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Chapt12summpt2 PDF
Chapt12summpt2 PDF
1
Turnover numbers
CH3COOH CH3OH
HI
H2O
CH3COI CH3I
[Rh(CO)2I2]-
C
O CH3
I I I I
H3C Rh Rh
C I I
C
O C C
O
O O
CO
Figure 12.1 A schematic of the catalytic cycle for Acetic acid
production via the Monsanto process.
2
A +H2 B +1/2 O 2
H H
O O O O O O O O O O O
+ 1/2 O 2
+ H2
- H 2O
- H 2O
H H H H
O O O O O O O O O H O H O
Figure 5.10 Catalytic cycles for the production of water a) via disproportion of
OH groups, b) via the reaction OH(ad)+H)ad)→H2O.
B A A B A B
B B B
B A B A A A A A
B B B
A B A B A B
A A A
B B B
A A A
3
RA
TN =
NS
(12.119)
Key plot:
Dehydrogenation
2 Hydrogenation
-1
10
Turnover Number, sec
0 Silicon
10
Deposition
GaAs
Deposition
-2
10
-4
10 Olefin
Isomerization
Alkane
-6
Hydrogenolysis
10 Cyclization
200 400 600 800 1000 1200 1400
Reaction Temperature, K
4
Next topic why catalytic kinetics weird?
450 K 450 K
2
12
10 440 K
440 K
425 K
410 K
415 K
390 K
11
10 -8 -7 -6 -8 -7 -6
10 10 10 10 10 10
CO pressure, torr O 2 pressure, torr
Figure 2.15 The influence of the CO pressure on the rate of CO oxidation on
Rh(111). Data of Schwartz, Schmidt, and Fisher.
5
PO =2.5E-8 torr PCO=2.E-7 torr
2
Rate, Molecules/cm 2-sec
1E+13
C
1E+12
F
B E
D
1E+11
A
400 600 800 400 600 800
Temperature, K Temperature, K
6
Physical interpretation:
AAd º Cad
4
5
Cad º C + S
6
(12.121)
S + B B ad
8
(12.122)
8
Next use the steady state approximation to
derive an equation for the production rate of
Cad (this must be equal to the production rate
of C).
rC = k 3[A ad ] − k 4 [C ad ]
(12.123)
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People usually ignore reactions 3 and 4
since their rates very low rates
compared to the other reactions.
k
[A ad ] = 1 PA [S]
k2
(12.126)
k6
[C ad ] = PC [S]
k5
(12.127)
Similarly for B
k8
[ ad ]
B = PB [S]
k7
(12.128)
10
Rearranging Equations (12.126), (12.127)
and (12.128) yields:
[A ad ] k1
=
PA [S] k 2
(12.129)
[Bad ] k 8
=
PB [S] k 7
(12.130)
[C ad ] = k 6
Pc [S] k 5
(12.131)
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Equations (12.129) and (12.130) imply that
there is an equilibrium in the reactions:
1
A + S º Aad
2
8
B + S ºBad
7
C + S ºC ad
5
(12.132)
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If sites are conserved
S 0 = [S] + [A ad ] + [Bad ] + [ C ad ]
(12.133)
S0
[S] =
k1 k8 k6
1+ PA + PB + PC
k2 k7 k5
(12.134)
13
Substituting Equation (12.134) into
Equations (12.126) and (12.127) yields:
k1
PA S 0
k2
[A ad ] =
k k k
1+ 1 PA + 8 PB + 6 PC
k2 k7 k5
(12.135)
k6
PC S 0
k5
[C ad ] =
k k k6
1+ 1 PA + 8 PB + PC
k2 k7 k5
(12.136)
k1
KA =
k2
(12.137)
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Similarly, the equilibrium constants for the
adsorption of B, and C are given by:
k8
KB =
k7
(12.138)
k
KC = 6
k5
(12.139)
K A PA S 0
[A ad ] =
1 + K A PA + K B PB + K C PC
(12.140)
K C PCS 0
[C ad ] =
1 + K A PA + K B PB + K C PC
(12.141)
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Substituting Equations (12.140) and
(12.141) into Equation (12.123) yields:
k 3 K A PA S 0 − k 4 K C PC S 0
r=
1 + K A PA + K B PB + K C PC
(12.142)
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Qualitative behavior for A + B ⇒ products:
2.5E+14
1.5E+14
1.0E+14
5.0E+13
0.0E+0
0 10 20 30 40 50
PA
13
10
Rate, Molecules/cm -sec
450 K 450 K
2
12
10 440 K
440 K
425 K
410 K
415 K
390 K
11
10 -8 -7 -6 -8 -7 -6
10 10 10 10 10 10
CO pressure, torr O 2 pressure, torr
Figure 2.15 The influence of the CO pressure on the rate of CO oxidation on
Rh(111). Data of Schwartz, Schmidt, and Fisher.
