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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
................................... ....................................
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
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
dG
t
T,P
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
Problems
Calculation of Equilibrium
Constant
G o298K
H o298K
C op
H
i
o
f , 298K
C
i
G
i
o
f , 298K
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 Solid
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
n i a ik A k
#2 Step:
G ofi
ni
R T ln
i P
n
k a ik 0
k
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