ln 10 (3.156)
Tr Tr
k=1 k=3
sat (3.157)
Pr = Pi ⁄ P ci
M2
ln αsuper – critical = 2M 1 ( 1 – T r ) (3.158)
1 dα
M 1 M 2 = –   (3.159)
2 dTr 0.9T c
364
Thermodynamic Calculation Models
M1 – 1
M 2 = 
 (3.160)
M1
2 2
0.42748R T ci (3.161)
a ci = 

P ci
0.08664RT ci
b i = 
 (3.162)
P ci
2 (3.163)
κ i = 0.48 + 1.574ωi – 0.176ωi
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, ξ ij, which is
defined as:
ξ ij = 1 – A ij + B ij T + C ij T
2 (3.164)
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
C
ξ ij = 1 – A ij + B ij T + ij (3.165)
T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
365
366 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, ξ ij, which is
defined as:
2
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T )
2 (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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.167)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
2 2
 (3.168)
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
366
Thermodynamic Calculation Models
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.169)
C C
x i A ij + B ij T + ij + x j A ji + B ji T + ji
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
RT  – 
a (3.170)
P = 
V – b V( V + b)
367
368 Equations of State
3 T
Watson = b (3.172)
SG
1 + 2f 2
ln G = ln G°  (3.173)
1 – 2f
2
f = 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
5 ( SG° – SG )
–1 (3.177)
368
Thermodynamic Calculation Models
G° – 1.358 a5
 1 N gv + a 6 F°
=  ln  (3.178)
426 – 1.358 a4 N gv – F°
– a4
1 + a6 e
N gv = 
 (3.179)
– a4
1–e
–a1 –a1 τ
1 + a3 e 1–e
F° =   (3.180)
–a1 –a1 τ
1–e 1 + a3 e
T b – 200.99 a 2
τ =  (3.181)
2000 – 200.99
Coefficients
a1 = a6 = 
0.405040 0.958481
a2 = 1.99638 c1 = 
0.178530
a3 = 34.9349 c2 = 1.41110
a4 = c3 =
0.507059 0.237806
a5 = 1.2589 c4 = 
1.97726
T
β = 1 – b (3.183)
Tc
Tb Tb –1
 = 0.533272 + 0.191017 × 10 T b + 0.779681 × 10 T b – 0.284376 × 10 T b + 95.9468  (3.184)
–3 –7 2 – 10 3
Tc ° 100
369
370 Equations of State
Property Methods
A quick reference of calculation methods is shown in the table
below for the KD EOS.
Applicable
Calculation Method Property Class Name
Phase
Z Factor Vapour and Liquid COTHKDZFactor Class
Molar Volume Vapour and Liquid COTHKDVolume Class
Enthalpy Vapour and Liquid COTHKDEnthalpy Class
Entropy Vapour and Liquid COTHKDEntropy Class
Isobaric heat capacity Vapour and Liquid COTHKDCp Class
Fugacity coefficient Vapour and Liquid COTHKDLnFugacityCoeff
calculation Class
Fugacity calculation Vapour and Liquid COTHKDLnFugacity Class
Isochoric heat capacity Vapour and Liquid COTHKDCv Class
Mixing Rule 1 Vapour and Liquid COTHKDab_1 Class
Mixing Rule 2 Vapour and Liquid COTHKDab_2 Class
Mixing Rule 3 Vapour and Liquid COTHKDab_3 Class
Mixing Rule 4 Vapour and Liquid COTHKDab_4 Class
Mixing Rule 5 Vapour and Liquid COTHKDab_5 Class
Mixing Rule 6 Vapour and Liquid COTHKDab_6 Class
KD Z Factor
The compressibility factor is calculated as the root for the
following equation:
3 2 2
Z – Z + Z ( A – B – B ) – AB = 0 (3.185)
aP
A = 
 (3.186)
2 2
R T
bP (3.187)
B = 
RT
370
Thermodynamic Calculation Models
KD Molar Volume
The following relation calculates the molar volume for a specific
phase.
V = ZRT
 (3.188)
P
371
372 Equations of State
KD Enthalpy
The following relation calculates the enthalpy.
1 ∂a V 
= PV – RT +  a – T  ln 
IG (3.189)
H–H
b ∂T V + b
KD Entropy
The following relation calculates the entropy.
V – b 1 ∂a V+b
= R ln  –   ln 
IG (3.190)
S–S
RT b ∂T V
372
Thermodynamic Calculation Models
KD Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
∂V 2
V T 
IG ∂2 P ∂T P
Cp – Cp = – T ∫ 2 dV + R +  (3.191)
∂T V ∂V

∞ ∂P T
KD Fugacity Coefficient
The following relation calculates the Fugacity Coefficient:
a b a V
b  +  +b (3.192)
ln φi = ln ( V – b ) +   –  – 1 ln 
V – b RTb b a V
2
a = ∂n
a (3.193)
∂n
b = ∂nb
 (3.194)
∂n i
373
374 Equations of State
KD Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.195)
KD Cv (isochoric)
The following relation calculates the isochoric heat capacity.
∂P 2
T 
∂T
C v = C p + V (3.196)
∂P

∂V T
374
Thermodynamic Calculation Models
375
376 Equations of State
Mixing Rules
The mixing rules available for the KD EOS state are shown
below.
nc nc nc
2
a = ∑ ∑ ( xi xj aij ) + ∑ ( x i x w a i' ) (3.197)
i =1 j = 1 i =1
nc
b = ∑ bi xi (3.198)
i =1
a ij = ξ ij a i a j αi αj (3.199)
0.5
( 1 + κ i ) ( 1 – T ri ) i≠w
(3.200)
αi =
0.8
1 + 0.662 ( 1 – T rw ) i =w
2 2
0.42747R T (3.201)
a i = ci
P ci
0.08664RT ci
b i = 
 (3.202)
P ci
0.8
G 1 – T rw T < T cw
a i' = i (3.204)
0.0 T ≥ T cw
376
Thermodynamic Calculation Models
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, ξ ij, which is
defined as:
ξ ij = 1 – A ij + B ij T + C ij T
2 (3.205)
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
C
ξ ij = 1 – A ij + B ij T + ij (3.206)
T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
ξ ij = 1 – x i ( A ij + B ij + C ij T ) – x j ( A ji + B ji T + C ji T ) (3.207)
377
378 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, ξ ij, which is
defined as:
C C
ξ ij = 1 – x i A ij + B ij T + ij – x j A ji + B ji + ji (3.208)
T T
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
2 2
( A ij + B ij T + C ij T ) ( A ji + B ji T + C ij T )
ξ ij = 1 – 
 (3.209)
2 2
x i ( A ij + B ij T + C ij T ) + x j ( A ji + B ji T + C ji T )
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
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, ξ ij, which is
defined as:
A + B T + C ij A ji + B ji T + ij
C
ij ij
T T
ξ ij = 1 –  (3.210)
C C
x i A ij + B ij T +  + x j A ji + B ji T + ji
ij
T T
378
Thermodynamic Calculation Models
where: Aij, Bij, and Cij are asymmetric binary interaction parameters
379
380 Equations of State
Z = PV
 = 1 + B C + 
D + …
 +  (3.211)
RT V V2 V3
2
Z = 1 + Bρ + Cρ + Dρ + …
3 (3.212)
and pressure:
2
Z = 1 + B'P + C'P + D'P + …
3 (3.213)
Z = 1 + Bρ + Cρ 2 + Dρ 3 + … (3.214)
380
Thermodynamic Calculation Models
∂Z
B = lim (3.216)
ρ →0 ∂ ρ T
∂2Z ∂3Z
C = lim 2 D = lim 3 (3.217)
ρ →0 ∂ ρ ρ →0 ∂ ρ
T T
Z = PV
 = 1 + B
 (3.218)
RT V
B = B
(0)
+ ωB
(1) (3.219)
381
382 Equations of State
382
Thermodynamic Calculation Models
B = B
(0)
+ ωB
(1)
+B
(2) (3.220)
5 2
10 µ P c (3.221)
µR =  × 0.9869
Tc
The method of 19
Hayden and O'Connell (1975) is used, where
they define:
F D
B ij = B ij + B ij
F F F (3.222)
B ij = ( B ij, non – polar ) + ( B ij, polar )
D D D D
B ij = ( B ij , metastable ) + ( B ij , bound ) + ( B ij , chemical )
383
384 Equations of State
D D 0 ∆H ij
( B ij , metastable ) + ( B ij , bound ) = b ij A ij exp  (3.225)
T ij∗
1500ηij (3.226)
= b ij E ij 1 – exp 
D 0
( B ij , chemical )
T
384
Thermodynamic Calculation Models
where:
1 1 – 1.6ω
 =  ij
*' *
T ij T ij
* T
T ij = 
( ε ij ⁄ k )
0 3 3
b ij = 1.26184σij ( cm ⁄ gmol )
*' * *
µij = µij if µij < 0.04
*' *
µij = 0 if 0.04 ≤µij < 0.25
*' * *
µij = µij – 0.25 if µij ≥ 0.25
*
A ij = – 0.3 – 0.05µij
*2
∆H ij = 1.99 + 0.2µij
* 7243.8µi µj
µij = 
ε
ij σ3
k ij
650
E ij = exp ηij  – 4.27 if ηij < 4.5
ε
ij
k + 300
42800
E ij = exp ηij  – 4.27 if ηij ≥ 4.5
ε
ij
k + 22400
2 3
ωi = 0.006026R Di + 0.02096R Di – 0.001366R Di
ε ε ij ′ C
ij =  1 – ξ C 1 1 – ξ 1 + 1
k k 2
(3.227)
1⁄ 3
σi = σi' ( 1 + ξ C 2 )
ε i

