CHE 3262: Thermodynamics

Class 22: March 22nd, 2013

Chapter 13: Chemical Reaction Euilibria

15

3/11,M

Analysis of VLE Data

17

3/11,M

18
19

3/13,W
3/15,F

20

3/18,M

21

3/20,W

21

3/22,F

22

4/1,M

23

4/3,W

24

4/5,F

25

4/8,M

26

4/10,W

27

4/12,F

28

4/15,M

Exam I, 17:30-19:30, Computer

Lab TBD
Go over Exam 1
Liquid Phase Properties from
Thermodynamic Data
Thermodynamic Consistency
Models for Excess Gibbs Free
Energy
Property Changes of Mixing,
Heat Effects of Mixing Processes
Enthalpy Concentration
Diagrams
Chemical Reaction Equilibria
Reaction Coordinate,
Reaction Stoichiometry
Multi Reaction Stoichiometry
Reaction Equilibrium Criteria
G0, Equilibrium Constant
Temperature Effects on
Equilibrium Constant
Equilbrium Composition and
Conversion: Gas Phase
Reactions
Equilbrium Composition and
Conversion: Gas, Liquid,
Heterogeneous Reactions
Reactions in Heterogeneous
Systems
Multireaction Equilibria, Fuel
Cells

29

4/17,W

30
31

4/19,F
4/22,M

32

4/24,W

33

4/26,F

Vapor/Liquid Equilibrium:
Gamma/Phi Formulation
BUBL P Calculations
DEW P, DEW T, BUBL T
Azeotropes, Flash Calculations
VLE from cubic equations of
state
Equilibrium and Stability

#7) 12.1, 12.3, 12.6, 12.12,

12.13, 12.16, 12.18, 12.26,
12.27, 12.29, 12.44, 12.48,
12.54 and 12.59 due 4/1

Ch. 13

#8) 13.1, 13.2, 13.3,13. 4, and

13.5, due 4/8

#9) 13.6, 13.11, 13.12, due

4/15

#10) 13.21, 13.28, 13.31,

13.33, 13.34, 13.36, 13.40,
13.41, 13.45 due 4/22

Ch. 14
#11) 14.1, 14.8, 14.15, 14.16,
and 14.24, due 5/3

Quiz 23 A: The endothermic reaction A B reaches

an equilibrium conversion of 25% in an adiabatic
steady-state flow reactor. Which of the following will
likely increase conversion?

A. Add a catalyst
B. Raise the inlet temperature
C. Use a bigger reactor
D. Remove inert from the feed
E. All of the above

G = H + TS

Quiz 23 B: The exothermic reaction A B reaches

an equilibrium conversion of 25% in an adiabatic
steady-state flow reactor. Which of the following will
likely increase conversion?

A. Add a catalyst
B. Raise the inlet temperature

C. Use a bigger reactor

D. Add an inert to the feed
E. All of the above

G = H + TS

A key concept in chemical engineering is the

difference between a thermodynamically limited
process and a kinetically limited process.

Reaction rates ARE NOT susceptible to

thermodynamic treatment.
Equilibrium conversions ARE susceptible to
thermodynamic treatment.
The purpose of Chapter 13 is to determine the
effects of TEMPERATURE, PRESSURE and
INITIAL COMPOSITION on the EQUILIBIRIUM
CONVERSION of chemical reactions.

Le Chatlier's Principle:
States that a system at
equilibrum will oppose
Ag+any
+ change
Cl- inAgCl
the
equilibrium conditions.
System: AgCl system
Stress Applied: added NH3
Observations: The addition of NH3 solution caused the
white precipitate of AgCl to disappear.
Chemical Explanation: The addition of NH3 decreased
the concentration of free silver ions in solution. This
decreased the rate of the forward reaction. As a result
the equilibrium shifted to the left. In doing so more

Le Chatlier's Principle:
States that a system at
equilibrum will oppose any
change in the equilibrium
conditions.
Ag+ + Cl- AgCl

System: AgCl system

Stress Applied: added NH3
Observations: The addition of NH3 solution caused the white
precipitate of AgCl to disappear.
Chemical Explanation: The addition of NH3 decreased the
concentration of free silver ions in solution. This decreased the rate
of the forward reaction. As a result the equilibrium shifted to the
left. In doing so more AgCl precipitate dissolved.

