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Project of the IK-CAPE

Model Description

(Translation by DECHEMA e.V.)

Last Update: 28.03.02

Table of contents
Page

1 INTRODUCTION 1-1

2 DESCRIPTION OF THE TEMPERATURE DEPENDENCY FOR PURE

COMPONENT PROPERTY DATA 2-1

2.1 Equations 2-1

2.2 Extrapolations 2-3

3 CALCULATION OF AVERAGES 3-1

4 ACTIVITY COEFFICIENTS 4-1

4.1 NRTL model 4-1

4.2 UNIQUAC model 4-1

4.3 Wilson model 4-2

4.4 Flory-Huggins model 4-2

4.5 UNIFAC model 4-2

5 POYNTING CORRECTION 5-1

6 HENRY CORRECTION 6-1

7 EQUATIONS OF STATE 7-1

7.1 Redlich-Kwong-Soave equation 7-1

7.2 Peng-Robinson equation 7-2

8 FUGACITY COEFFICIENTS 8-1

8.1 Redlich-Kwong-Soave equation 8-1

8.2 Peng-Robinson equation 8-1

8.3 Virial equation 8-1

8.4 Association in vapor phase 8-2

9 ENTHALPY 9-1

9.1 Enthalpy of liquid with starting phase in liquid 9-1

9.2 Enthalpy of the liquid with starting phase in vapor 9-1

9.3 Enthalpy of a gas with starting phase in liquid 9-2

 9.4 Enthalpy of a gas with starting phase in vapor 9-2

9.5 Enthalpy of a solid component 9-2

9.6 The excess enthalpy 9-3

9.6.1 NRTL equation 9-3
9.6.2 UNIQUAC equation 9-4
9.6.3 Wilson equation 9-4
9.6.4 Flory-Huggins equation 9-5
9.6.5 Redlich-Kister equation 9-5

9.7 The isothermal pressure dependency of the enthalpy in vapor phase 9-5
9.7.1 Redlich-Kwong-Soave equation 9-5
9.7.2 Peng-Robinson equation 9-5

9.8 The enthalpy of a gas with simultaneous association 9-6

10 CHEMICAL REACTIONS 10-1

10.1 Equilibrium reactions 10-1

10.2 Kinetically controlled reactions 10-2

10.3 Reactions of general nature 10-3

1 Introduction
Inside of this handbook all models included inside the IK-CAPE Thermodynamics Package are documented.

Common abbreviations:

R gas constant in J/kmol/K

T temperature in Kelvin
P pressure in Pascal
Tc critical temperature in Kelvin
Pc critical pressure in Pascal
v volume in m/kmol
xi mol fraction in liquid phase
yi mol fraction in vapor phase
i activity coefficients
i fugacity coefficients

1-1
2 Description of the temperature dependency for pure
component property data

2.1 Equations

To describe the temperature dependency of any pure component property at current stage the following functions can be
used:

POLY : Polynom

f ( T ) = a0 + a1 T + a2 T 2 + ............. + a9 T 9

EPOL : Polynom in exponent

f (T ) = 10 a0 +a1T +a2T + ....+ a9T 9

2

WATS : extended Watson equation

f ( T ) = a0 ( a2 T ) a1 + a3

ANTO : Antoine equation

a1
ln( f ( T )) = a0
T + a2

ANT1 : extended Antoine equation

a1
ln f (T ) = a 0 + + a3T + a 4 ln T + a5T a6
T + a2

KIRC : Kirchhoff equation

a1
ln( f ( T )) = a0 + a2 ln T
T

2-1
 SUTH : Sutherland equation

a0 T
f (T ) =
a
1+ 1
T

WAGN : Wagner equation

1
ln f ( T ) = ln a1 + ( a2 + a3 1.5 + a 4 3 + a5 6 )
Tr
T
Tr =
a0
= 1 Tr
a0 = Tc
a1 = Pc