′ ηi
 = T c, i 0.748 + 0.91ωi – 0.4 
k 2 + 20ωi
385
386 Equations of State
and
T c, i 1 ⁄ 3
σi' = ( 2.44 – ωi ) 1.0133 
P c, i
ξ = 0 if µi < 1.45
or (3.228)
7 4
1.7941 × 10 µ i
ξ =  if µi ≥ 1.45
1.882ω ε i′
2.882 – i T c, i σi' 
6
0.03 + ωi k
16 + 400ωi 3
C 1 =  and C 2 = 
 (3.229)
10 + 400ωi 10 + 400ωi
1
ωij =  ( ωi + ωj )
2
εij = εij′ ( 1 + ξ ′ C ′ )
k k 1
1

σij = ( σii σjj ) 2
2 ε jj
2⁄ 3
u i 
4
σjj
k
ξ ′ =  if µi ≥ 2 and µj = 0
εij′ σ6
k ij (3.231)
2 ε ii
2
u  σii
4
k
ξ ′ =  if µj ≥ 2 and µi = 0
ε
ij′ σ′ 6
k ij
386
Thermodynamic Calculation Models
16 + 400ωij 3
C 1′ =  and C 2′ =  (3.232)
10 + 400ωij 10 + 400ωij
Mixing Rules
For a multicomponent mixture, it can be shown that Bmix is
rigorously calculated by:
P
ln φi = 2 ∑yi B ij – B mix  (3.234)
j RT
387
388 Equations of State
i + j ↔ ij (3.235)
#
f ij Z ij φ ij
k ij = 
 = 
 (3.236)
f i f j Z Z φ# φ# P
i j i j
388
Thermodynamic Calculation Models
#
# φi Z i (3.237)
φ i Z i = φi y i or φi = 

yi
F
# Bi P (3.238)
ln φi = 
RT
φij Z ij P
k ij =  (3.239)
φi Z i Pφj Z j P
and finally:
F P
exp B ij 
Z ij 1 RT
k ij =   ×  (3.240)
Zi Zj P F P F P
exp B ii  exp B jj 
RT RT
D
– B ij ( 2 – δij )
k ij = 

RT
(3.241)
0 i≠j
δij =
1 i=j
389
390 Equations of State
390
Thermodynamic Calculation Models
Therefore:
F P
exp B ij 
Z ij 1 RT
k ij =   × 
Zi Zj P F P F P
exp B ii  exp B jj  (3.242)
RT RT
D
– B ij ( 2 – δij )
= 

RT
391
392 Equations of State
∑ yi Pc
i
T i=1
(3.243)
P ≤ 
m 
2
∑ yi Tc i
i=1
Property Methods
A quick reference of calculation methods is shown in the table
below for the Virial EOS.
Applicable
Calculation Method Property Class Name
Phase
Molar Volume Vapour COTHVirial_Volume Class
Enthalpy Vapour COTHVirial_Enthalpy Class
Entropy Vapour COTHVirial_Entropy Class
Isobaric heat capacity Vapour COTHVirial_Cp Class
Fugacity coefficient Vapour COTHVirial_LnFugacityCoeff
calculation Class
Fugacity calculation Vapour COTHVirial_LnFugacity Class
Density Vapour COTHVirial_Density Class
Isochoric Heat Vapour COTHVirial_Cv Class
Capacity
Gibbs Energy Vapour COTHVirial_GibbsEnergy Class
Helmholtz Energy Vapour COTHVirial_HelmholtzEnergy
Class
Z Factor Vapour COTHVirial_ZFactor Class
392
Thermodynamic Calculation Models
B (3.244)
V = 
Z–1
Virial Enthalpy
The following relation calculates the enthalpy.
H – H° = A – A° + T ( S – S° ) + RT ( Z – 1 ) (3.245)
Virial Entropy
The following relation calculates the entropy.
o ( dB ⁄ dT ) V  + R ln 
V (3.246)
S – S = – RT  – R ln 
V–B V–B Vo
393
394 Equations of State
2
V 2 ∂P
∂ P ∂T V
Cp – Cp ° = T ∫ 2 dV – T  – R (3.247)
∂T ∂P
∞ ∂T T
P
ln φi = 2 ∑yi B ij – B mix  (3.248)
j RT
394
Thermodynamic Calculation Models
Virial Fugacity
The following relation calculates the fugacity for a specific
phase.
f i = φi y i P (3.249)
Virial Density
The following relation calculates the molar density for a specific
phase.
P (3.250)
ρ = 
ZRT
Virial Cv (isochoric)
The following relation calculates the isochoric heat capacity.
V 2
∂ P
C v – C v ° = T ∫ 2 dV (3.251)
∂T
∞
395
396 Equations of State
G = A + RT ( Z – 1 ) (3.252)
V V (3.253)
A – A o = RT ln  – RT ln 
V–B Vo
396
Thermodynamic Calculation Models
Virial Z Factor
The following relation calculates the Z Factor.
Z = 1+B
 (3.254)
V
ω r (3.255)
Z = Z ° + r ( Z – Z ° )
ω
They chose the reduced form of the BWR EOS to represent both
Z o and Z r:
γ
–

2
Vr
B C D  D γ  e (3.256)
Z = 1 + 
 +  +  +  β – 
2 5 3 3 2
Vr Vr Vr Tr Vr Vr
397
398 Equations of State
where:
VP
V r = c
RT c
b b b
B = b 1 – 2 – 3 – 4
Tr T T 4 2
r r
c c
C = c 1 – 2 + 3
3
Tr Tr
d
D = d 1 + 2
Tr
Property Methods
A quick reference of calculation methods is shown in the table
below for the LK EOS.
Calculation
Applicable Phase Property Class Name
Method
Enthalpy Vapour and Liquid COTHLeeKeslerEnthalpy Class
Entropy Vapour and Liquid COTHLeeKeslerEntropy Class
Isobaric heat Vapour and Liquid COTHLeeKeslerCp Class
capacity
398
Thermodynamic Calculation Models
LK Enthalpy
The following relation calculates the enthalpy departure.
b3 b4 c3
IG
b 2 + 2  + 3 2 c 2 – 3 2
H –H  Tr Tr T d
 = T r Z – 1 –  2
 – r – 
 + 3E (3.257)
RT c Tr Vr 2T r V r
2
5T r V r
5
where:
T
T r =  (3.258)
Tc
V
V r =  (3.259)
Vc
LK Entropy
The following relation calculates the entropy departure.
b b4 c
IG b 1 + 3 + 2 3 c 1 – 3 3
2 2 (3.260)
S – S° P Tr Tr T d1
 = ln Z – ln  –  – r – 
 + 2E
R P° 2 2
Vr 2V r 5V r
399
3100 Equations of State
where:
T
T r =  (3.261)
Tc
V
V r =  (3.262)
Vc
LK Cp (Heat Capacity)
The following relation calculates the isobaric heat capacity.
∂V 2
V T 
IG ∂2 P ∂T
Cp – Cp = – T ∫ 2 dV + R + P (3.263)
∂T V ∂V

∞ ∂P T
3100
Thermodynamic Calculation Models
Mixing Rules
For mixtures, the Critical properties for the LK EOS state are
defined as follows.
N
ω= ∑ xi ωi
i=1
z c = 0.2905 – 0.0851ωi
i
Z c RT c
V c = 
i i
i Pc
i
N N 1 1 3
1 3 
3
V c = 
8 ∑ ∑ xi xj Vci + Vcj
i=1 j=1
N N 1 1 3
1 3 
3 0.5
T c = 
8V c ∑ ∑ xi xj Vci + Vcj ( Tci Tcj )
i=1 j=1
RT c
P c = ( 0.2905 – 0.085ω) 
Vc
3.1.11 LeeKeslerPlöcker
The LeeKeslerPlöcker The LeeKeslerPlöcker equation is an accurate general method
equation does not use the for nonpolar substances and mixtures. 3Plöcker et al, applied
COSTALD correlation in
computing liquid density. the LeeKesler equation to mixtures, which itself was modified
This may result in from the BWR equation.
differences when
comparing results
(o) ω (r) (o)
z = z +  (z – z ) (3.264)
(r)
ω
pv pr vr
z =   = z ( T r, v r, A k )
=  (3.265)
RT Tr
3101
3102 Equations of State
C + 
B +  C4
D + 
 β +  –γ
γ exp 
z = 1 + 
2 5 3 2

