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Lecture 15
Introduction to Catalysis
William F. Schneider
Department of Chemical and Biomolecular Engineering
Department of Chemistry and Biochemistry
University of Notre Dame
wschneider@nd.edu
Fall Semester 2005
k(T) = k0e-Ea/RT
Ea′ < Ea
k0′ > k0
Ea k′ > k Ea′
ΔG = ΔG
A+B A+B+
ΔG catalyst ΔG
C C + catalyst
uncatalyzed catalyzed
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
‡
H O
H2C C
O CH3 OH
C C
CH3 CH3 CH2 CH3
‡
propanone propenol
propenol
propanone
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
O−
C + H2O
CH2 CH3
OH− −OH−
Base catalyzed
O OH
rate = k[OH−][acetone]
C C
CH3 CH3 CH2 CH3
propanone propenol
‡ ‡
propenol
intermediate
propanone
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
propenol
different
propanone intermediate
propenol
O OH
propanone rate = k[H3O+][acetone]
C C
Acid catalyzed
CH3 CH3 CH2 CH3
H3O+ −H3O+
OH
C
+
CH3 CH3
+ H2O
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
Difficult to generalize
Termination:
beyond organic
transformations
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
10 Å
100 Å
Haber-Bosch process
N2 + 3 H2 → 2 NH3
Fe/Ru catalysts, high pressure and temperature
Critical for fertilizer and nitric acid production
Fischer-Tropsch chemistry
n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels
Fe/Co catalysts
Source of fuel for Axis in WWII
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
“Three-way” Catalyst
CO CO2
HC CO2 + H2O
NOx N2
Monolith reactor
M M M
support
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
Mass-based rate
r′ = moles / masscat · time
r′ = r / ρcat
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
1.48
O O
Physisorbed CO2 C
CO2 -2 kcal mol-1 GGA
2-
: :
:O:surf
1.51
1.77 2.10
Mg Chemisorbed SO2
SO2 (“sulfite”)
O -25 kcal mol-1 GGA
O O
:
S
2-
: :
:O:surf
2.60
1.45 1.48
SO3 Chemisorbed SO3
1.66 2.12 (“sulfate”)
-50 kcal mol-1 GGA
O
O O
MgO(001) supercell S
2-
: :
Schneider, Li, and Hass, J. Phys. Chem. B 2001, 105, 6972 :O:surf
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● 2.58
○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
θj = 1/6
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
(torr g /mol)
2 150
(mol/g )
cat
cat
1.8
1.6
CO CO
CO
P /n
n
0.8 50
200
100 300 400 100 200 300 400
Pressure (torr) Pressure (torr)
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
cz ΔHads/ΔHcond
V
Vmono (1 z )(1 (1 c) z )
( H ads H cond ) ΔHcond
z P , ce RT
Pvap
ΔHads
Solid Surface
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○