CPL : Equation for the specific heat capacity of liquids

a4
f ( T ) = a0 + a1T + a2 T 2 + a3 T 3 +
T2

ICPL : Equation for the specific heat capacity of liquids

a5
f (T ) = a0 + a1T + a2T 2 + a3T 3 + a4T 4 +
T

VISC : Equation for the dynamic viscosity

a1

f ( T ) = a0 e T + a 2

RACK : Rackett equation

a0
f (T ) = T
a11+(1 a2 )
a3

2-2
 KIR1 : extended Kirchhoff equation

a1
ln( f ( T )) = a0 + + a2 ln T + a3 T a4
T

ALYL : Aly-Lee equation

2 2
a2 a4

f (T ) = a 0 + a1 T + a3 T
sinh a 2 cosh a4
T T

DIP4 : DIPPR function for HVAP and ST

f (T ) = a1 (1 Tr ) h
with
h = a 2 + a3Tr + a 4Tr2 + a5Tr3
T
Tr =
a0
a 0 = Tc

DIP5 : DIPPR function for KVAP and VISV

a 0 T a1
f (T ) =
a a
1 + 2 + 32
T T

2.2 Extrapolations

To avoid nonsensical results as well as program crashes, one can use the possibility to extrapolate the above given
functions beyond the proofed temperature range using one of the given extrapolation methods.

Linear extrapolation

For linear extrapolation inside the f(T)-diagram applies for the case T > Tupper and f (Tupper ) > 0

f (T ) = f (Tupper ) (T Tupper ) + f (Tupper )

f (T ) = f (Tupper )

2-3
 and for the case T < Tlower and f (Tlower ) < 0

f (T ) = f (Tlower ) (T Tlower ) + f (Tlower )

f (T ) = f (Tlower )

Extrapolation to the value B

For T > Tupper and f (Tupper ) < 0 applies with 0 B < f (Tupper )

f (Tupper )
[ ]
f (T ) = f (Tupper ) B exp (T Tupper ) + B
f (Tupper ) B

f (Tupper )
f (T ) = f (Tupper ) exp (T Tupper )
f (Tupper ) B

For T < Tlower and f (Tlower ) > 0 gilt mit 0 B < f (Tlower )

f (Tlower )
f (T ) = [ f (Tlower ) B ]exp (T Tlower ) + B
f (Tlower ) B

f (Tlower )
f (T ) = f (Tlower ) exp (T Tlower )
f (Tlower ) B

linear extrapolation inside a logarithmic diagram

d ln f (T )
ln f (T ) = (T Tupper ) + ln f (Tupper )
dT T =Tupper

For T > Tupper and f (Tupper ) < 0 applies expressed in f(T)

f (Tupper )
f (T ) = exp (T Tupper ) + ln f (Tupper )
f (Tupper )

f (Tupper )
f (T ) = f (T )
f (Tupper )

2-4
 Extrapolation of the Wagner equation for vapor pressure

a 0 = Tc
a1 = Pc

Above the critical point the Wagner equation is extrapolated linear inside the ln(p) vs. 1/T diagram

1 1
a 2a 0
T a0
f ( T ) = a1 e
a a
f ( T) = 2 2 0 f ( T)
T
at T > Tc the vapor pressure represents a virtual value.

2-5
3 Calculation of averages

MOLA: average based on mole fractions

average = xi valuei
i

MASS: average based on mass fractions

x value mass ,i i
average = i

x i
mass ,i

MOLG: logarithmic average based on mole fractions

ln(average) = xi ln(valuei )
i

MALG: logarithmic average based on mass fractions

x mass ,i ln(valuei )
ln(average) = i

x i
mass ,i

LAMB: average for the heat conductivity of gaseous mixtures

1
m = 0 . 5 x i i +

xi



i

VISC: average for the viscosity of gaseous mixtures

x M
i i i
m = i

x M
i
i i

3-1
 VOLU: average for density based on volume

1
m =
x
ii
i

WILK: average from Wilke for viscosity of gaseous mixtures

y i valuei
average =
i y j Fi , j
j
2
valuei Mol j
1 + 4
Fi , j = value j Moli
Moli
81 +
Mol
j

