Physical Chemistry

of
Heterogeneous Catalysis

Prof. Kamal M.S. Khalil

Chapter 1
Introduction
What is Catalysis?
a phenomenon in which a small quantity of a
substance (the catalyst) increases the rate of a
chemical reaction without being consumed

A P
B
separation
Catalysis is a cycle of
elementary steps (at
catalyst least three); catalytic
P sites are regenerated
bonding catalyst

reaction
A B
catalyst
Catalyst is a complicated surface
Multiple length and time scales
Catalysis is a cycle…

A P
B
separation

catalyst
P
bonding catalyst

reaction
A B
catalyst
The Arrhenius Equation
k
+
A B AB

d [AB]
r = = k [A][B]
dt

- Eact /RT
k = ve
E Svante
Arrhenius
+ Eact 1859 - 1927
Nobel Prize 1903

reaction parameter
Energy profile of a catalytic reaction

non-catalytic
reaction

non-catalytic
E energy barrier
energy barrier

reaction

adsorption
desorption

reaction coordinate
Energy barrier of the catalytic route is much lower.
 The energy diagram illustrates :

1. The catalyst offers an alternative reaction path, which is

more complex, but energetically much more favorable.
2. The activation energy of the catalytic reaction is smaller
than that of the uncatalyzed reaction; hence, the rate of
the catalytic reaction is much higher.
3. The overall change in free energy for the catalytic
reaction equals that of the uncatalyzed reaction. Hence,
the catalyst does not affect the equilibrium constant for
the overall reaction of A + B to P.
4. Thus, if a reaction is thermodynamically unfavorable, a
catalyst cannot change this situation.
5. A catalyst changes the kinetics but not the
thermodynamics of the reaction.
 Cases in which the catalyst will not be
successful with reactants
1. If the bonding between reactants and catalyst is too weak, there
will not be any conversion into products.
2. If the bond between the catalyst and one of the reactants, say A,
is too strong, the catalyst will be occupied with A, and no space
for B to interact.
3. If A and B both form strong bonds with the catalyst, the
intermediate situation with A or B on the catalyst may be so
stable that reaction becomes unlikely.
4. In terms of Fig. 1.2, the second level lies so deep that the
activation energy to form P on the catalyst becomes too high.
The catalyst is poisoned by the reactant(s).
5. If the product P too strongly bound to the catalyst this prevent
separation to occur. The catalyst is poisoned by the product.
Catalysts forms, mediums, preparation and
characterization

Catalyst Forms Catalysts come in a multitude of forms

• atoms and molecules, and in large structures such as zeolites or
enzymes.

Catalyst mediums Catalysts may be employed in various mediums

• in liquids, gases or at the surface of solids.

Preparation
Characterization Preparation of a catalyst in the optimum form
• Studying its precise composition and shape are an important
specialism
 The sub disciplines in catalysis:

There are three sub disciplines in catalysis:

Homogeneous

Heterogeneous

Bio catalysis.
 Homogeneous Catalysis
In homogeneous catalysis, both the catalyst and the
reactants are in the same phase
i.e. all are molecules in the gas phase, or, more commonly,
in the liquid phase.
Example: Ozone in the atmosphere decomposes, among other routes,
via a reaction with chlorine atoms:
Cl + O3 → ClO3
ClO3 → ClO + O2
ClO + O → Cl + O2
or overall
O3 + O → 2O2`
O3 can decompose spontaneously, and also under the influence of
light, but a Cl atom accelerates the reaction tremendously.
 Heterogeneous Catalysis
• In heterogeneous catalysis, solids catalyze reactions
of molecules in gas or solution.
• For nonporous solid catalysts, catalytic reactions
occur at the surface.
• To use the often expensive materials (e.g. platinum)
in an economical way, catalysts are usually
nanometer-sized particles, supported on an inert,
porous structure (see Fig. 1.4).
• Heterogeneous catalysts are the workhorses of the
chemical and petrochemical industry.
• Heterogeneous catalysts and many of their
applications will be discuss throughout this course.
 Catalysis : Nanomaterials and nanotechnology

