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Project of the IK-CAPE

Model Description

(Translation by DECHEMA e.V.)

Last Update: 28.03.02

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

DESCRIPTION OF THE TEMPERATURE DEPENDENCY FOR PURE COMPONENT PROPERTY DATA

2

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

9.4

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

T c

P c

v

x i

y i

pressure in Pascal critical temperature in Kelvin

critical pressure in Pascal

volume in m³/kmol mol fraction in liquid phase

mol fraction in vapor phase

activity coefficients

fugacity coefficients

i

i

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) =+a

aT + aT

2

01

2

+

+aT

9

9

EPOL : Polynom in exponent

f

(

T

) = 10

a

aT

+

01

+

a T

2

2

++

aT

9

9

WATS : extended Watson equation

fT

() =

a

(

a

02

T

)

a

1

+

a

3

ANTO : Antoine equation

ln( fT(

))

=

a

0

a

1

T

+

a

2

ANT1 : extended Antoine equation

ln fT(

)

=

a

0

+

a

1

T

+

a

2

++

aT

34

a

ln

T

+

aT a

5

6

KIRC : Kirchhoff equation

ln( fT(

))

=

a

0

a

1

+

T

a

2

ln

T

SUTH : Sutherland equation

f

( T

) =

a T 0 a 1 1 +
a
T
0
a
1
1 +

T

WAGN : Wagner equation

ln

fT

(

)

=

T

r

=

a

a

=

1

0

1

=

=

T

a

T

0

c

P

c

T

r

ln

a

1

+

1

T

r

(

+

aa

23

1 5

.

+

a

4

3

+

a

5

6

)

CPL : Equation for the specific heat capacity of liquids

f

(

T

) =+

a

aT

01

+

aT

2

2

+

aT

3

3

+

a

4

T

2

ICPL : Equation for the specific heat capacity of liquids

f

(

T

) =+ a

aT

01

+

aT

2

2

+

aT

3

3

+

aT

4

4

+

a

5

T

VISC : Equation for the dynamic viscosity

f

(

T

) =

ae

0

a

1

T

+

a

2

RACK : Rackett equation

f

(

T

) =

a

0

a

1

1

+

(

1

T

a

2

)

a

3

KIR1 : extended Kirchhoff equation

ln( fT(

))

a

1

=++

a

0

a

T 2

ln

T

+

aT a

3

4

ALYL : Aly-Lee equation

fT

(

) =

a

0

+

a 2 a 1 T a 2 sinh T
a
2
a
1
T a
2
sinh
T
2 2 a 4 + a 3 T a 4 cosh T
2
2
a
4
+ a
3
T a
4
cosh
T

DIP4 : DIPPR function for HVAP and ST

(

f

with

h

T

=

a

)

=

a

1

(1

2

+

a T

3

r

T

r

a

0

=

=

T

a

T

0

c

T

r

)

h

+

2

a T

4

r

+

3

a T

5

r

DIP5 : DIPPR function for KVAP and VISV

f

(

T

) =

a T

0

a

1

1 +

a

2

+

T

a

3

T 2

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

f

f

(

’(

T

)

T

)

=

=

f

’(

T

upper

)

f

’(

T

upper

)

(

T

T

upper

)

+

f

(

T

upper

)

T > T

upper

and

f

’(

T

upper

) > 0

and for the case

f

f

(

’(

T

)

T

)

T < T

lower

and

=

=

f

’(

T

lower

)

f

’(

T

lower

)

(

f

T

Extrapolation to the value B

’(

T

lower

) < 0

T

lower

)

+

f

(

T

lower

)

For T > T and f ’( T ) < 0 applies with 0 B
For
T > T
and
f
’(
T
) < 0
applies with 0
B <
f
(
T
upper
upper
upper
f
’(
T
)
[
]
upper
f
(
T
)
=
f
(
T
)
B
exp
( T
T
)
+
B
upper
upper
f
( T
)
B
upper
f
’(
T
)
upper
f
’(
T
)
=
f
’(
T
) exp
( T
T
)
upper
upper
f
(
T
)
B
upper
For
T < T
and
f
’(
T
) > 0
gilt mit 0
B <
f
(
T
)
lower
lower
lower
f
’(
T
)
lower
f
(
T
)
=
[
f
(
T
)
B
]
exp
(
T
T
)
+ B
lower
lower
f
( T
)
B
lower
f
’(
T
)
lower
f
’(
T
)
=
f
’(
T
) exp
( T
T
)
lower
lower
f
( T
)
B
lower
∑ linear extrapolation inside a logarithmic diagram
d ln
f
(
T
)
ln
f
(
T
) =
(
T
T
)
+
ln
f
(
T
)
upper
upper
dT
T
= T
upper
For
T > T
and
f
’(
T
) < 0
applies expressed in f(T)
upper
upper
f
’( T
)
upper
(
)
f
(
T
)
=
exp
T
T
+ ln
f
(
T
)
upper
upper
f
( T
)
upper

f

’(

T

)

