CAT AL YSI

S
A guide for A level students

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

CATALYSIS
INTRODUCTION
This Powerpoint show is one of several produced to help students understand
selected topics at AS and A2 level Chemistry. It is based on the requirements of
the AQA and OCR specifications but is suitable for other examination boards.
Individual students may use the material at home for revision purposes or it
may be used for classroom teaching if an interactive white board is available.
Accompanying notes on this, and the full range of AS and A2 topics, are
available from the KNOCKHARDY SCIENCE WEBSITE at...

www.knockhardy.org.uk/sci.htm

Navigation is achieved by...

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 CATALYSIS
CONTENTS
• Enthalpy changes
• Activation Energy
• Heterogeneous catalysis
• Specificity
• Catalytic converters
• Homogeneous catalysis
• Autocatalysis
• Enzymes

• Check list
 CATALYSIS
Before you start it would be helpful to…

• know how the basics of collision theory

• understand the importance of activation energy
• understand the importance of increasing the rate of reaction
 CATALYSTS - background
All reactions are accompanied by changes in enthalpy.
The enthalpy rises as the reaction starts because energy is being put in to break bonds.
It reaches a maximum then starts to fall as bonds are formed and energy is released.

ENTHALPY CHANGE DURING

AN EXOTHERMIC REACTION
 CATALYSTS - background
All reactions are accompanied by changes in enthalpy.
The enthalpy rises as the reaction starts because energy is being put in to break bonds.
It reaches a maximum then starts to fall as bonds are formed and energy is released.

If the…

FINAL ENTHALPY < INITIAL ENTHALPY

it is an EXOTHERMIC REACTION

and ENERGY IS GIVEN OUT

ENTHALPY CHANGE DURING

AN EXOTHERMIC REACTION
 CATALYSTS - background
All reactions are accompanied by changes in enthalpy.
The enthalpy rises as the reaction starts because energy is being put in to break bonds.
It reaches a maximum then starts to fall as bonds are formed and energy is released.

If the…

FINAL ENTHALPY < INITIAL ENTHALPY

it is an EXOTHERMIC REACTION

and ENERGY IS GIVEN OUT

FINAL ENTHALPY > INITIAL ENTHALPY

it is an ENDOTHERMIC REACTION

and ENERGY IS TAKEN IN

ENTHALPY CHANGE DURING
AN EXOTHERMIC REACTION
 CATALYSTS - background
ACTIVATION ENERGY - Ea

• Reactants will only be able to proceed to products if they have enough energy

• The energy is required to overcome an energy barrier

• Only those reactants with enough energy will get over

• The minimum energy required is known as the ACTIVATION ENERGY

ACTIVATION ENERGY Ea FOR

AN EXOTHERMIC REACTION
 CATALYSTS - background
COLLISION THEORY

According to COLLISON THEORY a reaction will only take place if…

• PARTICLES COLLIDE
• PARTICLES HAVE AT LEAST A MINIMUM AMOUNT OF ENERGY
• PARTICLES ARE LINED UP CORRECTLY
 CATALYSTS - background
COLLISION THEORY

According to COLLISON THEORY a reaction will only take place if…

• PARTICLES COLLIDE
• PARTICLES HAVE AT LEAST A MINIMUM AMOUNT OF ENERGY
• PARTICLES ARE LINED UP CORRECTLY

To increase the chances of a successful reaction you need to...

• HAVE MORE FREQUENT COLLISONS

• GIVE PARTICLES MORE ENERGY or
• DECREASE THE MINIMUM ENERGY REQUIRED
 MAXWELL-BOLTZMANN DISTRIBUTION

DUE TO THE MANY COLLISONS

TAKING PLACE IN GASES, THERE
NUMBER OF MOLECUES WITH IS A SPREAD OF MOLECULAR
ENERGY AND VELOCITY
A PARTICULAR ENERGY

NUMBER OF
MOLECULES WITH
SUFFICIENT ENERGY
TO OVERCOME THE
ENERGY BARRIER

MOLECULAR ENERGY Ea

The area under the curve beyond Ea corresponds to the number of molecules with
sufficient energy to overcome the energy barrier and react.