WAMA: average from Wassiljewa,Mason,Saxena fr die heat conductivity of

gaseous mixtures

yi valuei
average =
i y j Fi, j
j
2
i Mol j
1 + 4
j Moli
Fi , j =
Moli
81 +
Mol
j

= gas vis cos ity

DIST: average for the surface tension based on DIPPR

xiVol i 4 valuei
4


average = i
i xiVoli

3-2
 DIKL: average for the heat conductivity of liquids based on DIPPR

2 xvi xv j
average =
1 1
i j
+
valuei value j
xiVol i
xvi =
x jVol j
j

3-3
4 Activity coefficients

4.1 NRTL model

G x j ,i
xG j ,i j
G x
l, j l, j l
ln i = + i, j
j j i, j l

G x k
G k ,i k j
k
k , j xk

G x
k
k, j k

S j ,i j ,i
G j ,i = e

b j ,i
j ,i = a j ,i + + e j ,i ln T + f j ,i T
T

S j ,i = c j ,i + d j ,i (T 27315
. )

4.2 UNIQUAC model

The volume part is defined by:

ri x i
Vi =
rj x j
j

The surface part is defined by:

qi x i q i xi
Fi = and F i =
qj xj qj
j xj
j

For the activity coefficient applies:

ln i = ln iC + ln iR

with

Vi KZ F V
ln iC = ln
xi
+
2
q i ln i + li i
Vi xi
x l
j
j j

and

F j i , j
ln R
= q i 1 ln F j j ,i
j F k k , j
i


j
k

li = 5 (ri q i ) (ri 1)

4-1
 b j ,i
a j ,i + + c j ,i ln T + d j ,i T
j ,i = e T

4.3 Wilson model

x k k ,i
ln i = 1 ln x j i, j
j k x jk, j
j

bi , j
ai , j + + ci , j ln T + d i , j T
i, j = e T

4.4 Flory-Huggins model

+ (1 1 ) 2 i 1, 2 i
1 1
ln i = 1 + ln
r r 2i

r2 k r2 k
ln 2 k = 1 + ln + 1r2 k 1, 2 k 2 i 1, 2i
r r 2i

with

x1
1 =
r
r x
2i = 2 i 2 i
r

r = x1 + x 2i r2i
2i

1
1,2i = 10,2i + 11,2i
T
ri segment number of component i
i volume fraction of component i
1,2i interaction parameter
solvent(1)-solved species(2i)

4.5 UNIFAC model

The volume part is defined by:

ri
Vi =
rj x j
j

ri = (ki ) Rk

4-2
The surface part is defined by:

qi
Fi =
qj xj
j

qi = (ki ) Qk

For the activity coefficient applies:

ln i = ln iC + ln iR

with the combinatorial part

V V
ln ic = 1 Vi + ln Vi 5qi 1 i + ln i
Fi Fi

and the residual part, that describes the interactions between the different functional groups.

ln iR = k( i ) ( ln k ln k( i ) )

m km
ln k = Qk 1 ln m km
m n n nm

Herein is m the area fraction of the functional group m

Qm X m
m =
Qn X n
n

with the mole fraction X m of the functional group m.

( j)
m xj
Xm =
j

j n
( j)
n xj

The parameter ji contains the group interaction coefficient between the groups j and i:

a j ,i

j ,i = e T

4-3
5 Poynting correction
v iL ( P Pi s )
ln Fp ,i =
RT

5-1
6 Henry correction

x j ln Hi, j
ln H i =
j

x j
j

whereas means:
i Index of the Henry components
j Index of the non Henry components

b
ln Hi , j = a + + c ln T + d T
T

6-1
7 Equations of state

7.1 Redlich-Kwong-Soave equation

The fugacity coefficients can be calculated using the following equation:

a as B v + bm
ln i =
Bi
bm
( z m 1) ln z m + ln
vm
m 2 i i ln m
v m bm bm RT a m bm vm

using the following mixture rule:

a m = x i x j ai, j
i j

asi = x j ai, j
j

and

Bi = 2 bsi bm

bm = x i x j bi, j
i j

bsi = x j bi, j
j

Herein means:

ai, j = (
Ai A j 1 ki , j )
bi + b j
bi, j =
2
(1 k )
bi , j

The pure component parameters a, b can be received from:

Ai ( T ) = ai i

[ ( )]
2
i = 1 + mi 1 Tr

. i 0176
mi = 0.48 + 1574 . i2

R 2Tc2
a i = 0.42748
Pc

7-1
 RTc
bi = 0.0867
Pc

7.2 Peng-Robinson equation

Pressure explicit representation:

RT a(T )
P=
v b v ( v + b) + b(v b)

Normal form of the cubic equation for the volume explicit representation:

RT 2 3Pb 2 + 2 RTb a Pb3 + RTb 2 ab

v3 + b v v + =0
P P P

Calculation of compressibility:

Pvm
zm =
RT
vm a m vm
zm=
vm bm RT vm ( vm + bm ) + bm ( vm bm )

using the following mixture rules:

am = xi x j ai , j
i j

bm = xibi
i

Herein means:

ai , j = Ai ( T ) A j ( T ) (1 ki , j )

The pure component parameters a, b can be received from:

Ai ( T ) = ai i

2
T
i = 1 + mi 1
Tci

mi = 0.37464 + 154226
. i 0.26992 i 2

7-2
 R 2 Tci 2
ai = 0.45724
Pci
RTci
bi = 0.07780
Pci

7-3
8 Fugacity coefficients

8.1 Redlich-Kwong-Soave equation

i0
i =
iv

Pi s A (T ) v i + bi
ln i0 = z i 1 ln
RT
( vi bi ) i ln
bi RT v i

and

a as B v + bm
ln iv =
Bi
bm
( z m 1) ln z m + ln
vm
m 2 i i ln m
v m bm bm RT a m bm vm

The mixture rules can be find in the previous chapter Equations of state.

8.2 Peng-Robinson equation

i 0
i =
i v

with

PS
ln i 0 = z i 1 ln i ( v i bi )
Ai (T )
ln
(
v i + 1 + 2 bi

)
RT (
2 2bi RT v i + 1 2 bi )
for a pure component at saturated vapor pressure

and

bi P am 2 ( )
bi v m + 1 + 2 bm
ln i v = ( z m 1) ln ( v m bm ) x a ln
bm RT 2 2bm RT a m j
j i, j
( )
bm v m + 1 2 bm

for a component inside a mixture

8.3 Virial equation

i0
i =
iv

8-1
 2
Bi , i
v
e
i0 =
Bi,i
1+
v

RT 4P0 B
v= 1 + 1 + i i ,i
2 Pi 0 RT

2
v j
y j Bi , j

e
iv =
Bm
1+
v

RT 4 PBm
v= 1 + 1 +
2P RT

Bm = yi y j Bi, j
i j

Bm
zm = 1 +
v
with

Bi,i = Pure component virial coefficient

Bi, j = Cross virial coefficient

8.4 Association in vapor phase

Prerequisites:
The vapor phase behaves ideal, temperature, pressure and concentration are given
up to 5 components can build Di-, Tetra- and Hexamers as well as mixed dimers among each other
any desired number of inerts is allowed

Notation:

"true" concentration z in
i,j ... components
n association degree n=1,2,4,6 for i 5
zi2 = zi4 = zi6 = 0 for i > 5

Mixed dimers z Mij i,j 5

Equilibrium constants:

For each association reaction n (i) (i)n

8-2
 (i) + (j) (ij)

z in
equilibrium constants K in =
z p n 1
n
i1

z Mij
K Mij =
z i1 z j1 p

Bin
are generated. For each applies: ln K in = Ain +
T

K Mij = 2 K i 2 K j 2

Set of equations to calculate the true monomer concentrations:

Material balance: K n
z p n 1 = 1
in i1
i n

Material rate for each component i:

nK z p n 1 +
n
in i1 K z z p
Mij i1 j1
yi
j i, j 5
=
n

nK
n
n
z p
1n 11
n 1
+ K
j i, j 5
z z p
M1 j 11 j1 y1

Set of equations for the variable z in to be solved iterative. Afterwards all z in and z Mij can be calculated.

