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Homogenous
Catalyst Form
Metal complex
Mode of Use
Solvent
Selectivity
Usually poor
Stability
Recyclability
Easy
Activity Loss
Poisoning or sintering
Active Centres
CHEM 409N06
Suitability of Catalyst:
Co$t aside, the suitability of a catalyst depends on:
o Activity
o Selectivity
o Stability
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
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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CHEM 409N06
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
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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CHEM 409N06
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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