2 2 (3.266)
vr vr vr Tr vr vr vr
where:
pc v b b b
v r = 
 B = b 1 – 2 – 3 – 4
RT c Tr Tr Tr
2 3
c c d
C = c 1 – 2 + 3 D = d 1 – 2
2
Tr Tr Tr
(o) (r)
ω = 0 ω = 0.3978
1
 ∑∑x i x j v c
T cm =  (3.267)
V ηcm ij
i j
where:
1⁄ 2
Tc = ( Tc Tc ) Tc = Tc Tc = Tc
ij i j ii i jj j
1 1⁄ 1⁄ 3 3
vc =
m ∑∑xi xj vc ij
v c =  ( v c
ij 8 i
3
+ vc
j
)
i j
RT c
v c = z c i z c = 0.2905 – 0.085ωi
i i p i
c i
RT c
p c = z c m z c = 0.2905 – 0.085ωm
m m v m
c m
ωm = ∑xi ωi
i
3102
Thermodynamic Calculation Models
Activity models generate Activity models are much more empirical in nature when
the best results when they
are applied in the compared to the property predictions in the hydrocarbon
operating region in which industry. For this reason, they cannot be used as reliably as the
the interaction parameters equations of state for generalized application or extrapolated
were generated.
into untested operating conditions. Their adjustable parameters
should be fitted against a representative sample of experimental
data and their application should be limited to moderate
pressures. Consequently, caution should be exercised when
selecting these models for your simulation.
y γ i fi °
K i = i = 
 (3.268)
xi Pφi
P = System pressure
3103
3104 Activity Models
E
G = RT ∑( n i ln γ i ) (3.269)
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 nonideal mixtures such as alcoholhydrocarbon
systems, particularly for dilute regions.
3104
Thermodynamic Calculation Models
If you are using the builtin 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
3105
3106 Activity Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the Ideal Solution model.
Calculation Applicable
Property Class Name
Method Phase
Activity coefficient Liquid COTHIdealSolLnActivityCoeff
Class
Fugacity coefficient Liquid COTHIdealSolLnFugacityCoeff
Class
Fugacity Liquid COTHIdealSolLnFugacity Class
Activity coefficient Liquid COTHIdealSolLnActivityCoeffDT
differential wrt Class
temperature
Enthalpy Liquid COTHIdealSolEnthalpy Class
Gibbs energy Liquid COTHIdealSolGibbsEnergy Class
3106
Thermodynamic Calculation Models
ln γ i = 0 (3.270)
3107
3108 Activity Models
std
f i
ln φi = ln  (3.271)
P
where: γ i = 1
P = pressure
3108
Thermodynamic Calculation Models
std
ln f i = ln ( x i f i ) (3.272)
where: γ i = 1
∂ ln γ i (3.273)
 = 0
∂T
3109
3110 Activity Models
n n
H = ∑xi Hi (3.275)
i
Hi = enthalpy of component i
3110
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the Regular Solution activity model.
Applicable
Calculation Method Property Class Name
Phase
Fugacity coefficient Liquid COTHRegSolLnFugacityCoeff Class
Activity coefficient Liquid COTHRegSolLnActivityCoeff Class
Fugacity Liquid COTHRegSolLnFugacity Class
Activity coefficient Liquid COTHRegSolLnActivityCoeffDT
differential wrt Class
temperature
Standard Fugacity Liquid COTHIdealStdFug Class
Excess Gibbs Energy Liquid COTHRegSolExcessGibbsEnergy
Class
3111
3112 Activity Models
following sections.
Vi 2
ln γ i =  δi – ∑ϕj δi (3.276)
RT
j
xj Vj
ϕj = 

(3.277)
∑k kx V
k
3112
Thermodynamic Calculation Models
relation.
std
fi
ln φi = ln γ i  (3.278)
P
P = pressure
std
ln f i = ln ( γ i x i f i ) (3.279)
3113
3114 Activity Models
d ln γ i
 (3.280)
dT
3114
Thermodynamic Calculation Models
n
E
G = RT ∑x i ln γ i (3.281)
i
T = temperature
G
E E
= U + PV – TS
E E (3.282)
simplifies to:
E
G = H = U
E E (3.283)
3115
3116 Activity Models
Figure 3.2
Ideal Gas
Mix Ideal Cases
(Ideal Gas)
Compress
Vapour
Mixture
Pure Liquid
Liquid Mixture
3116
Thermodynamic Calculation Models
E
U = U I + U II + U III (3.284)
∂U ∂P
∆U I = = T – P (3.285)
∂V T ∂T V
Therefore:
∂V
∂U = – P + T 
∂T P
 (3.287)
∂V T ∂V
∂P T
∂U = 
a (3.288)
∂V T 2
V
3117
3118 Activity Models
∞
id a1 x1 a1 x1
x 1 ( U – U )1 = ∫  dV = 
V
2 L

L
V 1
V1
(3.289)
∞
id a1 x1 a2 x2
x 2 ( U – U ) 2 = ∫ 
2
 dV = 

L
L
V V 1
V2
thus:
id id
∆U I = x 1 ( U – U ) 1 + x 2 ( U – U ) 2 (3.290)
and:
a1 x1 a2 x2
∆U I = 
 +  (3.291)
L L
V2 V1
∂P = – 
RT  + 2a  (3.292)
∂ V T 2 3
(V – b) V
∂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)
Therefore,
a1 x1 a2 x2
∆U I = 
 +  (3.294)
b1 b2
3118
Thermodynamic Calculation Models
It follows that:
∆U II = 0 (3.295)
a mix
∆U III = – 
 (3.296)
b mix
Using the simple mixing rules for the van der Waals equation:
2 2
a mix = ∑∑xi xj a i a j = x 1 a 1 + x 2 a 2 + 2x 1 x 2 a 1 a 2 (3.297)
nc
b mix = ∑ xi bi = x1 b1 + x2 b2 (3.298)
i =1
2
E x1 x2 b1 b2 a a
G =  1 – 2 (3.299)
x1 b1 + x2 b2 b1 b2
and:
A
ln γ 1 = 

A x 1 2
1+  
B x2
(3.300)
B
ln γ 2 = 

2
B x 2
1 +  
A x1
3119
3120 Activity Models
where:
b1 a a
A =  1 – 2
RT b 1 b2
(3.301)
b2 a a
B =  1 – 2
RT b 1 b2
System: T = 25 C
Aij = 4.976
Application of the van Laar Equation
The van Laar equation was the first Gibbs excess energy
representation with physical significance. The van Laar equation
is a modified form of that described in "Phase Equilibrium in
Process Design" by Null. 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
Raoult's Law, however, it cannot predict maximas or minimas in
The Van Laar equation also the activity coefficient. Therefore, it generally performs poorly
performs poorly for dilute for systems with halogenated hydrocarbons and alcohols. Due to
systems and cannot
represent many common
the empirical nature of the equation, caution should be
systems, such as alcohol exercised in analyzing multicomponent systems. It also has a
hydrocarbon mixtures, tendency to predict two liquid phases when they do not exist.
with acceptable accuracy.
The van Laar equation has some advantages over the other
3120
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the van Laar model.
Applicable
Calculation Method Property Class Name
Phase
Activity coefficient Liquid COTHVanLaarLnActivityCoeff Class
Fugacity coefficient Liquid COTHVanLaarLnFugacityCoeff
Class
Fugacity Liquid COTHVanLaarLnFugacity Class
Activity coefficient Liquid COTHVanLaarLnActivityCoeffDT
differential wrt Class
temperature
Excess Gibbs Liquid COTHVanLaarExcessGibbsEnergy
Class
Excess enthalpy Liquid COTHVanLaarExcessEnthalpy Class
Enthalpy Liquid COTHVanLaarEnthalpy Class
Gibbs energy Liquid COTHVanLaarGibbsEnergy Class
2 (3.302)
ln γ i = A i [ 1.0 – z i ] ( 1.0 + E i z i )
3121
3122 Activity Models
n ( a ij + b ij T )
Ai = ∑ x j 
( 1.0 – x i ) (3.303)
j =1
n ( a ji + b ji T )
Bi = ∑ x j 
( 1.0 – x i ) (3.304)
j =1
Ai xi (3.305)
z i = 

[ A i x i + B i ( 1.0 – x i ) ]
3122
Thermodynamic Calculation Models
std
fi
ln φi = ln γ i  (3.306)
P
P = pressure
std
ln f i = ln ( γ i x i f i ) (3.307)
3123
3124 Activity Models
3124
Thermodynamic Calculation Models
d ln γ i dA i dz i 2 dz i
2
 = ( 1 – z i ) ( 1 + E i zi )  – 2A i ( 1 – z i ) ( 1 + Ez i )  + A ( 1 – z i ) E i  (3.308)
dT dT dT dT
where:
n
dB i x j b ji
 =
dT ∑ 1
– xi

j=1
dA i dB i
dZ i x i ( 1 – x i )  B i –  A i
dT dT
 = 
dT [ Ai xi + Bi ( 1 – xi ) ]
2
n
dA i x j b ij
 =
dT ∑ 1
– xi

j=1
3125
3126 Activity Models
n
E
G = RT ∑x i ln γ i (3.309)
i
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.310)
i i
3126
Thermodynamic Calculation Models
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.311)
i
d ln γ i

