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What is catalysis?
J.W. Niemantsverdriet
Schuit Institute of Catalysis
Eindhoven University of Technology
Lecture presented at
Mumbai University Institute of Chemical Technology
February 2003
What is catalysis
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
A P
B
separation
catalyst
P
bonding catalyst
A
reaction
B
catalyst
P
potential energy
A + B
A
B
cataly st
P
A B
cataly st P cataly st
cataly st
reaction coordinate
What is catalysis
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
Langmuir - Hinshelwood Kinetics
1915 Langmuir:
Adsorption Isotherm
1927 Hinshelwood:
Kinetics of Catalytic
Reactions
Coverages:
1
θ A = K A pA θ * θB = KB pB θ* θ* = 1 + K p + K p
A A B B
N* k KAKB pA pB
Reaction rate: r=
(1 + KA pA + KB pB )2
Irving Langmuir
(1881 - 1957)
KA [A]
0A =
1 + KA [A]
Rate of reaction, Activation energy, Order of reaction:
N* k KAKB pA pB
r=
(1 + KA pA + KB pB )2
∂ ln r 2 ∂ ln r
E app
= −R = RT
∂(1 / T ) ∂T
a
= E rds
a + (1 − 2θ A ) ∆H A + (1 − 2θ B ) ∆H B
∂ ln r ∂ ln r
nA = = pA = 1 − 2θ A
∂ ln p A ∂ pA
Rate of a Catalytic Reaction: Eads(A) = Eads(B) = 125 kJ/mol
1,0
rate
0.8
0,8
0.6
0,6 θB θA θA
0.4
0,4
0.2 θB
θ,
0,2
0.0
0,0
θ*
-1,0 -0,8 -0,6 -0,4 -0,2 0,0 0,2 0,4 0,6 0,8
0.1 1.0 10
reaction order
positive in pA
pA/pB reaction order
negative in pA
negative in pB positive in pB
Rate of a Catalytic Reaction: Eads (A) = 135 kJ/mol
Eads (B) = 125 kJ/mol
Temperature Dependence s(B) pB = 10 s(A) pA
Eact = 50 kJ/mol
1,0
θ*
normalized rate
0,8 θA rate
0,6
0,4
0,2
θB
θ,
0,0
100 300 500 700 900
T (K)
reaction order reaction order
negative in pA positive in pA and pB
positive in pB
The Sabatier Effect
catalytic activity
optimum interaction
catalyst - adsorbate:
• not too strong
• not too weak
Cr Mn Fe Co Ni Cu
Mo Tc Ru Rh Pd Ag
W Re Os Ir Pt Au
CO CO2
catalyst
adsorption reaction desorption
anti
bonding
bonding
atomic molecular atomic
orbital orbitals orbital
strong weak no bond
and about . . . . .
Bonding in Metals
4p
energy
sp - band
4s
3d
d-band
-
distance
10
5d-series
Cohesive Energy (eV)
8 EF
6
4d-series
4
2
3d-series
0
Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Ba La Hf Ta W Re Os Ir Pt Au Hg
Atomic Adsorption in the ‘Resonant Level Model’
(the simplest description)
Core level 1
Core level 2
EF
EF
EF
σ* σ*
EF
EF 1s 1s 1s 1s
σ σ
EF
EF d-band
bonding bonding
s-band
Evac antibonding
σ*
antibonding
EF 1s 1s
bonding
bonding
Evac antibonding
2π*
antibonding
EF
bonding
5σ
bonding
“back donation”
“relieved repulsion” binds molecule to surface
favors on-top adsorption weakens internal CO bond!
often called “donation” favors multiple coordination
a catalyst breaks bonds……...
How?
Atoms prefer high coordination sites
hcp fcc top bridge
Carbon
on
Rh(111)
1.99 eV
0.67 eV
0.00 eV 0.24 eV
2.13 eV
0.72 eV
0.00 eV 0.14 eV
∆Hads (AB)
–150 kJ/mol
Eact
75 kJ/mol
Driving
Force
∆Hads (A+B)
–600 kJ/mol
Trends in chemisorption
Strong atomic adsorption
Cr Mn Fe Co Ni Cu
585 564
Mo Tc Ru Rh Pd Ag
543
W Re Os Ir Pt Au
531 531 N/Metal, kJ/mo
Weaker adsorption
Evac Evac
antibonding antibonding
EF
EF d-band
bonding bonding
s-band
δEact Rh
∆Hads (AB)
Cr Mn Fe Co Ni Cu
Mo Tc Ru Rh Pd Ag
W Re Os Ir Pt Au
no dissociation
δEact Rh
∆Hads (AB)
energy
sp - band
Fermi
level d-band
energy
energy sp - band
Fermi
level d-band
Evac
antibonding
antibonding
EF
r ong er
bonding st !
bonding
bond
What is catalysis?
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
If you can explain catalysis along
these three lines you have
a pretty good understanding of
what catalysis on metals means.