Lecture 8

Chapter 5
Chapter 6
-

Thermodynamic Web
Departure Functions
Review Equations of state (chapter 4, briefly)
Equilibrium (chemical potential)
* Pure Component
* Mixtures

Ch t 7
Chapter
- Fugacity (chemical potential fugacity equilibrium calculations)
* Vapor (overview), liquid, solids
- Activityy Coefficients [Fugacity
[ g y Coefficients (overview)]
(
)]
Chapter 8
- Phase Equilibrium
* Diagrams
* Vapor Liquid (VLE)
* Liquid Liquid (LLE)
* Solid Liquid (SLE)
Chapter 9
- Reaction Equilibria

Fugacity Coefficient (methods to calculate)

i
1.
2.
3.
a.
1.

a.

Data
Equations of State
Generalized correlations b.

Pure Fluid
Data

dP

ln i Z 1
P
0
P dP
ln i
1
RT
P
0

dP
ln i
RT P
0
P

Pure Fluid

Multicomponent system:

CO

oC, 13.79 bar

at
38
2

P [bar]
1
5
10
20

Z
0.9964
0.9805
0.9607
0.9195

data
CO
0.95
2

Fugacity Coefficient (methods to calculate)

i

a.

Pure Fluid
2.

Equations of State
See handout on website from Kyle
for Peng-Robinson
Peng Robinson EOS

Z 3 ( B 1) Z 2 ( A 3B 2 2 B ) Z ( B 3 B 2 AB ) 0

Z 1 2 B
A
ln Z 1 ln( Z B )
ln

2 2 B Z 1 2 B

CO

at 38oC, 13.79 bar

PREOS
CO
0.935
2

Fugacity Coefficient (methods to calculate)

1.
2.
3.
vdw EOS

Data
Equations of State
Generalized correlations

a.

Pure Fluid

b. Multicomponent system:i

fav
2 y a a a y b a a ab
P bmix
ba
v

ln
ln a ln
bmix
RT
RT
ya P
Peng Robinson EOS (see Kyle handout on web)
c

2 j Aij

Z 1 2 B Bi
A Bi
j 1

ln

ln i
Z 1
A
Z 1 2 B B
2 2BB

ln Z B

Fugacity Coefficient (Continued)

Fugacity Coefficient (Continued)

Fugacity Coefficient (PREOS)

c

2 j Aij

Z 1 2 B Bi
A Bi

j 1

ln i

ln
Z 1 ln Z B
A
Z 1 2 B B
2 2BB

2
Pri
1
Ai 0.45724 2 1 i 1 T r i 2

Tri
c

A i j Aij
i 1 j 1

Bi 0.07780

Pri
Tri

B i Bi
i 1

Aij A ji 1 kij Ai A j
Z 3 ( B 1) Z 2 ( A 3B 2 2 B ) Z ( B 3 B 2 AB ) 0

Fugacity Coefficient (AspenPlus Examples)

1. i for ethylene at 25oC and 40 bar

2. CO2 for CO2 in 50:50 (mole) mixture with toluene at

45oC and 40 bar

Fugacity Coefficient (multicomponent approximation)

Lewis fugacity approximation (rule)

i i
Valid near ideal solution conditions,
i.e. yi in excess ( >0.9))

Fugacity / Equilibrium (SUMMARY)

fiV fi L
1)

yi PiV xi PiL

2)

yi PiV xi i Pi satisat P.C .

3)

yi PiV xi H i

Vapor phase: good; liquid phase: good for

HC or moderate high pressures
(compressible liquid phase)

Typically used for liquid phase

fugacity calculations

Used for special cases (like gases

dissolving into liquid phase)

10

Fugacity (Liquid Phase)

fi L
1.

1.
2.
3.

Compressible liquids
Ideal and real solutions
Dissolved gases

Compressible liquids (mod high P, and hydrocarbons)

fi L xi PiL
2.