The term, dT , in the above equation is exclusively
calculated using the van Laar Activity Coefficient Differential
wrt Temperature.
3127
3128 Activity Models
n
E
H = ∑xi Hi + H (3.312)
i
Hi = enthalpy of component i
3128
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the Margules property model.
Applicable
Calculation Method Property Class Name
Phase
Activity Coefficient Liquid COTHMargulesLnActivityCoeff
Class
Fugacity coefficient Liquid COTHMargulesLnFugacityCoeff
calculation Class
Fugacity calculation Liquid COTHMargulesLnFugacity Class
Activity coefficient Liquid COTHMargulesLnActivityCoeffDT
differential wrt Class
temperature
Excess Gibbs Liquid COTHMargulesExcessGibbsEnergy
Class
Excess enthalpy Liquid COTHMargulesExcessEnthalpy
Class
Enthalpy Liquid COTHMargulesEnthalpy Class
Gibbs energy Liquid COTHMargulesGibbsEnergy Class
2
ln γ i = [ 1.0 – x i ] [ A i + 2x i ( B i – A i ) ] (3.313)
n
( a ij + b ij T )
Ai = ∑ x j 
( 1.0 – x i ) (3.314)
j =1
3129
3130 Activity Models
n ( a ji + b ji T )
Bi = ∑ x j 
( 1.0 – x i )
(3.315)
j =1
std
fi
ln φi = ln γ i  (3.316)
P
3130
Thermodynamic Calculation Models
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 ( γ i x i f i ) (3.317)
3131
3132 Activity Models
∂ ln γ
i (3.318)
∂T
n
E
G = RT ∑x i ln γ i (3.319)
i
3132
Thermodynamic Calculation Models
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.320)
i i
3133
3134 Activity Models
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.321)
i
d ln γ 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
E
H = ∑xi Hi + H (3.322)
i
Hi = enthalpy of component i
3134
Thermodynamic Calculation Models
a 21
x 2 exp – 
x 21 RT (3.323)
 = 
x 11 a
x 1 exp –  11
RT
The parameters a21 and a11 are related to the potential energies
of the 11 and 12 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
 =  (3.324)
x 22 a 22
x 2 exp – 
RT
3135
3136 Activity Models
V 1 x 11 V 2 x 22
φ1 = 
 φ2 = 
 (3.325)
V 1 x 11 + V 2 x 21 V 1 x 12 + V 2 x 22
φi is the volume fraction of When the above relations for φ are substituted into the Flory
component i.
Huggins equation:
E φi E
G = G (3.326)

RT ∑xi ln xi  = – x 1 ln ( x 1 + Λ 12 x 2 ) – x 2 ln ( x 2 + Λ 21 x 1 )
RT
where:
V2 λ 12
Λ 12 =  exp – 

V1 RT
(3.327)
V1 λ 21
Λ 21 =  exp – 

V2 RT
and:
Λ 12 Λ 21
ln γ 1 = – ln ( x 1 + Λ 12 x 2 ) + x 2 
 – 

x 1 + Λ 12 x 2 x 2 + Λ 21 x 1
(3.328)
Λ 12 Λ 21
ln γ 2 = – ln ( x 2 + Λ 21 x 1 ) + x 1 
 – 

x 1 + Λ 12 x 2 x 2 + Λ 21 x 1
3136
Thermodynamic Calculation Models
a ij = Λ ij – Λ ji (3.329)
a ij = b ij + c ij T (3.330)
3137
3138 Activity Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the Wilson property model.
Calculation Applicable
Property Class Name
Method Phase
Activity Coefficient Liquid COTHWilsonLnActivityCoeff Class
Fugacity coefficient Liquid COTHWilsonLnFugacityCoeff Class
calculation
Fugacity calculation Liquid COTHWilsonLnFugacity Class
Activity coefficient Liquid COTHWilsonLnActivityCoeffDT
differential wrt Class
temperature
Excess Gibbs Liquid COTHWilsonExcessGibbsEnergy
Class
3138
Thermodynamic Calculation Models
Calculation Applicable
Property Class Name
Method Phase
Excess enthalpy Liquid COTHWilsonExcessEnthalpy Class
Enthalpy Liquid COTHWilsonEnthalpy Class
Gibbs energy Liquid COTHWilsonGibbsEnergy Class
3139
3140 Activity Models
n n xk Λ ki
ln γ i = 1.0 – ln ∑ xj Λ ij – ∑  (3.331)
n
j=1 k =1 ∑ xk Λ kj
j=1
Vj ( a ij + b ij T )
Λ ij =  exp – 

Vi RT
T = Temperature (K)
3140
Thermodynamic Calculation Models
std
fi
ln φi = ln γ i  (3.332)
P
P = Pressure
3141
3142 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.
ln f i = ln ( γ i x i f i )
std (3.333)
n
n
dΛ ki n dΛ
x j dΛ ij
x k  ∑ x j Λ kj – x k Λ ij ∑ x j 
kj
∑ 
dT
 n dT dT
d ln γ i j = 1 j = 1
 – ∑ 
 = – j
=1 (3.334)
dT n n 2
k=1
∑ xj Λ ij ∑ j kj
x Λ
j=1 j = 1
3142
Thermodynamic Calculation Models
n
E
G = RT ∑x i ln γ i (3.335)
i
T = temperature
3143
3144 Activity Models
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.336)
i i
3144
Thermodynamic Calculation Models
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.337)
i
d ln γ 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
E
H = ∑xi Hi + H (3.338)
i
Hi = enthalpy of component i
3145
3146 Activity Models
α12 g 21
–
x 2 exp RT

x 21
 =   (3.339)
x 11 x1 – α12 g 11
exp 
RT
α12 g 12
–
x 1 exp RT

x 21
 = 
 
 (3.340)
x 22 x2
– α12 g 22
exp 
RT
3146
Thermodynamic Calculation Models
x 21 x 12 ( 2g 12 – g 11 – g 22 )
 ×  = exp – α12 
 (3.341)
x 11 x 22 RT
( 2g 12 – g 11 – g 22 )
( 1 – x 21 ) ( 1 – x 12 ) exp – α12  = x 21 x 12 (3.342)
RT
Ideal Gas
Mix Ideal Cases
(Ideal Gas)
Compress
Vapour
Mixture
Pure Liquid
Liquid Mixture
3147
3148 Activity Models
( g 21 – g 11 )
x 2 exp – α12 
RT (3.344)
x 21 = 
( g 21 – g 11 )
x 1 + x 2 exp – α12 
RT
and
( g 12 – g 22 )
x 1 exp – α12 
RT (3.345)
x 12 = 
( g 12 – g 22 )
x 1 + x 2 exp – α12 
RT
(1)
g = x 11 g 11 + x 21 g 21
(3.346)
(1)
g pure = g 11
3148
Thermodynamic Calculation Models
(2)
g = x 22 g 22 + x 12 g 12
(3.347)
(2)
g pure = g 22
Consequently:
g
E
= x 1 x 21 ( g 21 – g 11 ) + x 2 x 12 ( g 12 – g 22 ) (3.349)
3149
3150 Activity Models
where:
g 12 – g 22
τ 12 = 
RT
g 21 – g 11
τ 21 =  (3.352)
RT
g 12 = exp ( – α12 τ 12 )
g 21 = exp ( – α12 τ 21 )
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.
3150
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the NRTL property model.
Applicable
Calculation Method Property Class Name
Phase
Activity Coefficient Liquid COTHNRTLLnActivityCoeff Class
Fugacity coefficient Liquid COTHNRTLLnFugacityCoeff
calculation Class
Fugacity calculation Liquid COTHNRTLLnFugacity Class
Activity coefficient Liquid COTHNRTLLnActivityCoeffDT
differential wrt temperature Class
NRTL temperature Liquid COTHNRTLTempDep Class
dependent binary
interaction parameters
Excess Gibbs Liquid COTHNRTLExcessGibbsEnergy
Class
Excess enthalpy Liquid COTHNRTLExcessEnthalpy Class
Enthalpy Liquid COTHNRTLEnthalpy Class
Gibbs energy Liquid COTHNRTLGibbsEnergy Class
n n
∑ τ ji xj Gji n ∑ mi m mi
τ x G
j=1 x j G ij m=1
ln γ i =  + ∑  τ ij –  (3.353)
n x k G kj n
∑ xk Gki j = 1
∑ x k G kj
k=1 k = 1
3151
3152 Activity Models
std
fi
ln φi = ln γ i  (3.354)
P
P = Pressure
3152
Thermodynamic Calculation Models
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 ( γ i x i f i ) (3.355)
3153
3154 Activity Models
d ln γ i
 (3.356)
dT
b e
τ ij = a ij + ij + c ij ln T + d ij T + ij (3.357)
T T
2
3154
Thermodynamic Calculation Models
G ij = EXP ( – ατ ij ) (3.358)
where:
α = α0 + α1 T
a ij = 0 ; b ij = 0 ; cij = 0 ; d ij = 0 ; e ij = 0
τ ij = 0
3155
3156 Activity Models
n
E
G = RT ∑x i ln γ i (3.359)
i
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.360)
i i
3156
Thermodynamic Calculation Models
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.361)
i
d ln γ i

