CHEM 409N06

Ashley Causton 2015

Catalysts

Most industrial and biological reactions require catalysts

75% of all the industrial chemicals produced are produced by catalytic processes
A catalyst is a substance that increases the rate of reaction, but is neither created or
destroyed in the process:
o Homogeneous catalysts are in the same phase as the reacting substances
o Heterogeneous catalysts are in a different phase as the reacting substances
o Mixed - e.g. a homogenous catalyst on a solid supported
A catalyst changes the activation energy, Ea, of a reaction by providing an alternate
pathway for the reaction. The rate and rate constant k of a reaction are related to Ea in
the following ways:
rate = k * function of concentration
k = A exp(- Ea / RT)
where A is a constant related to collision rates - thus, a change in Ea changes the
rate of a reaction.
This is the Arrhenius equation http://en.wikipedia.org/wiki/Arrhenius_equation
The Arrhenius equation can show the effect of a change of temperature, or addition of a
catalyst on the rate constant (and therefore on the rate of the reaction)

Sketch the energy profile of a catalyzed versus unanalyzed reaction:

A B
Sketch a simple catalytic cycle:
Heterogeneous

Homogenous

Catalyst Form

Solid, often metal or metal

oxide

Metal complex

Mode of Use

Fixed bed or slurry

Dissolved in reaction medium

Solvent

Usually not required

Usually required can be product or

byproduct

Selectivity

Usually poor

Limited but can be tuned

Stability

Stable to high temperatures

Often decompose < 100 C

Recyclability

Easy

Can be very difficult

Activity Loss

Poisoning or sintering

Poisoning or irreversible reaction

Active Centres

Only surface atoms

All metal atoms

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Suitability of Catalyst:
Co$t aside, the suitability of a catalyst depends on:
o Activity
o Selectivity
o Stability

Ashley Causton 2015

Activity:
Activity is a measure of how fast a reaction proceeds in the presence of a catalyst
The units for activity are mol/L.h or mol/kg.h
Kinetic activities are derived from the fundamental rate laws
The Catalyst Activity can be expressed in terms of:
o Turnover Frequency (TOF) - Quantifies the specific activity of a catalyst centre - i.e.
the number of catalytic cycles occurring at the centre per unit time
o Turnover Number (TON) - Specifies the maximum use that can be made of a
catalyst or reaction cycles occurring at the reaction centre up to the decay of
activity
Selectivity:
Selectivity is the fraction of the starting material that is converted to the desired product
P
It is expressed by the ratio of the amount of desired product to the reacted quantity of
the reactant A
In addition to the desired reaction parallel and sequential reactions can also happen
Selectivity is of great importance in industrial catalysis is important as illustrated
by the synthesis gas chemistry:

Stability:
The chemical, thermal and mechanical stability of a catalyst determines its lifetime in
industrial reactors
Catalytic stability is influenced by numerous factors, including decomposition, coking and
poisoning
Catalyst deactivation can be followed by measuring activity or selectivity as a function of
time
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CHEM 409N06

Ashley Causton 2015

Deactivation of Catalysts: Irreversible Loss of Activity

o Types of deactivation:
Poisoning: strong chemisorption of impurity in feed (reversible)
Fouling: secondary reactions of reactants or products,coke formation
Thermal degradation: sintering (loss of surface area), evaporation
Mechanical damage (attrition)
Corrosion/leaching
In most cases the catalysts can often be regenerated before they ultimately have to be
replaced
Looking at catalyst, the target qualities should be given the following order of priority:
Selectivity > Stability > Activity

Heterogeneous Catalysts:
Are used extensively in industry
Usually solids
Can also be on a solid support such as alumina (Al2O3) or other metal oxide
Robust and can be used at high temperature
No extra steps needed to separate products
Loss of catalyst is minimized
General Mechanism of Heterogeneous Catalysis:
The catalyst is in a different phase to the reactants and products
The reactant(s) are adsorbed on to the surface of the catalyst
The products are then desorbed
Draw the mechanism for the hydrogenation of ethene using a metal catalyst:
H

H
C C

H2 / Pt

H H
H C C H

H H

Physical Adsorption:
Small molecules become attached to the surface (no penetration of bulk solid this would
be absorption)
Adsorption energy is exothermic (~ -20 kJ mol-1 for non-polar molecules)
No chemical bonds are formed or broken
Small molecules may be several molecular layers deep
Chemisorption:
Small molecules become attached to the surface
Adsorption energy is strongly exothermic (~ -40 to -800 kJ mol-1)
Chemical bonds are formed or broken
Involve only first monomolecular layer of absorbate
Draw the potential energy diagram for the interaction of hydrogen with nickel:
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Ashley Causton 2015

If physical adsorption is too weak then the reactant may not interact significantly with the
surface
If the chemisorption is too strong then the adsorbed species will poison the catalyst

How do transition metal catalysts interact with molecules ?

Chemisorption Bond Strength for Common Gaseous Reagents:
For all metals except gold, the chemisorption bond strength order is:
O2 > alkynes > alkenes > CO > H2 > CO2 > N2
Strength of Interaction for Metals:
Increases from right to left across the transition metals in the periodic table
The elements Sc, Ti, V, Cr and Mn interact strongly even with N2 - therefore they are
poisoned very easily by adsorbates
The relative strengths allow simple predictions regarding suitable metal catalysts for
specific reactions (i.e. related to selectivity)
Choice of buffer or carrier gases that will not interact with the surface of the catalyst
How do the relative chemisorption strengths of other transition metals compare when exposed
to the following adsorbates ?
O2 > alkynes > alkenes > CO > H2 > CO2 > N2

Another important consideration for heterogeneous catalysts is surface area

Zeolites:
Are naturally occurring or synthesized aluminosilicates which are used extensively in
chemical industry (http://en.wikipedia.org/wiki/Zeolite)
Can be prepared as very fine crystals that contain large regular channels
o the channel size depends on the cations that are present
Can be size / shape selective
Also used as supports for other catalysts (other supports used in heterogeneous catalysis
include TiO2, Cr2O3, ZnO, MgO, C)
GROUP WORK: Give examples of zeolites in action:
Homogeneous Catalysts:
The catalyst is in the same phase to the reactants and products
Involve a transition metal catalyst
The transition metal is usually a complex
Explain how the tris(ethylenediamine)nickel(II) complex is formed:
Ni2+ + 3 NH2CH2CH2NH2 [Ni(en)3]2+
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Ashley Causton 2015
The 18/16 Electron Rule:
In main group chemistry, the electron count (electronic structure) is often described by
the octet rule to explain the formation of compounds (filling of s- and p- orbitals)
Similarly, in organo-metallic chemistry, the electronic structures of many compounds are
based on a total valence count of 18 on the central metal atom (filling of s-, p- and dorbitals)
However, there are exceptions to the 18-electron rule
GENERALIZATION: Organo-metallic reactions including catalytic processes proceed by
elemental steps involving intermediates with 16 or 18 electrons (Tolmans rule)
Give a schematic diagram illustrating Tolmans rule:
Homogeneous Catalytic Reactions:
A catalytic cycle involves:
o the coordination of the ligand reactants
o reaction of the ligands
o separation of products from the metal centre
Suggested Reading: Chapter 2.3 (pp. 43-61) of "Chemical Technology: An Integral Textbook" by
Andreas Jess & Peter Wasserscheid

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