= f

(

T

)

f

’(

T

upper

)

f

(

T

upper

)

)

Extrapolation of the Wagner equation for vapor pressure

a

a

0

1

=

=

T

P

c

c

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

f

f

(

T

) =

ae

1

a

2

a

0

1

T

’(

T

)

=

a a

2

0

T

2

f

1

a

0

(

T

)

at T > T c the vapor pressure represents a virtual value.

3

Calculation of averages

MOLA: average based on mole fractions

average

=

i

x

i

value

i

MASS: average based on mass fractions

average =

i

x

mass i

,

value

i

i

x

mass i

,

MOLG: logarithmic average based on mole fractions

ln(

)

average =

i

x

i

ln(

value

i

)

MALG: logarithmic average based on mass fractions

ln(

average

) =

i

x

mass i

,

ln(

value

i

)

i

x

mass i

,

LAMB: average for the heat conductivity of gaseous mixtures

m = 0.5

1 x + i i x i i
1
x
+
i
i
x
i
i

VISC: average for the viscosity of gaseous mixtures

x M i i i i = m x M i i
x
M
i
i
i
i
=
m
x
M
i
i

i

VOLU: average for density based on volume

1

m =

x

i

i

i

WILK: average from Wilke for viscosity of gaseous mixtures

y i value i average = i y j F i , j j 2
y
i value
i
average
=
i y
j F
i
, j
j
2
1 +
value
Mol
j
i
4
value
Mol
j
i
F
=
i
, j
Mol
8
1 +
i
Mol
j

WAMA: average from Wassiljewa,Mason,Saxena für die heat conductivity of gaseous mixtures

y i value = i average i y j F i , j j 2
y
i value
=
i
average
i y
j F
i
, j
j
2
1 +
Mol
j
i
4
Mol
j
i
F
=
i
, j
Mol
8
1 +
Mol
i
j
= gas vis
cos
ity

DIST: average for the surface tension based on DIPPR

average =

x Vol 4 value i i i i x Vol i i i
x Vol
4 value
i
i
i
i
x Vol
i
i
i

4

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

2 xv xv i j average = 1 1 i j + value value i
2 xv xv
i
j
average =
1
1
i
j
+
value
value
i
j
x Vol
i
i
xv
=
i x Vol
j
j

j

4

Activity coefficients

4.1 NRTL model

G x G x ji , ji , j x G lj , lj ,
G
x
G
x
ji ,
ji ,
j
x G
lj ,
lj ,
l
j
j
ij
,
l
ln
=+
i
i
,
j
G
x
G
x
G
x
ki
,
k
j
kj
,
k
kj
,
k
k
k
k
G
=
e
S ji
,
ji
,
j i
,
b
j i
,
=++
a
e
ln
T
+
fT
ji
,
ji
,
ji
,
ji
,
T
S
=+
c
dT
(
27315.)
ji,,,ji
ji
4.2 UNIQUAC model
The volume part is defined by:
r x
i
i
V
=
i
r x
j
j
j
The surface part is defined by:
q x
x
i
q
i
i
F i
i and F
=
q
x
i =
q
x
j
j
j
j
j
j
For the activity coefficient applies:
C
R
ln
=
ln
+
ln
i
i
i
with
V i KZ
F
V
C
i
i
ln
=
ln
+
q
ln
+
l
x l
i
i
i
j
j
x
2
V
x
i
i
i
j
and
F ’
j
ij
,
R
ln
=
q
1
ln
F
i
i
j
ji
,
F ’
j
j
k
kj
,
k
l
= 5
(rq )(r
1
)
i
ii
i
b j , i ++ c ln Td + T a j , i T
b j
, i
++
c
ln
Td +
T
a j
, i
T ji
,
ji
,
= e
j , i
4.3 Wilson model
ln
=
1
ln
x
i
j
ij
,
j
k
b
i
,
j
a
++
c
ln
Td +
T
i
,
j
ij
,
ij
,
= e
T
i
,
j