The fugacity coefficients can be calculated afterwards as follows:

z i1
i =
yi

8-3
9 Enthalpy

The following abbreviations are used:

h io Reference enthalpy of the pure component

h il Enthalpy of the liquid, component i
h iv Enthalpy of the vapor, component i
ri Enthalpy of vaporization, component i
cp i specific heat capacity of the ideal gas, component i
ps (T )
h v
h
p
dp
0

9.1 Enthalpy of liquid with starting phase in liquid

The enthalpy of the liquid follows from:

hl = h E + xi hil
i

with

h =h + cl dT
l 0
i i i
T0 ,i

9.2 Enthalpy of the liquid with starting phase in vapor

The enthalpy of the liquid follows from:

hl = h E + xi hil
i

If the temperature for the phase change is set equal to the systems temperature, the enthalpy of the pure component can
be calculated using:

T
hiv 0

h = h + cpi dT
l 0
dp ri (T )
i i
T0 ,i ps (T )
p i

If the temperature for the phase change is predetermined, the enthalpy of the pure component has to be calculated using:

hiv
Tui 0 T

h = h + cpi dT
l 0
dp ri (Tui ) + cli dT
i i
T0,i pis ( Tui )
p Tui

9-1
9.3 Enthalpy of a gas with starting phase in liquid

The enthalpy of the gas follows from:

h
P

hv = v dp + yi hiv
0
p i

If the temperature for the phase change is set equal to the systems temperature, the enthalpy of the pure component can
be calculated using:

T
hiv
0

h = h + cli dT + ri (T ) +
v 0
dp
i i
T0,i ps (T )
i
p

If the temperature for the phase change is predetermined, the enthalpy of the pure component has to be calculated using:

hiv
Tui 0 T

h = h + cli dT + ri (Tui ) +
v 0
dp + cpi dT
i i
T0,i pis ( Tui )
p Tui

9.4 Enthalpy of a gas with starting phase in vapor

The enthalpy of the gas follows from:

h
P

hv = v dp + yi hiv
0
p i

with

h = h + cpi dT
i
v
i
0

T0, i

9.5 Enthalpy of a solid component

The enthalpy of a solid component follows from:

hs = si his
i

with

his = hi0 + cs dT
T0,i
i

9-2
9.6 The excess enthalpy

gE

ln i 1 i
= RT 2 xi = RT 2 xi
T
h E = T 2
T i T i i T

The excess enthalpy can be calculated using different methods.

9.6.1 NRTL equation

gE
x G j j ,i j ,i
= xi
j

RT i x Gj
j j ,i

Ai Bi Bi Ai
h E = T 2 R xi
i Bi2

with

Ai = x j G j ,i j ,i
j

Ai
T
(
= Ai = x j G j ,i j ,i + G j ,i j ,i
j
)
Bi = G j ,i x j
j

Bi
= Bi = x j G j ,i
T j

S j ,i j ,i
G j ,i = e
S j ,i = c j ,i + d j ,i (T 27315
. )
b j ,i
j ,i = a j ,i + + e j ,i ln T + f j ,i T
T

G j ,i S j ,i j ,i
= G j ,i = G j ,i j ,i + S j ,i
T T T
j ,i b j ,i e j ,i
= j ,i = + + f j ,i
T T2 T
S j ,i
= d j ,i
T

9-3
9.6.2 UNIQUAC equation

gE F
= xi ln Vi + 5 q i xi ln i q i xi ln x j F j j ,i
RT i i Vi i j

i , j
A A j i , j Aj
T
h E = RT 2 q i xi i + F j
i iA j Aj 2

with

Ai = F j j ,i
j

j ,i
Ai = F j
j T

q i xi
F i =
q j j xj

and
b j ,i
a j ,i + + c j ,i ln T + d j ,i T
j ,i = e T

9.6.3 Wilson equation

gE
= R x i ln x j i, j
T i j

j ,i j j ,i j
h E = RT 2 xi i + x j
i i j 2j

i
= i = x j i , j
T j

i = x j i , j
j

i , j bi , j ci , j
= i , j = i , j 2 + + di, j
T T T
bi , j
ai , j + + ci , j ln T + d i , j T
i, j = e T

