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TKM 406 Termodinamika Teknik

Kimia 2

Chemical Equilibria

Reaction Coordinate
1 A 1 2 A 2 ...... 3 A 3 3 A 3 ......

CH 4 H 2 O CO 3 H 2
CH 4 1

H 2O 1

CO 1

H 2 3

dn1 dn 2 dn 3 dn 4
dn i

.....
d
1
2
3
4
i

dn CH 4
1

dn H 2O
1

dn CO dn H 2
dn i

.....
d
1
3
i

Reaction Coordinate
n i n i0 i
yi

n i n i0 i

n
n0

n n0
n

ni

n0

n i0

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:
n CH 4 ,0 2

n H 2 O, 0 1

n CO,0 1

n H 2 ,0 4

n 0 n CH 4 ,0 n H 2O,0 n CO,0 n H 2 ,0 2 1 1 4 8
n CH 4 2

n H 2O 1

n CO 1

n H2 4 3

CH 4 H 2O CO H 2 1 1 1 3 2
n n CH 4 n H 2O n CO n H 2 8 2
y CH 4

2
8 2

y H 2O

1
8 2

y CO

1
8 2

y H2

4 3
8 2

Reaction Coordinate

Reaction Coordinate: Multiple


Reactions
1 1 A1,1 2 1 A 2,1 ...... 3 1 A 3,1 3 1 A 3,1 ......
1 2 A1,2 2 2 A 2,2 ...... 3 2 A 3,2 3 2 A 3,2 ......

................................... ....................................
1 j A1, j 2 j A 2, j ...... 3 j A 3, j 3 j A 3, j ......

CH 4 H 2 O CO 3 H 2
CH 4 2 H 2 O CO 2 4 H 2

Reaction Coordinate: Multiple


Reactions
dn1,1
1,1
dn1,2
1,2

dn1, j
1, j

dn CH 4 ,1
1
dn CH 4 ,2
1

dn 2,1
2,1
dn 2,2
2,2

dn 2, j
2, j

dn H 2O,1
1
dn H 2O,2
2

dn 3,1
3,1
dn 3,2
3,2

dn 3, j
3, j

dn CO,1
1

4,1
dn 4,2
4, 2

dn 4, j

dn CO 2 ,2
1

dn 4,1

4, j

.....
.....

.....

dn H 2 ,1
3

i,1
dn i,2
i, 2

dn i, j
i, j

.....

dn H 2 ,2
4

dn i,1

d1
d 2

d j

dn i,1
i,1

.....

d1

dn i,2
i, 2

d 2

Reaction Coordinate
n i n i0

i, j j
j

n i0

yi

ni

n
n0

i, j j
j

1, j j
j

n n0
n

1, j j

ni

n0

n i0

i, j
i

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:

y CH 4

2 1 2
8 2 1 2 2

y H 2O

y CO 2

2
8 2 1 2 2

y H2

1 1 2 2
8 2 1 2 2

4 3 1 4 2
8 2 1 2 2

y CO

1 1
8 2 1 2 2

Reaction Coordinate

Reaction Coordinate &


Equilibrium Condition

dG
t

T,P

Reaction Coordinate &


Equilibrium Condition (Cont)

Method of Equilibrium Constant


K

For gases:

(a i )

exp

i G i 0

R T

(f i )

CH 4 H 2 O CO 3 H 2

K fCH 4

fH 2O

K K y K P
For ideal gases:

K K y P

f CO fH 2

Method of
Equilibriu
m
Constant

Problems

Problem Hint: Different Way


Leads to The Same Results

Problems

Calculation of Equilibrium
Constant
G o298K

H o298K

C op

H
i

o
f , 298K

C
i

G
i

o
f , 298K

G o298K R 298 ln K 298

o
p

H T H o298

C op dT

298

d ln K H T

dT
R T2

ln K T

H T

d ln K R T 2 dT

ln K 298 K

G f ( 298K )

G f ( 298K )

G f

( 298K )

G f

( 298K )

H f

( 298K )

H f

( 298K )

H f

( 298K )

H f

( 298K )

Heat Capacity Data Gases

Heat Capacity Data Gases

Heat
Capacity
Data Solid

Heat Capacity Data - Liquid

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Multiple Reactions
A bed of coal (assume pure carbon) in a coal
gasifier is fed with steam and air and produce a
gas stream containing H2, CO, O2, H2O, CO2, and
N2. If the feed to the gasifier consists of 1 mol of
steam and 2.38 mol of air, calculate the
equilibrium composition of the gas stream at P
= 20 bar and T = 1500K

Multiple Reactions

Problems

Problems

Problems

Lagrange Multiplier for


Complex Reaction
First Step: Atomic Balances

n i a ik A k

#2 Step:

G ofi

ni

R T ln
i P
n

No. of eqn = no. of


involved atom

k a ik 0
k

No. of eqn = no. of


species involved
Use Computer to Solve All The Equation Simultaneously.

Problem
Calculate the equilibrium composition at 1000 K
and 1 bar of a gas-phase system containing the
species CH4, H2O, CO, CO2, and H2. In the initial
unreacted state ther are present 2 mol of CH4
and 3 mol of H2O. Assume ideal gases.
At 1000 K:

G of CH 19720 J mol -1
4

G of H

2O

192420 J mol -1

G of CO 200240 J mol -1
G of CO 395790 J mol -1
2