x

k

ki

,

j

x

j

kj

,

4.4 Flory-Huggins model

with

1 1 ln =+ 1 ln + ( 1 ) i 1 2 ii 12
1
1
ln
=+
1
ln
+
(
1
)
i
1
2
ii
12
,
r
r
2 i
r
r
2
k
2
k
ln
=+
1
ln
+
r
2 k
1
2
k
12
,
k
2
ii
12
,
r r
2 i
x
1
=
1
r
r
x
2
i
2
i
=
2 i
r
r
=
x
+
xr
1
22
i
i
2 i
1
0
1
=
+
12 ,
i
12
,,
ii
1 2
T
r i
i
1,2i
segment number of component i
volume fraction of component i
interaction parameter
solvent(1)-solved species(2i)

4.5 UNIFAC model

The volume part is defined by:

V

i

r

i

r

i

=

r x

j

j

j

=

i

( )

k

R

k

The surface part is defined by:

q i F = i q x j j j ( i ) q =
q
i
F
=
i
q
x
j
j
j
( i )
q
=
Q
i
k
k

For the activity coefficient applies:

C

ln

i

=

ln

i

+

ln

R

i

with the combinatorial part

ln

c

i

=

1

V

i

+

ln

Vq

51

ii

V

i

+

V

i

ln

F

i

F

i

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

R () i () i ln = (ln ln ) i k k k ln
R ()
i
()
i
ln
=
(ln
ln
)
i
k
k
k
ln
= Q
1
ln
k
k
m
km
m

m km n nm n
m
km
n
nm
n

Herein is

m the area fraction of the functional group m

m

Q

m

X

m

=

Q X

n

n

n

with the mole fraction X m

of the functional group m.

X

m

( j ) x m j j = ( j ) x n j j
(
j
)
x
m
j
j
=
(
j
)
x
n
j
j
n

The parameter

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

j , i

= e

a

j

,

i

T

5

Poynting correction

ln F

p i

,

=

vPP

i

i

L

(

s

)

RT

6

Henry correction

ln H

i

=

j

x

j

ln

H

ij

,

j

x

j

whereas means:

i Index of the Henry components

j Index of the non Henry components

ln

H

i ,

j =+

a

b

T

+

c

ln

T

+

dT

7

Equations of state

7.1 Redlich-Kwong-Soave equation

The fugacity coefficients can be calculated using the following equation:

ln

i

=

B

i

b

m

(

z

m

1

)

ln

z

+

m

using the following mixture rule:

a m = x xa i j i , j i j as i =
a
m
=
x
xa
i
j
i
, j
i
j
as i
=
x a
j
ij ,
j
and
B
= 2
bs
b
i
im
b
m
= x
xb
i
j
ij ,
i
j
bs
i
= x b
j
ij ,
j
Herein means:
(
)
a
=
AA
1
k
ij,
i
j
ij,
b
+ b
i
j
(
=
1
k
b i
, j
bi, j
2

)

ln

 

v

m

a

m

2

as

i

B

i

ln

v

m

+

b

m

v

m

b

m

b

m

RT

a

m

b

m

 

v

m

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

A ( T ) = a i ii )] 2 =+1 [ m ( 1
A
(
T
) =
a
i
ii
)]
2
=+1
[
m
(
1
T
i
ir
2
=+0 48
1574
0176
.
m i
ii
2
2
R T
c
a
=
0 42748
.
i
P
c

b i = 0.0867

RT

c

P

c

7.2 Peng-Robinson equation

Pressure explicit representation:

P =

RT

a

(

T

)

v

b

vv

(

++

b

)(

bv

b

)

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

v

3

+

b

RT

 

3

Pb

2

+

2

RTb

 

32

ab

 

2

a

Pb

+

RTb

 

v

   

P

P

 

P

Calculation of compressibility:

z

=

Pv

m

m RT

z m

=

v

m

v

m

b

m

a

m

v

m

RT

v

v

++)(

m

b

b

(

mm

v

mm

RT v v ++ )( m b b ( mm v mm b m )

b

m

)

using the following mixture rules:

a

m

b

m

=

=

i

i

j

xb

ii

xxa

i

j

ij

,

Herein means:

a ij,

=

ATA

i

(

)

j

(

T

i j ij , Herein means: a ij , = ATA i ( ) j (

)(1

k

ij,

)

=

0

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

AT ( ) = a i ii T =+ 1 m 1 i i Tc
AT
(
) =
a
i
ii
T
=+
1
m
1
i
i
Tc
i
=+0 37464
154226
m i

2

0 26992

ii

.