The term, dT , in the above equation is exclusively
calculated using the NRTL Activity Coefficient Differential
wrt Temperature.
3157
3158 Activity Models
NRTL Enthalpy
This method calculates the enthalpy using the NRTL activity
model from the following relation.
n
E
H = ∑xi Hi + H (3.362)
i
Hi = enthalpy of component i
3158
Thermodynamic Calculation Models
a ij + b ij T (3.364)
τ ij = 

RT
3159
3160 Activity Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the HYPNRTL property model.
Calculation Applicable
Property Class Name
Method Phase
Activity Coefficient Liquid COTHHYPNRTLLnActivityCoeff
Class
Fugacity coefficient Liquid COTHHYPNRTLLnFugacityCoeff
calculation Class
Fugacity calculation Liquid COTHHYPNRTLLnFugacity Class
Activity coefficient Liquid COTHHYPNRTLLnActivityCoeffDT
differential wrt Class
temperature
Excess Gibbs Liquid COTHHYPNRTLExcessGibbsEnerg
y Class
Excess enthalpy Liquid COTHHYPNRTLExcessEnthalpy
Class
Enthalpy Liquid COTHHYPNRTLEnthalpy Class
Gibbs energy Liquid COTHHYPNRTLGibbsEnergy Class
3160
Thermodynamic Calculation Models
B
A ij + ij
T
τ ij = 
RT
αij = Alp1 ij
B
τ ij = A ij + ij + F ij T + G ij ln ( T )
T
αij = Alp1 ij + Alp2 ij T
C
τ ij = A ij + B ij t + ij
T
αij = Alp1 ij + Alp2 ij T
where: T is in K and t is °C
B
τ ij = A ij + ij
T
αij = Alp1 ij
3161
3162 Activity Models
i=1
ActivityLiquid1Fugacit Fugacity
std
y fi = γ i xi fi
CavettEnthalpy Enthalpy
l steam67 Cavett
H = x water H water + ∑xi H °i + ∆H i
i
CavettEntropy Entropy
l steam67 Cavett
S = x S
water water
+ ∑xi S° + ∆S
i
i
CavettCp Cp
steam67 Cavett
Cp l = x water Cp water + ∑xi Cp °i + ∆Cp i
i
CavettCv Cv
Cv = Cp – R
3162
Thermodynamic Calculation Models
E E ∆A  – RT ( x ln x + x ln x ) (3.365)
g ≅ a =  1 1 2 2
n1 + n2
n = number of moles
3163
3164 Activity Models
x = mole fraction
G
E E
= G combinational + G resdiual
E (3.366)
and:
Combinational refers to
the nonideality caused by φ1 φ2 Z θ1 θ2
G combinational = x 1 ln  + x 2 ln  +  q 1 x 1 ln  + q 2 x 2 ln 
E
(3.367)
differences in size and x 1 x 2 2 φ1 φ2
shape (entropic effects).
where:
q1 x1 q2 x2
θ 1 = 
 θ 2 = 

q1 x1 + q2 x2 q1 x1 + q2 x2
(3.370)
r1 x1 r2 x2
φ1 = 
 φ2 = 

r1 x1 + r2 x2 r1 x1 + r2 x2
3164
Thermodynamic Calculation Models
φ1 Z θ1 r1 τ 21 τ 12
ln γ 1 = ln  +  q 1 ln  + φ2 l 1 –  l 2 – q 1 ln ( θ 1 + θ 2 τ 21 ) + θ 2 q 1  – 
x 1 2 φ1 r2 θ + θ τ θ
1 2 21 2 θ 1 τ 21
+ (3.371)
Z
l 1 =  ( r 1 – q 1 ) – ( r 1 – 1 )
2
Application of UNIQUAC
The UNIQUAC (UNIversal QUASIChemical) equation uses
statistical mechanics and the quasichemical 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
nonrandomness factor. The UNIQUAC equation is significantly
more detailed and sophisticated than any of the other activity
3165
3166 Activity Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the UNIQUAC property model.
Applicable
Calculation Method Property Class Name
Phase
Activity Coefficient Liquid COTHUNIQUACLnActivityCoeff
Class
Fugacity coefficient Liquid COTHUNIQUACLnFugacityCoeff
calculation Class
Fugacity calculation Liquid COTHUNIQUACLnFugacity Class
Activity coefficient Liquid COTHUNIQUACLnActivityCoeffDT
differential wrt Class
temperature
Excess Gibbs Liquid COTHUNIQUACExcessGibbsEnergy
Class
3166
Thermodynamic Calculation Models
Applicable
Calculation Method Property Class Name
Phase
Excess enthalpy Liquid COTHUNIQUACExcessEnthalpy
Class
Enthalpy Liquid COTHUNIQUACEnthalpy Class
Gibbs energy Liquid COTHUNIQUACGibbsEnergy Class
Φi θi Φi n n n θ τ
ln γ i = ln  + 0.5Zq i ln  + L i –  1.0 – ln
∑ j ji – q i ∑ 
j ji
xi Φi xi ∑ j j i
L x + q θ τ
n (3.372)
j = 1
∑ θ k τ kj
j=1 j=1
k=1
T = Temperature (K)
L j = 0.5Z ( r j – q j ) – r j + 1 (3.373)
qi xi
θ i = 
 (3.374)
∑qj xj
a ij + b ij T
τ ij = exp –  (3.375)
RT
3167
3168 Activity Models
std
fi
ln φi = ln γ i  (3.376)
P
3168
Thermodynamic Calculation Models
3169
3170 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 ( γ i x i f i ) (3.377)
d ln γ i (3.378)

dT
3170
Thermodynamic Calculation Models
n
E
G = RT ∑x i ln γ i (3.379)
i
3171
3172 Activity Models
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.380)
i i
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.381)
i
3172
Thermodynamic Calculation Models
d ln γ 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
E
H = ∑xi Hi + H (3.382)
i
Hi = enthalpy of component i
3173
3174 Activity Models
Figure 3.4
CH2 OH Solution of
CH3 CH3 Groups
H2O Point
CH2 OH H2O of View
3174
Thermodynamic Calculation Models
3175
3176 Activity Models
3176
Thermodynamic Calculation Models
(1)
( 0 ) a mk (2) (3.383)
 + a mk ln T
a mk = a mk + 
T
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
CH2 OH Solution of
CH3 CH3 Groups
H2O Point
CH2 OH H2O of View
3177
3178 Activity Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the UNIFAC property model.
Calculation Applicable
Property Class Name
Method Phase
Activity Coefficient Liquid COTHUNIFAC1_VLELnActivityCoef
(VLE) f Class
Fugacity coefficient Liquid COTHUNIFAC1_VLELnFugacityCoe
calculation (VLE) ff Class
Fugacity calculation Liquid COTHUNIFAC1_VLELnFugacity
(VLE) Class
Activity coefficient Liquid COTHUNIFAC1_VLELnActivityCoef
differential wrt fDT Class
temperature (VLE)
Enthalpy (VLE) Liquid COTHUNIFAC1_VLEEnthalpy Class
Gibbs energy (VLE) Liquid COTHUNIFAC1_VLEGibbsEnergy
Class
Activity Coefficient Liquid COTHUNIFAC1_LLELnActivityCoeff
(LLE) Class
Fugacity coefficient Liquid COTHUNIFAC1_LLELnFugacityCoe
calculation (LLE) ff Class
Fugacity calculation Liquid COTHUNIFAC1_LLELnFugacity
(LLE) Class
Activity coefficient Liquid COTHUNIFAC1_LLELnActivityCoeff
differential wrt DT Class
temperature (LLE)
Enthalpy (LLE) Liquid COTHUNIFAC1_LLEEnthalpy Class
Gibbs energy (LLE) Liquid COTHUNIFAC1_LLEGibbsEnergy
Class
3178
Thermodynamic Calculation Models
e (i) (i)
ln γ i = ∑vk ln ( Γ k – ln Γ k ) (3.385)
k
θ τ
ln Γ k = Q k 1 – ln ∑θ m τ mk – ∑ 
m mk
(3.386)
m
m ∑ θ n τ nm
n
3179
3180 Activity Models
xm Qk
θ m = 
 (3.387)
∑θ n τ nm
n
∑xm Qm
j
x m =  (3.388)
∑θ n τ nm
n
(j)
vm xj
τ mk = 
(j) (3.389)
∑∑vm xj
j n
In which amk = 0 when m = k. Also, the area and volume for the
molecules are computed by:
(i) (i)
ri = ∑vk Rk qi = ∑vk Qk (3.390)
k k
3180
Thermodynamic Calculation Models
std
fi
ln φi = ln γ i  (3.391)
P
P = Pressure
3181
3182 Activity Models
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 ( γ i x i f i ) (3.392)
3182
Thermodynamic Calculation Models
d ln γ i (3.393)

dT
3183
3184 Activity Models
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.394)
i i
3184
Thermodynamic Calculation Models
UNIFAC Enthalpy
This method calculates the enthalpy using the UNIFAC activity
model from the following relation.
n
E
H = ∑xi Hi + H (3.395)
i
Hi = enthalpy of component i
3185
3186 Activity Models
ChienNull Form
The ChienNull generalized multicomponent equation can be
expressed as:
∑A j, i x j ∑R j, i x j ∑A j, k x j ∑R j, k x j
L j j j j
2 ln Γ i =  + ∑x k  ⋅
∑S j, i x j ∑V j, i x j k ∑S j, k x j ∑V j, i x j
j j j j (3.396)
A i, k R i, k S i, k V i, k