9-4
9.6.4 Flory-Huggins equation

gE
= x1 ln 1 + x 2i ln 2i + x1 2i 1,2i
RT x1 2i x2i 2i

h E = RTx1 2i 1,2i
2i

9.6.5 Redlich-Kister equation

h E = 0,5 hiE, j
i j

xi x j
hiE, j =
xi + x j
( A(T ) + B(T ) x d + C (T ) x d2 + D(T ) x d3 + E (T ) x d4 + F (T ) x d5 )

x d = xi x j

The temperature dependency of the coefficients in most cases can be characterized well by a polynom:

A( T ) = a0 + a1T + a2 T 2 ...

9.7 The isothermal pressure dependency of the enthalpy in vapor phase

9.7.1 Redlich-Kwong-Soave equation

The pressure dependency of the pure component is characterized as follows:

dai
T ai b p s
hi = RT ( z 1) + dT ln 1 + i i
bi zRT

The pressure dependency of the mixture:

dam
T am
b p
hm = RT ( z 1) + dT ln 1 + m
bm zRT

9.7.2 Peng-Robinson equation

The pressure dependency of the pure component is characterized as follows:

9-5
 1 Ai (T ) vi + (1 + 2 )bi
hi = RT ( zi 1) Ai (T ) T ln
2 2bi T vi + (1 2 )bi

with

2
T
Ai (T ) = ai 1 + mi 1
Tci

Ai (T ) T ai mi
= 1 + mi 1
T Tci Tci T

The pressure dependency of the mixture:

1 a m v m + (1 + 2 )bm
hm = RT ( zm 1) am T ln
2 2bm T v m + (1 2 )bm

with

a m 1 A j (T ) Ai (T )
= xi x j (1 k i , j ) Ai (T ) + A j (T )
T i j 2 Ai (T ) A j (T ) T T

9.8 The enthalpy of a gas with simultaneous association

hv = RE + yi hiv
i

z in hin + z Mij hMij

j i
RE =
i n i

nz
i n
in + 2 z Mij
i j i

hin = RBin
R
(
hMij = Bi 2 + B j 2
2
)

9-6
10 Chemical reactions

10.1 Equilibrium reactions

a1
ln f ( T ) = a0 + + a2 ln T + a3 T + a 4 T 2 + a5 T 3
T

EQLM

x
i
i
i
= f (T )

EQVM

y
i
i
i
= f (T )

EQLC

i
x
i Vi = f (T )
xi
V =
i i

EQVC

y
i

i Vi = f (T )
z RT
V=
P

EQLA

( x )

= f (T )
i
i i
i

EQVP

( Py )
i
i = f (T )
i

EQLF

10-1

i0 Pi s i Fpi i
i f 0 xi = f (T )

EQVF

iv P i
i f 0 yi = f (T )

10.2 Kinetically controlled reactions

a1
ln f ( T ) = a 0 + + a 2 ln T + a3 T
T
a
ln ( T ) = a0 + 1 + a2 ln T + a3 T
T

KILM

= V f k x i 1 + l i,l x i
i ,k

k i l i

KIVM

= V f k y i 1 + l i,l y i
i ,k

k i l i

KILC

i , k
= V
fk
i i l 1 + Vsl i i,l xi
x
Vs
k i,k

x
Vs = i
i i

KIVC

= V 1 + l
fk
y i , k
i ,l y i
Vs i ,k
k
i
l Vs i
i
zRT
Vs =
P

KILW

10-2

= VmVs 1 + l
fk
x i , k
i ,l x i
Vs i , k
k
i
l Vs i
i
Vs = x i Mwi
i

KIVW

i , k
= VmVs
fk
i i l 1 + Vsl i i,l yi
y
Vs
k i ,k

Vs = y i Mwi
i

zRT
m =
P

10.3 Reactions of general nature

COOR

= value

CONV

ratio * M ref = r ref

STAT

ratio * M ref = r ref (ratio 1)

10-3