2

a

i

b

i

= 0 45724

.

= 0.07780

R

2

Tc

i

2

Pc

RTc

i

i

Pc

i

8

Fugacity coefficients

8.1 Redlich-Kwong-Soave equation

0

i = i v i s P A ( T ) v + b i
i
=
i
v
i
s
P
A
(
T
)
v
+
b
i
i
i
i
ln
0 =
z
1
ln
(
v
b
)
ln
i
i
i
i
RT
b RT
v
i
i
and
B
v
a
as
B
v
+
b
v
i
ln
=
(
z
1
)
m
m
i
i
m
m
ln
z
+
ln
2
ln
i
m
m
b
v
b
b
RT
a
b
v
m
m
m
m
m
m
m
The mixture rules can be find in the previous chapter „Equations of state“.
8.2
Peng-Robinson equation
0
i
=
i
v
i
with
S
v
+ (
1
+
2
)
P
A
(
T
)
i
i
0
i
i
ln
=
z
1
ln
(
b
)
ln
b
v
i
i
i
i
RT
2
2 b RT
v
+ (
2
)
i
i
1 b
i
for a pure component at saturated vapor pressure
and
v
+ (
b
P
1
+
b
a
2
b
m
m
v
i
m
i
ln
=
(
z
)
1
ln
(
v
b
)
x a
ln
i
m
mm
j
ij
,
b
RT
2
2 b RT
a
b
v
+ (
1
b
m
m
m
j
m
m
m
for a component inside a mixture

8.3 Virial equation

i

=

0

i

v

i

2 B i , i v 0 e = i B i i , 1
2
B i
, i
v
0 e
=
i
B i i
,
1 +
v
0
RT
4 P B
i
ii ,
v =
1
++
1
0
2 P
RT
i
2
v
y
B
j
ij ,
j
v e
=
i
B
m
1 +
v RT 4 PB m v = 1 ++ 1 2 P RT B =
v
RT
4 PB
m
v =
1
++
1
2 P
RT
B
=
yyB
m
i
j
ij ,
i
j
B
m
z
=
1 +
m

with

v

B i,i = Pure component virial coefficient

B i, 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

Mixed dimers z Mij

Equilibrium constants:

For each association reaction

z in

i,j

n association degree

z i2 = z i4 = z i6 = 0 for i > 5

components

n=1,2,4,6 for i 5

i,j

5

n (i)

(i) n

equilibrium constants

are generated. For each applies:

(i) + (j) (ij) z in K = in n n 1 z 1 p
(i) + (j)
(ij)
z in
K
=
in
n
n
1
z
1 p
i
z Mij
=
K Mij
zz
p
i
1
j
1
B
in
ln K
=
A
+
in
in
T
K
= 2
KK
Mij
i
2
j
2

Set of equations to calculate the true monomer concentrations:

Material balance:

Material rate for each component i:

 

n

Kzp

in

i

1

n

1

= 1

 

i

n

nK

in

z

n

i 1

n

p

1

K

+ Mij

z

i

1

z

j

1

p

n

j

π

,

ij

5

 

nK

1

n

z

n

11

n

p

1

K

+ Mj 1

z

11

z

j

1

p

n

j

π

,

ij

 

5

=

y

y

i

1

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:

i

=

z i 1

y

i

9

Enthalpy

The following abbreviations are used:

o

h i

h i

h i

r i

cp i

l

v

Reference enthalpy of the pure component

Enthalpy of the liquid, component i

Enthalpy of the vapor, component i

Enthalpy of vaporization, component i specific heat capacity of the ideal gas, component i

s p ( T ) h 0
s
p
(
T
)
h
0

h

p

v

dp

9.1 Enthalpy of liquid with starting phase in liquid

The enthalpy of the liquid follows from:

h

l

with

h

l

i

E = h + i T 0 = h + i
E
=
h
+
i
T
0
=
h
+
i

T 0, i

xh

i

l

i

cl dT

i

9.2 Enthalpy of the liquid with starting phase in vapor

The enthalpy of the liquid follows from:

h

l

=

h

E

+

i

xh

i

l

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:

h

l

i

=+

i

h

0

T

T 0, i

cp dT

i

0 s p ( T ) i
0
s
p
(
T
)
i

h

v

i

p

dp
dp

r i

(

T

)

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

h

l

i

=+

i

h

0

T ui

cp dT

i

0

T 0, i

p

i s (

T

ui

)

v T

h

i

p

dp

r

i

(

T

ui

)