Le Chatlier's Principle:
States that a system at
equilibrum will oppose any
change in the equilibrium
conditions.

L V

System: single component, two-phase, liquid in equilibrium with its vapor

at given temperature
Stress Applied: Vapor is injected
Observations: Liquid will condense
Chemical Explanation: Saturation vapor pressure (and overall pressure)
of the system does not change since T does not change.
What would happen if we injected liquid? What about a two-component,
two-phase system?

The Reaction Coordinate

n1 = -1

n2 = -1

n3 = 1

n4 = 3

Reaction Coordinate = 0 at initial state

13.4

13.5

See Examples 13.1 and 13.2

Example 13.1
nu1A1 + nu2A2 --> nu3A3 + nu4A4

nu1 =
nu2 =
nu3 =
nu4 =
nu =

-1
-1
1
3
2

n10 =
n20 =
n30 =
n40 =
n0 =

2
1
1
4
8

G n
i
v
e

Mole Fractions vs Reaction Coordinate

1.0

yCH4
yH2O
yCO
yH2
Syi

0.9
yCH4
0.25
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.18
0.17
0.17
0.16
0.15
0.15
0.14
0.13
0.13
0.12
0.11
0.11
0.10

yH2O
0.13
0.12
0.11
0.10
0.10
0.09
0.08
0.07
0.07
0.06
0.06
0.05
0.04
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0.00

yCO
0.13
0.13
0.13
0.14
0.14
0.15
0.15
0.16
0.16
0.16
0.17
0.17
0.17
0.18
0.18
0.18
0.19
0.19
0.19
0.20
0.20

yH2
0.50
0.51
0.52
0.54
0.55
0.56
0.57
0.58
0.59
0.60
0.61
0.62
0.63
0.64
0.65
0.66
0.67
0.68
0.68
0.69
0.70

Syi
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

0.8
0.7
0.6

yi

e (mols)
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

0.5
0.4
0.3
0.2
0.1
0.0
0

0.2

0.4

0.6

0.8

Example 13.2
calculate number of moles of each species as a function of reaction coordinate.
n1A1 --> n2A2+ nu3A3

nu1 =
nu2 =
nu3 =

-1
1
0.5

n10 =
n20 =
n30 =

2
1
1

Moles vs Reaction Coordinate

2.5

e (mols)
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00

0.5

n1

n0 =

n2
2.00
1.95
1.90
1.85
1.80
1.75
1.70
1.65
1.60
1.55
1.50
1.45
1.40
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00

n3
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
1.80
1.85
1.90
1.95
2.00

1.00
1.03
1.05
1.08
1.10
1.13
1.15
1.18
1.20
1.23
1.25
1.28
1.30
1.33
1.35
1.38
1.40
1.43
1.45
1.48
1.50

n1
n2
n3

yH2O
0.50
0.48
0.47
0.45
0.44
0.42
0.41
0.40
0.38
0.37
0.35
0.34
0.33
0.31
0.30
0.29
0.27
0.26
0.25
0.23
0.22

yH2
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
0.34
0.35
0.36
0.37
0.38
0.39
0.40
0.41
0.42
0.43
0.44
0.44

yO2
0.25
0.25
0.26
0.26
0.27
0.27
0.28
0.28
0.29
0.29
0.29
0.30
0.30
0.31
0.31
0.31
0.32
0.32
0.33
0.33
0.33

2.0

1.5

ni

nu =

1.0

0.5

0.0
0.0

0.2

0.4

0.6

0.8

1.0

nu1A1 + nu2A2 --> nu3A3 + nu4A4

n10 =
n20 =
n30 =
n40 =
n0 =
y2

y3
0.71
0.67
0.63
0.59
0.56
0.52
0.48
0.44
0.41
0.37
0.33

2
5
0
0
7

0.9
Syi

y4
0.00
0.03
0.06
0.08
0.11
0.14
0.16
0.19
0.22
0.24
0.27

1.0

0.00
0.04
0.08
0.13
0.17
0.21
0.25
0.29
0.32
0.36
0.40

1
1
1
1
1
1
1
1
1
1
1

0.8
0.7
0.6

yi

nu1 =
-4
nu2 =
-5
nu3 =
4
nu4 =
6
nu =
1
e (mols)
y1
0
0.29
0.05
0.26
0.1
0.23
0.15
0.20
0.2
0.17
0.25
0.14
0.3
0.11
0.35
0.08
0.4
0.05
0.45
0.03
0.5
0.00

Mole Fractions vs Reaction Coordinate

Epsilon has units of moles (see
Eq 13.3). This leads to the
concept of moles of reaction.
A change in epsilon of one
y1
mole means the reaction
y2
proceeds to the extent that the
y3
change in mole number of
y4
each reactant and procuct is
equal to its stoichiometric
number. If n10=2, we need
two moles of reaction, etc.