 + 
 –  – 

∑ j, k j ∑ j, k j ∑ j, k j ∑ j, k j
A x R x S x V x
j j j j
Description of Terms
The Regular Solution equation uses the following:
L 2
v i ( δi – δj ) A i, j
A i, = 
 R i, = 
 V i, = R i, S i, = R i, (3.397)
j j j j j j
RT A j, i
3186
Thermodynamic Calculation Models
L
v i = v ω, i ( 5.7 + 3T r, i ) (3.398)
∞ b i, j
ln γ i,  + c ij T
= a i, j +  (3.399)
j
T
where: T must be in K
b i,
A i, j = 2τ i, j V i, j R i, j = 1 V i, j = exp ( – c i, j τ i, j ) S i, j = 1 τ i, j = a i, j +  (3.400)
T(K
3187
3188 Activity Models
the R term of NRTL into the values for aij and bij. As such, the
values initialized for NRTL under ChienNull 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 α term for the
original NRTL, and will be assumed to be symmetric.
b i, j A i, j
A i, j = a i, j + 
 R i, j = 
 V i, j = C i, j S i, j = C i, j (3.401)
T(K) A j, i
In all cases:
A i, i = 0 R i, i = S i, i = V i, i = 1 (3.402)
3188
Thermodynamic Calculation Models
Property Methods
A quick reference of calculation methods is shown in the table
below for the ChienNull (CN) property model.
Applicable
Calculation Method Property Class Name
Phase
Activity Coefficient Liquid COTHCNLnActivityCoeff Class
Fugacity coefficient Liquid COTHCNLnFugacityCoeff Class
calculation
Fugacity calculation Liquid COTHCNLnFugacity Class
Activity coefficient Liquid COTHCNLnActivityCoeffDT
differential wrt Class
temperature
NRTL temperature Liquid COTHNRTLTempDep Class
dependent properties
Excess Gibbs Liquid COTHCNExcessGibbsEnergy
Class
Excess enthalpy Liquid COTHCNExcessEnthalpy Class
Enthalpy Liquid COTHCNEnthalpy Class
Gibbs energy Liquid COTHCNGibbsEnergy Class
3189
3190 Activity Models
std
fi
ln φi = ln γ i  (3.403)
P
ChienNull 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 ( γ i x i f i ) (3.404)
3190
Thermodynamic Calculation Models
∂ ln γ
i (3.405)
∂T
3191
3192 Activity Models
n
E
G = RT ∑x i ln γ i (3.406)
i
n n
E
G = ∑xi Gi + RT ∑xi ln xi + G (3.407)
i i
3192
Thermodynamic Calculation Models
n
E 2 d ln γ i
H = – RT ∑xi 
dT
 (3.408)
i
d ln γ i

The term, dT , in the above equation is exclusively
calculated using the ChienNull Activity Coefficient
Differential wrt Temperature.
3193
3194 Activity Models
ChienNull Enthalpy
This method calculates the enthalpy using the CN activity model
from the following relation.
n
E
H = ∑xi Hi + H (3.409)
i
Hi = enthalpy of component i
3194
Thermodynamic Calculation Models
Model Description
ChaoSeader Use this method for heavy hydrocarbons, where the
pressure is less than 10342 kPa (1500 psia), and
temperatures range between 17.78 and 260°C (0
500°F).
Press. Press.
Method Temp. (°C) Temp. (°C)
(psia) (kPa)
CS 0 to 500 18 to 260 < 1,500 < 10,000
Conditions of Applicability
For all hydrocarbons (except 0.5 < Tri < 1.3 and Prmixture < 0.8
CH4):
If CH4 or H2 is present: • molal average Tr < 0.93
• CH4 mole fraction < 0.3
• mole fraction dissolved gases < 0.2
When predicting K values for:
Paraffinic or Olefinic Mixtures liquid phase aromatic mole fraction <
Aromatic Mixtures 0.5
liquid phase aromatic mole fraction >
0.5
3195
3196 GraysonStreed Model
GraysonStreed
Description
Model
GraysonStreed Recommended for simulating heavy hydrocarbon
systems with a high hydrogen content.
Press. Press.
Method Temp. (°C) Temp. (°C)
(psia) (kPa)
GS 0 to 800 18 to 425 < 3,000 < 20,000
Conditions of Applicability
For all hydrocarbons (except 0.5 < Tri < 1.3 and Prmixture < 0.8
CH4):
If CH4 or H2 is present: • molal average Tr < 0.93
• CH4 mole fraction < 0.3
• mole fraction dissolved gases < 0.2
When predicting K values for:
Paraffinic or Olefinic Mixtures liquid phase aromatic mole fraction <
Aromatic Mixtures 0.5
liquid phase aromatic mole fraction >
0.5
3196
Thermodynamic Calculation Models
3197
3198 GraysonStreed Model
3198
Physical Property Calculation Methods 41
4 Physical Property
Calculation Methods
41
42 Cavett Method
Property Methods
A quick reference of calculation methods is shown in the table
below for the Cavett method.
Phase
Calculation Method Property Class Name
Applicable
Enthalpy Liquid COTHCavettEnthalpy Class
Entropy Liquid COTHCavettEntropy Class
Isobaric heat capacity Liquid COTHNCavettCp Class
Helmholtz energy Liquid COTHCavettHelmholtz Class
Gibbs energy Liquid COTHCavettGibbs Class
Internal energy Liquid COTHCavettInternalEnergy
Class
42
Physical Property Calculation Methods 43
Cavett Enthalpy
This method calculates the liquid enthalpy using the Cavett
model from the following relation.
l steam67 Cavett
H = x water H water + ∑x i ( H °i + ∆H i ) (4.1)
i
nc
cavett cavett
∆H non – aqueous = ∑ min ( ∆H i )x i (4.2)
i = 1; i ≠ 1
1
∆H i = T c, i ( a1 + a2 ( 1 – T r, i ) )
e1 (4.3)
2 3 (4.4)
a1 = b1 + b2χi + b3χi + b4χi
e1 = 1 – a3 ( T r, i – 0.1 ) (4.7)
2 2 3 4 2 (4.8)
∆H i = T c, i ( max ( c1 + c2T r, i + c3T r, i + c4T r, i + c5T r, i, 0 ) )
∆H i
cavett
= ∆H i
1 (4.9)
43
44 Cavett Method
∆H i
cavett 1
= min ( ∆H i , ∆H i )
2 (4.10)
∆H i
cavett
= ∆H i
2 (4.11)
Cavett Entropy
This method calculates the liquid entropy using the Cavett
model from the following relation:
l steam67 Cavett
S = x water S water + ∑x i ( S °i + ∆S i ) (4.12)
i
1
cavett ∆H i (4.13)
∆S i = 

T
44
Physical Property Calculation Methods 45
is:
1 2
cavett min ( ∆H i , ∆H i ) (4.14)
∆S i = 

T
2
cavett ∆H i (4.15)
∆S i = 

T
T = Temperature (K)
Cavett Cp (Isobaric)
This method calculates the liquid isobaric heat capacity using
the Cavett model from the following relation.
l steam67 Cavett
Cp = x water Cp water + ∑x i ( Cp °i + ∆Cp i ) (4.16)
i
cavett
∆Cp i = T r, i ( 2 ( c2 + c5P r, i ) + T r, i ( 3c3 + T r, i ( 4c4 ) ) ) (4.17)
45
46 Cavett Method
1
∆H i e1
 a 3 log ( 1 – T r, i ) + 
cavett
∆Cp i = a 1 –   (4.18)
T c, i 1 – T r, i
∆Cp i
cavett
= 0 (4.19)
cavett
∆Cp i = T r, i ( 2 ( c 2 + c 5 P r, i ) + T r, i ( 3c 3 + T r, i ( 4c 4 ) ) ) (4.20)
where:
46
Physical Property Calculation Methods 47
A = G – PV (4.21)
G = H – TS (4.22)
47
48 Rackett Method
U = H – PV (4.23)
48
Physical Property Calculation Methods 49
Property Methods
A quick reference of liquid density and volume calculations are
shown in the table below for the Rackett method.
Calculation Phase
Property Class Name
Method Applicable
Liquid Volume Liquid COTHRackettVolume
Class
Liquid Density Liquid COTHRackettDensity
Class
2