+

T ui

cl dT

i

9.3

Enthalpy of a gas with starting phase in liquid

The enthalpy of the gas follows from:

h

v

=

P

0

h

p

v

dp

+

i

y h

i

v

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:

h

v

i

=+

i

h

0

T

T

0, i

cl dT

i

+

r

i

(

T

)

+

p

s

i

0

(

T

)

h

v

i

p

dp

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

h

v

i

=+

i

h

0

T

ui

T

0, i

cl dT

i

+

r

i

(

T

ui

)

+

0

h

v

i

p

dp

+

T

cp dT

i

p

s

i

(

T

ui

)

T

ui

9.4 Enthalpy of a gas with starting phase in vapor

The enthalpy of the gas follows from:

h

v

with

v

h

i

=

=

P

0

0

h

i

h

p

v

T

+

T 0, i

dp

+

cp dT

i

i

y h

i

v

i

9.5 Enthalpy of a solid component

The enthalpy of a solid component follows from:

h

s

with

h

s

i

=

=

i

h

0

i

s

sh

ii

+

T

T 0, i

cs dT

i

9.6

The excess enthalpy

h

E

=

T

g

E

T

22

T

=

RT

i

x

i

ln

T

i

=

RT

2

i

x

i

1

i

i

T

The excess enthalpy can be calculated using different methods.

9.6.1 NRTL equation

with

x G j ji , ji , E g j = x i RT x
x G
j
ji ,
ji ,
E
g
j
=
x
i
RT
x G
i
j
ji
,
j
AB
BA
E
2
ii
ii
h
=
TR
x
2
i B
i
i
=
xG
i
A ji
j
,
ji
,
j
∂ A
i
==
A
i
xG
(
+
G
)
j
ji
,,
ji
ji
,,
ji
T
j
B
= Gx
i
ji
,
j
j
∂ B
i
=
B
i
=
xG ’
j
j i
,
T
j
S
G
= e
ji
,
ji
,
j , i
=+
c
dT
(
27315 .)
S ji
,,,
ji
ji
b j i
,
=++
a
e
ln
T
+
fT
ji
,
ji
,
T ji
,
ji
,
∂ G
∂ S
j , i
j i
,
j , i
= G
=
G
+
ji ,
ji ,
j , i
∂ T
∂ T
∂ T
j
, i
b ji ,
e ji ,
= =
+
2 +
j
, i
f j i
,
T
T
T
∂ S
j
, i
= d
j
, i
∂ T

S

j i

,

9.6.2

UNIQUAC equation

E g F =+ i x ln V 5 qx ln q ’ x ln
E
g
F
=+
i
x
ln
V
5
qx
ln
q
x
ln
xF
i
i
i
i
i
i
j
j
ji
,
RT
V
i
i i
i
j
i
,
j
A
A ’
A ’
j
ij
,
j
T
E
2
i
h
=
RT
q
x
+
F ’
i
i
j
2
A
A
i
i
j
j
with
A i
=
F ’
j
ji
,
j
j i
,
A
=
F
i
j
T
j
q
x
i
i
F ’
i
=
q
x
j
j
j
and
b
j
,
i
a
++
c
ln
Td +
T
j
,
i
ji
,
ji
,
= e
T
j i
,
9.6.3
Wilson equation
E
g
=
Rx
ln
x
i
j
ij
,
T
i
j
ji ,
j
ji ,
j
E
2
i
h
=
RT
x
+
x
i
j
2
i
i
j
j
i
=
=
x
i
j
ij
,
T
j
=
x
i
j
ij
,
j
b
c
i
,
j
ij
,
ij
,
=
=
++
d
ij
,
ij
,
2
i
,
j
T
T
T
b
i
,
j
a
++
c
ln
Td +
T
i
,
j
ij
,
ij
,
= e
T
i
,
j

9.6.4

Flory-Huggins equation

E

g

ln

1

RT

h

E

2 i

2 i

x

2

i

=+

=

x

1

RTx

 

x

1

1

2 i

2

i

x

ln

2 i

12 i

,

+ x

1

2 i

2

i

12 ,

i

9.6.5 Redlich-Kister equation

h

E

= 0,5

i

j

h

E

,

j

i

h

E

,

j

i

=

x x

i

j

x

i

+

x

j

x

dij

=

xx

(

()

AT

+++++

dd

()

BT x

()

CT x

2345

d

dd

()

DT x

()

ET x

()

FT x

)

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

AT(

) =+a

aT + aT

2

01

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:

h

i

=

RT(z

1

)

+

T da

i a

i

dT

b p