0.5
0.4
0.3
0.2
0.1
0.0
0

0.1

0.2

0.3

0.4

0.5

e
Pr 13.1a

Ex 13.2

1
2
3
4
5

Species
CH4
H2O
CO
H2
CO2
Total

e1 (mols) e2 (mols)
0.00
0.00
0.05
0.05
0.10
0.10
0.15
0.15
0.20
0.20
0.25
0.25
0.30
0.30
0.35
0.35
0.40
0.40
0.45
0.45
0.50
0.50
0.55
0.55
0.60
0.60
0.65
0.65
0.70
0.70
0.75
0.75
0.80
0.80
0.85
0.85
0.90
0.90
0.95
0.95
1.00
1.00

ni0

nui1
3
3
1
1
1
9

yCH4
0.33
0.32
0.30
0.28
0.27
0.25
0.24
0.22
0.21
0.19
0.18
0.17
0.16
0.15
0.14
0.13
0.11
0.10
0.10
0.09
0.08

nui2
-1
-1
1
3
0
2

yH2O
0.33
0.31
0.29
0.27
0.24
0.23
0.21
0.19
0.17
0.15
0.14
0.12
0.11
0.09
0.08
0.06
0.05
0.04
0.02
0.01
0.00

-1
-2
0
4
1
2
yCO
0.11
0.11
0.12
0.12
0.12
0.13
0.13
0.13
0.13
0.13
0.14
0.14
0.14
0.14
0.14
0.15
0.15
0.15
0.15
0.15
0.15

yH2
0.11
0.15
0.18
0.21
0.24
0.28
0.30
0.33
0.36
0.38
0.41
0.43
0.46
0.48
0.50
0.52
0.54
0.56
0.58
0.60
0.62

yCO2
0.11
0.11
0.12
0.12
0.12
0.13
0.13
0.13
0.13
0.13
0.14
0.14
0.14
0.14
0.14
0.15
0.15
0.15
0.15
0.15
0.15

Syi
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

n1
3
2.9
2.8
2.7
2.6
2.5
2.4
2.3
2.2
2.1
2
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1

n2
3
2.85
2.7
2.55
2.4
2.25
2.1
1.95
1.8
1.65
1.5
1.35
1.2
1.05
0.9
0.75
0.6
0.45
0.3
0.15
0

n3
1
1.05
1.1
1.15
1.2
1.25
1.3
1.35
1.4
1.45
1.5
1.55
1.6
1.65
1.7
1.75
1.8
1.85
1.9
1.95
2

n4
1
1.35
1.7
2.05
2.4
2.75
3.1
3.45
3.8
4.15
4.5
4.85
5.2
5.55
5.9
6.25
6.6
6.95
7.3
7.65
8

n5
1
1.05
1.1
1.15
1.2
1.25
1.3
1.35
1.4
1.45
1.5
1.55
1.6
1.65
1.7
1.75
1.8
1.85
1.9
1.95
2

Sn
9
9.2
9.4
9.6
9.8
10
10.2
10.4
10.6
10.8
11
11.2
11.4
11.6
11.8
12
12.2
12.4
12.6
12.8
13

n
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
2.6
2.8
3
3.2
3.4
3.6
3.8
4 Ex 13.3

1
2
3
4
5

Species ni0 nui1 nui2

CH4
3
-1
-1
H2O
3
-1
-2
CO
1
1
0
H2
1
3
4
CO2
1
0
1
Total
9
2
2

Methane
Only

e1/e2
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95

0.00
0.33
0.32
0.32
0.31
0.30
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19