RT c 1 + ( 1 – Tr ) 7 (4.24)
V s =  Z RA
Pc
49
410 Rackett Method
2

RT c 1 + ( 1 – Tr )
7
(4.25)
ρ s = 1 ⁄  Z RA
Pc
410
Physical Property Calculation Methods 411
411
412 COSTALD Method
Property Methods
A quick reference of liquid density and volume calculations are
shown in the table below for the Rackett method.
Calculation Phase
Property Class Name
Method Applicable
Liquid Volume Liquid COTHCOSTALDVolume Class
Liquid Density Liquid COTHCOSTALDDensity Class
(o) ( δ)
V s ⁄ V∗ = V r [ 1 – ωSRK V r ]
4
(o) k⁄ 3
Vr = 1+ ∑ Ak ( 1 – Tr ) 0.25 < T r < 0.95
(4.26)
k=1
3
( δ) k
Vr = ∑ Bk Tr ⁄ ( T r – 1.00001 ) 0.25 < T r < 1.0
k=0
412
Physical Property Calculation Methods 413
T cm = ∑∑x i x j V ij∗ T c ⁄ V m∗
ij
i j
2 1
 
3 3
V m∗ = 1 ⁄ 4 ∑x i V i∗ + 3 ∑x i V i∗ ∑x i V i∗
i i i (4.27)
1

2
V ij∗ T c = ( V i∗ T c V j∗ T c )
ij i j
ωSRK =
m ∑xi ωSRK i
i
413
414 Viscosity
1
ρ =  (4.28)
Vs
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),
Twu's model, or a modification of the LetsouStiel correlation.
This method will select the appropriate model using the
following criteria:
414
Physical Property Calculation Methods 415
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.
415
416 Viscosity
416
Physical Property Calculation Methods 417
3.6 ( 1 – ν oil )
µeff = µoil e (4.29)
417
418 Thermal Conductivity
follows:
Cp
eff
= ∑xi Cp i
(mixture specific heat)
418
Physical Property Calculation Methods 419
419
420 Thermal Conductivity
2 2
λL = φ1 λ L + 2φ1 φ2 λ 12 + φ2 λ L (4.32)
mix 1 2
φ1 = x1 V1


