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Lecture 23 Thursday 4/1/08
OCNB Explosion
Noble Prize 2007
Catalytic Steps
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
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.
Catalysts affect both
Selectivity and Yeild
Steps in a Catalytic Reaction
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.
The Adsorption Step
The Surface Reaction Step
The Rate Limiting Step:
Which Step Has the Largest
Resistance?
Octane Numbers
Catalytic Reforming
Normal Pentane Octane Number = 62
Iso-Pentane Octane Number = 95
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)
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











/
/
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

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Catalysis

  • 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
  • 3.
  • 4.
  • 5.
  • 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.
  • 8.
  • 9.
  • 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.
  • 13.
  • 15.
  • 16.
  • 17.
  • 18.
  • 19.
  • 20.
  • 21. The Rate Limiting Step: Which Step Has the Largest Resistance?
  • 22.
  • 23. Octane Numbers Catalytic Reforming Normal Pentane Octane Number = 62 Iso-Pentane Octane Number = 95
  • 24.
  • 25.
  • 26.
  • 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