0.05
0.32
0.32
0.31
0.30
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18

0.10
0.32
0.31
0.30
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18

0.15
0.31
0.30
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17

0.20
0.30
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16

0.25
0.29
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16

0.30
0.28
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15

0.35
0.27
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15

0.40
0.27
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14

0.45
0.26
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14

0.50
0.25
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13

0.55
0.24
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13

0.60
0.24
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12

0.65
0.23
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11

0.70
0.22
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11

0.75
0.21
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10

0.80
0.21
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10

0.85
0.20
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.10

0.90
0.19
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.10
0.09

0.95
0.19
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.10
0.09
0.09

1.00
0.18
0.18
0.17
0.16
0.16
0.15
0.15
0.14
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.10
0.09
0.09
0.08

0.00

0.70
0.80
0.90
1.00

0.60

0.50

0.40

0.30

0.20

0.10

1.00
0.00

0.90

0.80

0.70

0.60

0.50

0.40

eps1

0.30

0.20

0.10

0.00

Mole Fraction CH4 vs eps1 and eps2

0.35

0.30

0.25

0.20

yCH4
0.15

0.10

0.05

eps2

1
2
3
4
5

Species
ni0
C2H4
O2
((CH2)2)O
CO2
H2O
Total

e1 (mols) e2 (mols)
0.00
0.00
0.05
0.05
0.10
0.10
0.15
0.15
0.20
0.20
0.25
0.25
0.30
0.30
0.35
0.35
0.40
0.40
0.45
0.45
0.50
0.50
0.55
0.55
0.60
0.60
0.65
0.65
0.70
0.70
0.75
0.75
0.80
0.80
0.85
0.85
0.86
0.86

yCH4
0.40
0.38
0.36
0.35
0.33
0.31
0.29
0.27
0.25
0.23
0.21
0.19
0.17
0.15
0.13
0.11
0.09
0.07
0.06

nui1
2
3
0
0
0
5

nui2
-1
-0.5
1
0
0
-0.5

yH2O
0.60
0.57
0.54
0.50
0.47
0.44
0.40
0.37
0.33
0.30
0.26
0.23
0.19
0.16
0.12
0.08
0.04
0.01
0.00

-1
-3
0
2
2
0
yCO
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.19
0.19

yH2
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.15
0.17
0.19
0.21
0.23
0.26
0.28
0.30
0.32
0.35
0.37
0.38

yCO2
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.15
0.17
0.19
0.21
0.23
0.26
0.28
0.30
0.32
0.35
0.37
0.38

Syi
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

n1
2
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.28

n2
3
2.825
2.65
2.475
2.3
2.125
1.95
1.775
1.6
1.425
1.25
1.075
0.9
0.725
0.55
0.375
0.2
0.025
-0.01

n3
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.86

n4
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.72

n5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.72

Sn
5
4.975
4.95
4.925
4.9
4.875
4.85
4.825
4.8
4.775
4.75
4.725
4.7
4.675
4.65
4.625
4.6
4.575
4.57

n
0
-0.03
-0.05
-0.08
-0.1
-0.13
-0.15
-0.18
-0.2
-0.23
-0.25
-0.28
-0.3
-0.33
-0.35
-0.38
-0.4
-0.43
-0.43

Pr 13.2

1
2
3
4
5

Species
CO2
H2O
CH3OH
H2O
CO
Total

e1 (mols) e2 (mols)
0.00
0.00
0.05
0.05
0.10
0.10
0.15
0.15
0.20
0.20
0.25
0.25
0.30
0.30
0.35
0.35
0.40
0.40
0.45
0.45
0.50
0.50
0.55
0.55
0.60
0.60
0.65
0.65
0.70
0.70
0.75
0.75
0.80
0.80
0.85
0.85
0.90
0.90
0.95
0.95
1.00
1.00

ni0

nui1
2
5
0
0
1
8

yCH4
0.25
0.24
0.23
0.22
0.21
0.20
0.19
0.18
0.17
0.15
0.14
0.13
0.12
0.10
0.09
0.08
0.06
0.05
0.03
0.02
0.00

nui2
-1
-3
1
1
0
-2

yH2O
0.63
0.61
0.59
0.57
0.55
0.53
0.51
0.49
0.47
0.45
0.43
0.41
0.38
0.36
0.33
0.31
0.28
0.25
0.23
0.20
0.17

-1
-1
0
1
1
0
yCO
0.00
0.01
0.01
0.02
0.03
0.03
0.04
0.05
0.06
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.13
0.15
0.16
0.17

yH2
0.00
0.01
0.03
0.04
0.05
0.07
0.08
0.10
0.11
0.13
0.14
0.16
0.18
0.19
0.21
0.23
0.25
0.27
0.29
0.31
0.33

yCO2
0.13
0.13
0.14
0.15
0.16
0.17
0.18
0.18
0.19
0.20
0.21
0.22
0.24
0.25
0.26
0.27
0.28
0.29
0.31
0.32
0.33