17
Qualitative behavior for A⇒C
2.0E-8
PB =0
1.0E-8
5.0E-9 PB =25
0.0E+0
0 10 20 30 40 50
PA
1E+20
Rate, Molecules/cm 2-sec
1670 K 1270 K
1E+19
1070 K
1E+18 870 K
770 K
1E+17
1E+16
0.01 0.1 1 10 100
Ammonia pressure, torr
18
Langmuir-Hinshelwood-Hougan-Watson
rate laws
19
Example:
S + A ⇒ A ad (1)
S + B ⇒ Bad (2)
A ad + Bad ⇒ C + 2S (3)
(12.157)
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My solution
rC = k3[Aad][Bad] (1)
21
Combining equations (4) and (7)
K1K 2 k 3 PA PB (So )
2
rC = (8)
(1 + K1PA + K 2 PB )2
22
Next what does this look like?
2.5E+14
1.5E+14
1.0E+14
5.0E+13
0.0E+0
0 10 20 30 40 50
PA
13
10
Rate, Molecules/cm -sec
450 K 450 K
2
12
10 440 K
440 K
425 K
410 K
415 K
390 K
11
10 -8 -7 -6 -8 -7 -6
10 10 10 10 10 10
CO pressure, torr O 2 pressure, torr
Figure 2.15 The influence of the CO pressure on the rate of CO oxidation on
Rh(111). Data of Schwartz, Schmidt, and Fisher.
23
Discussion problem:
A⇒C
(12.120)
1
S + A º Aad
2
AAd º Cad
4
Cad º C + S
6
(12.121)
rC Ad = k 3[A ad ] − k 4 [C ad ]
(12.123)
1.5E-8
1.0E-8
5.0E-9 PB =25
0.0E+0
0 10 20 30 40 50
PA
25
1E+20
1E+18 870 K
770 K
1E+17
1E+16
0.01 0.1 1 10 100
0 Ammonia pressure, torr
26
Summary:
28
Mass transfer control is good:
- design pore structure to pass desired
products much faster than undesired
products.
Cavity
H
Diffusion
C
H
H
C
Channel
H
H
H
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Equations for mass transfer limitations
Reaction Rate
Φp =
Diffusion Rate
Derive equation:
30
Consider a spherical catalyst particle
Center of Edge of
Pellet Pellet
0.8
Concentration
Avg conc in pellet Gas
0.6 Phase
0.4
0.2
Conc in pellet
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Distance from the center of the pellet
Solution:
with
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yP k A
ΦP =
3 De
1 1 1
ηe = −
Φ P tanh (3Φ P ) 3Φ P
10
Mass Transfer
1
Factor
0.1
0.01
0.001
0.01 0.1 1 10 100
Thele Parameter, ΦP
A plot of the mass transfer factor versus the Thiele parameter for diffusion in a porous catalyst
pellet.
32
The mass transfer factor does not
measure the effectiveness of a catalyst.
Good catalysts can have low mass transfer
factors while bad catalysts can have high
mass transfer factors. Generally if a catalyst
is not speeding up the reaction very much
the Thiele parameter will be small, which
means that according to the Figure the mass
transfer factor will be close to unity. Thus, a
bad catalyst can have a large mass transfer
factor.
33
Actual equations not useful - never know
De, but ideas useful.
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