Figure 1.4. Catalysts are nanomaterials and catalysis is

nanotechnology.
Catalysis represents a field where nanomaterials have
been applied.
Modern catalysis is principally nanotechnology
Biomass derived P-containing activated carbons as a novel green catalyst/support for

methanol conversion to dimethyl ether alternative fuel

Catalytic conversion of methanol

Dimethyl ether
DME

Stock
Green
Based
Biomass catalyst
Catalyst
WO3/P-containing activated carbons
The catalytic oxidation of CO
on the surface of noble metals
such as platinum, palladium and rhodium

Figure 1.5.
The catalytic oxidation of CO
on the surface of noble metals
such as platinum, palladium and rhodium

Figure 1.5.
The catalytic oxidation of CO
on the surface of noble metals
such as platinum, palladium and rhodium

Figure 1.5.
The catalytic oxidation of CO
on the surface of noble metals
such as platinum, palladium and rhodium

Figure 1.5.
The catalytic oxidation of CO
on the surface of noble metals
such as platinum, palladium and rhodium

Figure 1.5.
The adsorbed O atom and the adsorbed CO molecule react on the
surface to form CO2, which, being very stable and relatively unreactive,
interacts only weakly with the platinum surface and desorbs almost
instantaneously
The Arrhenius Equation
- Eact /RT
k = ve Activation energy lower:

Reaction temperature lower!!

Example: Suppose

reaction without catalyst: Eact = 250 kJ/mol

then Treaction ≈ 1000 K

however, if with a catalyst Eact = 100 kJ/mol

then Treaction ≈ 400 K !!!
Ammonia Synthesis
N2 + 3 H2 = 2 NH3 + heat
equilibrium reaction !
What are favorable conditions?
• pressure: high
• temperature: low
• kinetics slow: catalyst !!
Ammonia Synthesis
Source of nitrogen:
air
Source of hydrogen:
natural gas and water
Steam Reforming: Ni on a support

Courtesy
Haldor Topsoe

CH4 + H2O = CO + H2
 Water Gas Shift: More H2
Low Temperature :
Cu+ ZnO + Al2O3

High-temperature:
Fe3O4
Courtesy
Haldor Topsoe

CO + H2O = CO2 + H2
Ammonia Synthesis:
Fe3O4 + K + Al2O3

N2 + 3H2 = 2NH3
What is the essential action of the catalyst?

Why iron?

Courtesy
Haldor Topsoe
 Ammonia Synthesis
CH4 + H2O +N2

Ammonia
Synthesis

Steam Water Gas Methanation

Reforming Shift CO2
removal NH3

5 catalytic processes!
Metal Catalysts in NH3 Synthesis
N2 dissociation

Cr Fe Co Ni Cu
M
n Ru Rh Pd Ag

Mo Tc Os Ir Pt Au

Nitride formation
W Re no N2 dissociation = no reaction

Rate
(log)

Interaction
Ammonia Synthesis
(1908 - 1913)

Haber Bosch Mittasch

• conditions understood in early 20th century
• screening of 2500 catalysts in 6000 tests
• 1913: plant opened at Oppau - Ludwigshafen
• produced ammonium sulfate (fertilizer)
• 1914 redesigned to produce nitrate
Development of ammonia synthesis:
• start of chemical engineering
• high pressure reaction technology
• stimulus for catalysis
Catalysts
• increase the rate of a reaction
• without being consumed in the process
✓offer alternative, energetically
favorable pathways for reactions
✓ enable reactions to occur under
industrially achievable conditions
✓allow selective production routes
without or with less undesirable
byproducts
supported
catalyst ✓ are the work horses of the chemical
industry
✓ are the key enablers for
sustainable (green)production
catalyst
pellets and
extrudates
Courtesy
Haldor Topsoe