Use EOS for:

iL & Z L or L

Ideal liquid solution

fi L fi ideal xi f i ideal xi f i o

f i o Pure species fugacity

real solution

fi L i fi ideal xi i f i o

Activity coefficient

Lewis/Randall basis

fi L
id l
fi ideal

fi L

xi f i o

11

Fugacity (Liquid Phase)

real
ea solution
so u o

fi L xi i f i o

P
L

o
sat sat
f i Pi i exp
p i dP
Pisat RT

Lewis/Randall
ew s/ a da basis
bas s

at system T and P

P L

L
sat
sat
fi xi i Pi i exp i dP
Pisat RT

12

13

Fugacity (Typical Liquid Phase Models)

real
ea solution
so u o

fi L xi i Pi satisat P.C
C.

Lewis/Randall
ew s/ a da basis
bas s

i ?
real solution behaves ideally in the liquid phase then:

fi L xi Pi sat

real solution behaves non-ideally in the liquid phase then:

fi L xi i Pi sat

14

Activity Coefficient (ways to calculate)

id l
Gi E Gi Gi ideal ui uiideal
RT ln
l

Gi RT ln i
E

n
g
Gi E T
ni

Now, need models for calculating

1
1.

fi
fi

ideal

nT g E
RT ln i
ni

T , P , n j

RT ln
l 2 A
Ax12

ln 1

ln i
0
0

fi ideal

T , P , n j

g E and then can find i

22-suffix
suffix Margules (simple,
(simple symmetric) [binary]

RT ln 1 Ax22

b : i
but

fi L

A
1 x1 2
1 expp
RT

ln 2

x1

g E Ax1 x2

A
lim 1 exp
x1 0
RT

15

Activity Coefficient (2 suffix Margules model)

1..

2-suffix
su
Margules
a gu es (s
(simple,
p e, symmetric)
sy
e c) [binary]
[b a y]
Find A: take data

g E Ax1 x2

yi P xi i Pi sat

Example: binary mix of cyclohexane (a) and dodecane (b) at 39.33oC

cyclo
C 6 0.88

C12 0.86

A
lim 1 exp
x1 0
RT

Activity Coefficient (Models)

1..

2-suffix
su
Margules
a gu es (s
(simple,
p e, symmetric)
sy
e c) [binary]
[b a y]

g E Ax1 x2

Asymmetric models:
2.
3.
4.
5
5.
6.
7.

Three-suffix Margules: (additional parameter)

Van Laar: (older model but still good and easy to work with)
Wilson: (not good for liquid-liquid-equilibria)
NRTL (Non-Random-Two-Liquid;
NRTL:
(N R d
T
Li id goodd first
fi choice,
h i usually)
ll )
UNIQUAC: (UNIversal QUAsi-Chemical; also good)
UNIFAC: (only predictive model)

16

Activity Coefficient (Binary Models)

17

Koretsky, 2004

Activity Coefficient (Binary Models)

18

Activity Coefficient (Binary Models)

19

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

20

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

21

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

22

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

23

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

24

Prausnitz, et.al., 1999

25

Activity Coefficient (Binary Models)

r and q depend on
molecular size
(volume) and external
surface areas of pure
components.

Prausnitz, et.al., 1999

Activity Coefficient (Binary Models)

26

Prausnitz, et.al., 1999

27

Activity Coefficient (Example)

Temperature-composition diagram at
1.013 bar (1 atm) pressure for system:
formic acid (1) and acetic acid (2)

Prausnitz, et.al., 1999

Lecture 8
Chapter 5
Chapter 6
-

Thermodynamic Web
Departure Functions
Review Equations of state (chapter 4, briefly)
Equilibrium (chemical potential)
* Pure Component
* Mixtures

Ch t 7
Chapter
- Fugacity (chemical potential fugacity equilibrium calculations)
* Vapor (overview), liquid, solids
- Activityy Coefficients [Fugacity
[ g y Coefficients (overview)]
(
)]
Chapter 8
- Phase Equilibrium
* Diagrams
* Vapor Liquid (VLE)
* Liquid Liquid (LLE)
* Solid Liquid (SLE)
Chapter 9
- Reaction Equilibria

28