2
∑ xi Vi
i=1
φ2 = x2 V2


2
∑ xi Vi
i=1
420
Physical Property Calculation Methods 421
2⁄ 3 1⁄ 3 a
σ = Pc Tc Q ( 1 – TR ) × b (4.33)
421
422 Insoluble Solids
Property Methods
A quick reference of calculation methods for insoluble solids is
shown in the table below.
Calculation Phase
Property Class Name
Method Applicable
MolarDensity xptInsolubleSoli COTHSolidDensity Class
d
MolarVolume xptInsolubleSoli COTHSolidVolume Class
d
Enthalpy xptInsolubleSoli COTHSolidEnthalpy Class
d
Entropy xptInsolubleSoli COTHSolidEntropy Class
d
Cp xptInsolubleSoli COTHSolidCp Class
d
422
Physical Property Calculation Methods 423
423
424 Insoluble Solids
Insoluble Solid Cp
Property Class Name and Phases Applicable
Property Class Name Phase Applicable
COTHSolidCp Class xptInsolubleSolid
424
References & Standard States 51
5 References &
Standard States
51
52 Enthalpy Reference States
Property Methods
The enthalpy reference state calculation methods are shown in
the table below.
Property Class
Calculation Method Phase Applicable
Name
Ideal Gas Enthalpy Vapour & Liquid COTHOffsetIGH
Offset Class
Enthalpy Offset Vapour & Liquid COTHOffsetH Class
ig
H i + offset Hi (5.1)
52
References & Standard States
ig ( 25° C )
Offset Hi = – H i
fig ( 25° C )
+ Hi (5.2)
53
54 Entropy Reference States
Property Methods
The entropy reference state calculation methods are shown in
the table below.
Property Class
Calculation Method Phase Applicable
Name
Ideal Gas Entropy Vapour & Liquid COTHOffsetIGS
Offset Class
Entropy Offset Vapour & Liquid COTHOffsetS Class
ig
S i + offset Si (5.3)
Offset S = 0 (5.4)
54
References & Standard States
std (5.5)
fi = γ i xi fi
P
std sat sat V
f i = P i φi exp ∫ i dP (5.6)
RT
sat
Pi
55
56 Standard State Fugacity
the system
R = gas constant
T = temperature of system
Property Methods
The standard state fugacity calculation methods are shown in
the following table.
Calculation Phase
Property Class Name
Method Applicable
LnStdFugacity Liquid COTHIdealStdFug Class
LnStdFugacity Liquid COTHPoyntingStdFug
Class
LnStdFugacity Liquid COTHPhiStdFug Class
LnStdFugacity Liquid COTHPoyntingPhiStdFug
Class
56
References & Standard States
Notes
For noncondensible components in the presence of any
condensible components, Henry’s law is used as shown below.
std
f i = H i, j
(5.9)
57
58 Standard State Fugacity
Notes
For noncondensible components in the presence of any
condensible components, Henry’s law is used as shown below.
std
f i = H i, j
(5.12)
58
References & Standard States
Notes
For noncondensible components in the presence of any
condensible components, Henry’s law is used as shown below.
std sat
f i = H i, j exp [ ( P – P i )V i ⁄ ( RT ) ] (5.15)
59
510 Standard State Fugacity
Notes
For noncondensible components in the presence of any
condensible components, Henry’s law is used as shown below.
std sat
f i = H i, j exp [ ( P – P i )V i ⁄ ( RT ) ] (5.18)
510
References & Standard States
vapour model.
511
512 Standard State Fugacity
512
Flash Calculations 61
6 Flash Calculations
6.1 Introduction................................................................................... 2
61
62 Introduction
6.1 Introduction
Specified variables can Rigorous three phase calculations are performed for all
only be respecified by you
or via the Recycle Adjust,
equations of state and activity models with the exception of the
or SpreadSheet Wilson equation, which only performs two phase vapourliquid
operations. They will not calculations.
change through any heat
or material balance
calculations COMThermo uses internal intelligence to determine when it can
perform a flash calculation on a stream, and then what type of
flash calculation needs to be performed on the stream. This is
based completely on the degrees of freedom concept. When the
composition of a stream and two property variables are known,
(vapour fraction, temperature, pressure, enthalpy or entropy,
one of which must be either temperature or pressure), the
thermodynamic state of the stream is defined.
62
Flash Calculations 63
63
64 Vapour Fraction Flash
64
Flash Calculations 65
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.
65
66 Vapour Fraction Flash
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.
66
Flash Calculations 67
Flash control values are stored in the flash control object and
can be set through interface functions. The Flash XML file is
described by the COMThermo property manager. It identifies
the flash control settings and sets it into the flash control object
where flash can now get the controls.
Control Description
Fixed Control Fixed controls are hard coded controls that have
fixed names and default values. If the user does
not set the controls, the default values are used.
Additional Control Additional controls are called SecantSetting
controls. SecantSettings such as Temperature and
Pressure are set by default, as others can be
defined by COMThermo flash and/or the user. If
the user defines a control (the name given by the
user), in the user created flash object users can
use the same name to get the values of that
control set in the flash XML file.
Refer to the Flash Control Settings in the Flash XML File section
in the Programmer’s guide of the COMThermo development kit
for more information.
67
68 Flash Control Settings
68
Property Packages 71
7 Property Packages
7.1 Introduction................................................................................... 2
71
72 Introduction
7.1 Introduction
A summary of the property packages used within the
COMThermo framework are grouped into the following sections:
• Section 7.2  Vapour Phase Models
• Section 7.3  Liquid Phase Models
Ideal Gas
PV=nRT can be used to model the vapour phase but is only
suggested for ideal systems under moderate conditions.
72
Property Packages
PengRobinson
This model is ideal for VLE calculations as well as calculating
liquid densities for hydrocarbon systems. However, in situations
where highly nonideal systems are encountered, the use of
Activity Models is recommended.
73
74 Vapour Phase Models
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.
74
Property Packages
PengRobinsonStryjekVera
This is a twofold modification of the PR equation of state that
extends the application of the original PR method for moderately
nonideal systems. It provides a better pure component vapour
pressure prediction as well as a more flexible mixing rule than
Peng robinson.
75
76 Vapour Phase Models
SoaveRedlichKwong
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 nonideal systems.
76
Property Packages
RedlichKwong
The RedlichKwong 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.
77
78 Vapour Phase Models
ZudkevitchJoffee
This is a modification of the RedlichKwong 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 vapourliquid
equilibrium for hydrocarbon systems, and systems containing
Hydrogen.
78
Property Packages
KabadiDanner
This model is a modification of the original SRK equation of
state, enhanced to improve the vapourliquidliquid equilibrium
calculations for waterhydrocarbon systems, particularly in
dilute regions.
79
710 Vapour Phase Models
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.
710
Property Packages
LeeKeslerPlöcker
This model is the most accurate general method for nonpolar
substances and mixtures.
711
712 Vapour Phase Models
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 Kvalue is calculated at system temperature
and 10 psia (68.95 kPa).
712
Property Packages
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.
713
714 Liquid Phase Models
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.
714
Property Packages
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 Raoult’s Law; however, it
cannot predict maxima or minima in the activity coefficient.
Therefore it generally performs poorly for systems with
halogenated hydrocarbons and alcohols.
715
716 Liquid Phase Models
716
Property Packages
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.
717
718 Liquid Phase Models
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 multi
component behaviour from regressed binary equilibrium data.
However the Wilson model cannot be used for systems with two
liquid phases.
718
Property Packages
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.
719
720 Liquid Phase Models
UNIQUAC
This model uses statistical mechanics and the quasichemical
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
720
Property Packages
721
722 Liquid Phase Models
722
Property Packages
ChienNull
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.
723
724 Liquid Phase Models
Antoine
This model is applicable for low pressure systems that behave
ideally.
724
Property Packages
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 Kvalue is calculated at system temperature
and 10 psia (68.95 kPa).
725
726 Liquid Phase Models
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.
726
Property Packages
727
728 Liquid Phase Models
ChaoSeader
This method for heavy hydrocarbons, where the pressure is less
than 10342 kPa (1500 psia), and temperatures range between 
17.78 and 260°C (0500°F).
728
Property Packages
GraysonStreed
This model is recommended for simulating heavy hydrocarbon
systems with a high hydrogen content.
729
730 Liquid Phase Models
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.
730
Property Packages
KabadiDanner
This model is a modification of the original SRK equation of
state, enhanced to improve the vapourliquidliquid equilibrium
calculations for waterhydrocarbon systems, particularly in
dilute regions.
731
732 Liquid Phase Models
PengRobinson
This model is ideal for VLE calculations as well as calculating
liquid densities for hydrocarbon systems. However, in situations
where highly nonideal systems are encountered, the use of
Activity Models is recommended.
732
Property Packages
PengRobinsonStryjekVera
This is a twofold modification of the PR equation of state that
extends the application of the original PR method for moderately
nonideal systems. It provides a better pure component vapour
pressure prediction as well as a more flexible Mixing Rule than
Peng robinson.
733
734 Liquid Phase Models
734
Property Packages
SoaveRedlichKwong
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 nonideal systems.
735
736 Liquid Phase Models
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.
736
Property Packages
ZudkevitchJoffee
This is a modification of the RedlichKwong 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 vapourliquid
equilibrium for hydrocarbon systems, and systems containing
Hydrogen.
737
738 Liquid Phase Models
LeeKeslerPlöcker
This model is the most accurate general method for nonpolar
substances and mixtures.
738
Utilities 81
8 Utilities
8.1 Introduction................................................................................... 2
81
82 Introduction
8.1 Introduction
The utility commands are a set of tools, which interact with a
process by providing additional information or analysis of
streams or operations. In HYSYS, utilities become a permanent
part of the Flowsheet and are calculated automatically when
appropriate.
82
References
9 References
1
Prausnitz, J.M.; Lichtenthaler, R.N., and de Azeuedo, E.G. “Molecular
Thermodynamics of Fluid Phase Equilibria”, 2nd Ed. Prentice Hall,
Inc. (1986).
2
Prausnitz, J.M.; Anderson, T.; Grens, E.; Eckert, C.; Hsieh, R.; and
O'Connell, J.P. “Computer Calculations for MultiComponent
VapourLiquid and LiquidLiquid Equilibria” PrenticeHall Inc.
(1980).
3
Modell, M. and Reid, R.D., “Thermodynamics and its Applications”,
2nd Ed., PrenticeHall, Inc. (1983).
4
Michelsen, M.L., “The Isothermal Flash Problem. Part I. Stability, Part
II. Phase Split Calculation, Fluid Phase Equilibria”, 9 119; 2140.
(1982).
5
Gautam, R. and Seider, J.D., “Computation of Phase and Chemical
Equilibrium. I. Local and Constrained Minima in Gibbs Free Energy;
II. Phase Splitting, III. Electrolytic Solutions.”, AIChE J. 24, 991
1015. (1979).
6
Reid, J.C.; Prausnitz, J.M. and Poling, B.E. “The Properties of Gases
and Liquid” McGrawHill Inc. (1987).
7
Henley, E.J.; Seader, J.D., “EquilibriumStage Separation Operations
in Chemical Engineering”, John Wiley and Sons. (1981).
8
Feynman, R.P., Leighton, R.B., and Sands, M., “The Feyman Lectures
on Physics” AddisonWesley Publishing Company. (1966).
9
Peng, D.Y. and Robinson, D.B. “A New Two Constant Equation of
State” Ind. Eng. Chem. Fundamen. 15, 5964. (1976).
10
Stryjek, R. and Vera, J.H. “PRSV: An Improved PengRobinson
Equation of State for Pure components and Mixtures” The Canadian
Journal of Chemical Eng. 64. (1986).
11
Soave, G. “Equilibrium Constants from a Modified RedlichKwong
Equation of State”. Chem. Eng. Sci. 27, 11971203. (1972).
12
Graboski, M.S. and Daubert, T.E., “A Modified Soave Equation of
State for Phase Equilibrium Calculations. 3. Systems Containing
Hydrogen” Ind. Eng. Chem. Fundamen. 15, 5964. (1976).
13
Zudkevitch, D. and Joffee, J., Correlation and Prediction of Vapor
Liquid Equilibria with the Redlich Kwong Equation of State, AIChE
91
92
92
References
93
94
43
Twu, C.H., “An Internally Consistent Correlation for Predicting the
Critical Properties and Molecular Weight of Petroleum and Coaltar
Liquids”, Fluid Phase Equilibria, 16, 137150. (1984).
44
Wilson, G.M. “VapourLiquid Equilibria, Correlation by Means of a
Modified Redlich Kwong Equation of State”.
45
Wilson, G.M. “Calculation of Enthalpy Data from a Modified Redlich
Kwong Equation of State”.
46
Soave, G. “Improvement of the van der Waals Equation of State”
Chem. Eng. Sci 39, 2, 357369. (1984).
47
Chao, K.C and Seader, J.D. “A General Correlation of VapourLiquid
Equilibria in Hydrocarbon Mixtures” AIChE Journal 7, 598605.
(1961).
48
Larsen, B.L.; Fredenslund, A. and Rasmussen, P. “Predictions of VLE,
LLE, and HE with Superfac” CHISA. (1984).
49 Pierotti,
G.J.; Deal, C.H. and Derr, E.L. Ind. Eng. Chem. 51, 95.
(1959).
50 Lee,
B.I. and Kesler, M.G. AIChE Journal 21, 510. (1975).
51
Woelflin, W., “Viscosity of CrudeOil Emulsions”, presented at the
spring meeting, Pacific Coast District, Division of Production, Los
Angeles, California, March 10, 1942.
52 Gambill,
W.R., Chem. Eng., March 9, 1959.
53 Perry,
R.H. and Green, D.W. Perry’s Chemical Engineers’ Handbook
(Seventh Edition) McGrawHill. (1997).
54
Reid, C.R., Prausnitz, J.M. and Sherwood, T.K., “The Properties of
Gases and Liquids”, McGrawHill Book Company. (1977).
94
Index
A Flash Calculations
temperaturepressure (TP) 62
Activity Coefficient Models
Flash calculations 224
vapour phase options 231
Fugacity 28
Activity Coefficients 29
ideal gas 218
See individual activity models
simplifications 218
Activity Models 3103
See individual Activity models G
Asymmetric Phase Representation 226
General NRTL Model 3160
B Gibbs Free Energy 234
GibbsDuhem Equation 216
Bubble Point 65
Grayson Streed 3196
BWR Equation 3101
semiempirical method 3196
C GraysonStreed Model 3196
carboxylic acid 224 H
Cavett Method 42
Henry’s Law 212, 231
Chao Seader 3195
estimation of constants 215
semiempirical method 3195
HypNRTL Model 3159
ChaoSeader Model 3195
HysysPR Equation of State 317
Chemical Potential
mixing rules 323
ideal gas 27
property classes 318
real gas 28
property methods 318
ChienNull Model 3186
property classes 3189 I
property methods 3189
Ideal Gas Cp 55
COSTALD Method 411
Ideal Gas Equation of State 33
Cp 238
property classes 34
D property methods 34
Ideal Gas Law 231
Departure Functions
Ideal Solution Activity Model 3106
Enthalpy 238
property classes 3106
Dew Point 64
property methods 3106
Dimerization 221
Insoluble Solids 422
E Interaction Parameters 227
Internal Energy 23
Enthalpy Flash 65
Enthalpy Reference States 52 K
Entropy Flash 66
KabadiDanner Equation of State 367
Entropy Reference States 53
mixing rules 376
Equations of State
property classes 370
See also individual equations of state
property methods 370
Equilibrium Calculations 224
Kvalues 224
Equilibrium calculations 224
L
F
LeeKesler Equation of State 397
Flash
mixing rules 3101
TP Flash 63
property classes 398
vapour fraction 63–64
I1
I2
I2
I3
Z
ZudkevitchJoffee Equation of State 358
mixing rules 364
property classes 358
property methods 358
I3
I4
I4