Syi
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

n1
2
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

n2
5
4.8
4.6
4.4
4.2
4
3.8
3.6
3.4
3.2
3
2.8
2.6
2.4
2.2
2
1.8
1.6
1.4
1.2
1

n3
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

n4
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2

n5
1
1.05
1.1
1.15
1.2
1.25
1.3
1.35
1.4
1.45
1.5
1.55
1.6
1.65
1.7
1.75
1.8
1.85
1.9
1.95
2

Sn
8
7.9
7.8
7.7
7.6
7.5
7.4
7.3
7.2
7.1
7
6.9
6.8
6.7
6.6
6.5
6.4
6.3
6.2
6.1
6

n
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1
-1.1
-1.2
-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
-1.9
-2

Pr 13.3

Criteria for
Equilibrium:
Gt = min

dGt/de = 0

Pr 13.4

1
2
3
4

Species
H2
CO2
H2O
CO
Totals
eps =
T=
G=
R=

nui

eps

G
-208492.9
-208627
-208662
-208675
-208638
-208518
-208314

0.35
0.4
0.425
0.45309
0.5
0.55
0.6

ni0

-1
-1
1
1
0
0.425
1000 K
-208661.6
8.314 J/mol-K

yi
1
1
0
0
2

0.2875
0.2875
0.2125
0.2125
1

G0f (J/mol)
0
-395790
-192420
-200240

G vs eps at 1000 K

-208250
-208300 0
-208350
-208400
-208450
-208500
-208550
-208600
-208650
-208700

0.1

0.2

0.3

0.4

0.5

0.6

0.7

eps

Pr 13.4

For non-ideal gases, we defined the Gibbs free energy by introducing

the concept of fugacity.
For pure species i in its standard state at the same temperature:

Criterion for Chemical

Equilibrium (13.8)
Combine to eliminate mi
for the equilibrium state
of a chemical reaction.

Eqs 13.10 13.12

The fugacity ratios connect the equilibrium state

of interest and the standard states of the
individual species (see section 13.5).

(13.14)

More rigorous approach:

T

= -ln K

-ln K =

(see eq, 5.15)

Same as ICPS

-ln K =

Index

Species
1 C2H4
2 H2O
3 C2H5OH
T=
145
T=
418.15
T0 =
298.15
tau =
1.402481972
R=
8.314

A =
B =
C =
D =
0
H 298 =
G0298 =
T/K
298.15
418.15
523.15
593.15
1273.15

nui

Ai
-1
-1
1

Bi
Ci
Di
1.44E-02 -4.39E-06
0
1.45E-03
0 1.21E+04
2.00E-02 -6.00E-06
0

K
K

IDCPH =
IDCPS =

-23.12095 eq 13.19
-0.069235 eq 5.15

J/mol-K

G0T =
ln K =
K=

1.935548
-1.935548
0.144345

eq 13.18

-1.376E+00
4.157E-03
-1.610E-06
-1.210E+04
-4.579E+04 J/mol
-8.378E+03
1/T
0.003354016
0.002391486
0.001911498
0.001685914
0.000785453

1.424
3.47
3.518

H0f298
G0f298
(J/mol)
(J/mol)
52510
68460
-241818 -2.29E+05
-235100
-168490

J/mol
tau
1
1.40248
1.754637
1.989435
4.270166

K0 = 29.36593 eq 13.21
K1 = 0.004984 eq 13.22
K2 = 0.986155 eq 13.23
K=
K0
29.36593
29.36593
29.36593
29.36593
29.36593

0.144345
K1
1
0.004984
0.000354
0.000102
7.18E-07

eq 13.20
K2
1
0.986155
0.977841
0.979368
1.213823

K
29.36593
0.144345
0.010176
0.002942
2.56E-05

ln K
3.379835
-1.935548
-4.587704
-5.828616
-10.57357

Example 13.4

Temperature Dependence of K
6
4
2

lnK

0
-2

0.0005

0.001

0.0015

0.002

-4
-6
-8
-10
-12

1/T (K-1)

0.0025

0.003

0.0035

0.004