catalysis course

1. Lecture 23 Thursday 4/1/08
OCNB Explosion
Noble Prize 2007
Catalytic Steps

2. pW
W
pB
B
pA
A
rx
A
C
N
C
N
C
N
DH
V
r
T
T
UA
dt
dT





0
0
0 )
)(
(
)
(
p
r
g
NC
Q
Q
dt
dT 

9:55
t = 0
10:40 10:50 midnight 12:18
Isothermal
Operation
Cooling Restored
Qr = 0
200
175
400
Temperature
o
C
Temperature-time trajectory
fuse

6. Catalysts and Catalysis
A Catalyst is a substance that affects the
rate of chemical reaction but emerges
from the process unchanged.
Catalysis is the occurrence, study, and use
of catalysts and catalytic processes.
Approximately 1/3 of the GNP of materials
produced in the U.S. involves a catalytic
process.

7. Catalysts affect both
Selectivity and Yeild

10. Steps in a Catalytic Reaction

11. Active Site
• Reactions are not catalyzed over the
entire surface but only at certain active
sites or centers that result from
unsaturated atoms in the surface.
• An active site is a point on the surface
that can form strong chemical bonds with
an adsorbed atom or molecule.

12. The Adsorption Step

14. The Surface Reaction Step

21. The Rate Limiting Step:
Which Step Has the Largest
Resistance?

23. Octane Numbers
Catalytic Reforming
Normal Pentane Octane Number = 62
Iso-Pentane Octane Number = 95

27. Intro to Catalysis
Reforming catalyst –
Algorithm
1) Postulate a mechanism
2) Postulate a rate-limiting step
3) Express Ci·s in terms of partial pressures
4) Site balance (Total number of sites constant)
5) Derive rate law
6) Evaluate parameters
12
5
2
10
5
10
5
10
5
2
10
5
12
5
C
-
c
C
step)
(slow
C
C
-
n
C
C
-
n
pentane
-
c
pentane
-
n
5
2
H
H
H
c
H
c
H
H
H
n
H
Pt
O
Al
Pt






 






Pt (sputtered on)
Al2O5 (scaffold)

28. CV=concentration of vacant sites
Postulate a mechanism: (single site)
In 75% of heterogeneous catalysis, surface reaction is the slow step
S
I
S
I
S
I
S
N
S
N
S
N









 
 
 
 
V
I
I
S
I
D
DI
V
I
S
I
D
D
N
S
S
I
S
N
S
S
N
N
A
N
N
S
N
V
V
N
ADN
S
N
N
V
N
N
N
C
P
k
C
k
k
C
P
C
k
r
r
k
C
C
k
r
r
k
k
k
k
C
C
P
k
r
C
k
C
P
k
r

























/
/
/
/
'
'
S
I
S
I
S
I
S
N
S
N
S
N








  
 
 
V
I
I
S
I
D
D
S
S
I
S
N
S
S
N
S
N
V
N
N
AD
C
P
K
C
k
r
k
C
C
k
r
k
C
C
P
k
r











/
/

29. V
I
I
S
I
V
I
I
S
I
D
D
V
N
N
S
N
N
S
N
V
N
N
AD
C
k
P
C
C
P
k
C
k
r
C
k
P
C
k
C
C
P
k
r












0
/
/
0
/
 
  V
D
I
N
N
S
S
V
S
I
D
N
N
S
S
N
C
k
P
P
k
k
r
C
k
P
k
P
k
k
r
r
/
/







Site Balance:
Is this consistent with the data?
Linear when PNi0 is low
Low slope when PNi0 is large
0
0
0
1
0
@
Ni
Ni
Ni
I
kP
kP
r
P




Consistent!!
PNi0
rNi0
 
 
I
I
N
N
P
I
N
k
T
S
N
S
N
I
I
N
N
V
T
S
I
S
N
V
T
P
k
P
k
k
P
P
C
k
k
r
r
P
K
P
k
C
C
C
C
C
C











 

1
/
1
'





I
I
N
N
T
V
P
k
P
k
C
C



1