If a catalyst is added, the Activation Energy is lowered - Ea will move to the left.
 MAXWELL-BOLTZMANN DISTRIBUTION

DUE TO THE MANY COLLISONS

TAKING PLACE IN GASES, THERE
NUMBER OF MOLECUES WITH IS A SPREAD OF MOLECULAR
ENERGY AND VELOCITY
A PARTICULAR ENERGY

EXTRA NUMBER OF
MOLECULES WITH
SUFFICIENT ENERGY
TO OVERCOME THE
ENERGY BARRIER

MOLECULAR ENERGY Ea

The area under the curve beyond Ea corresponds to the number of molecules with
sufficient energy to overcome the energy barrier and react.

Lowering the Activation Energy, Ea, results in a greater area under the curve after Ea
showing that more molecules have energies in excess of the Activation Energy
 CATALYSTS - lower Ea
Catalysts work by providing…
“AN ALTERNATIVE REACTION PATHWAY WHICH HAS A LOWER ACTIVATION ENERGY”

WITHOUT A CATALYST WITH A CATALYST

A GREATER PROPORTION OF PARTICLES WILL HAVE ENERGIES

IN EXCESS OF THE MINIMUM REQUIRED SO MORE WILL REACT
PRINCIPLES OF CATALYTIC ACTION

The two basic types of catalytic action are …

HETEROGENEOUS CATALYSIS
and

HOMOGENEOUS CATALYSIS
 Heterogeneous Catalysis

Format Catalysts are in a different phase to the reactants

e.g. a solid catalyst in a gaseous reaction

Action takes place at active sites on the surface of a solid

gases are adsorbed onto the surface
they form weak bonds with metal atoms
 Heterogeneous Catalysis

Format Catalysts are in a different phase to the reactants

e.g. a solid catalyst in a gaseous reaction

Action takes place at active sites on the surface of a solid

gases are adsorbed onto the surface
they form weak bonds with metal atoms

Catalysis is thought to work in three stages...

Adsorption

Reaction

Desorption
 Heterogeneous Catalysis

For an explanation of what happens click on the numbers in turn, starting with 
 Heterogeneous Catalysis

Adsorption (STEP 1)
Incoming species lands on an active site and forms bonds with the catalyst. It may use some of the
bonding electrons in the molecules thus weakening them and making a subsequent reaction easier.
 Heterogeneous Catalysis

Adsorption (STEP 1)
Incoming species lands on an active site and forms bonds with the catalyst. It may use some of the
bonding electrons in the molecules thus weakening them and making a subsequent reaction easier.

Reaction (STEPS 2 and 3)

Adsorbed gases may be held on the surface in just the right orientation for a reaction to occur.
This increases the chances of favourable collisions taking place.
 Heterogeneous Catalysis

Adsorption (STEP 1)
Incoming species lands on an active site and forms bonds with the catalyst. It may use some of the
bonding electrons in the molecules thus weakening them and making a subsequent reaction easier.

Reaction (STEPS 2 and 3)

Adsorbed gases may be held on the surface in just the right orientation for a reaction to occur.
This increases the chances of favourable collisions taking place.

Desorption (STEP 4)
There is a re-arrangement of electrons and the products are then released from the active sites
 Heterogeneous Catalysis

ANIMATION

Adsorption (STEP 1)
Incoming species lands on an active site and forms bonds with the catalyst. It may use some of the
bonding electrons in the molecules thus weakening them and making a subsequent reaction easier.

Reaction (STEPS 2 and 3)

Adsorbed gases may be held on the surface in just the right orientation for a reaction to occur.
This increases the chances of favourable collisions taking place.

Desorption (STEP 4)
There is a re-arrangement of electrons and the products are then released from the active sites
Heterogeneous Catalysis
ANIMATION
 STRENGTH OF ADSORPTION

The STRENGTH OF ADSORPTION is critical ...

too weak Ag little adsorption - few available d orbitals

too strong W molecules remain on the surface preventing further reaction
just right Ni/Pt molecules are held but not too strongly so they can get away

Catalysis of gaseous reactions can lead to an increase in rate in several ways

• one species is adsorbed onto the surface and is more likely to undergo a collision
• one species is held in a favourable position for reaction to occur
• adsorption onto the surface allows bonds to break and fragments react quicker
• two reactants are adsorbed alongside each other give a greater concentration
 EXAMPLES OF CATALYSTS

Metals Ni, Pt hydrogenation reactions

Fe Haber Process
Rh, Pd catalytic converters

Oxides Al2O3 dehydration reactions

V2O5 Contact Process

Format FINELY DIVIDED increases the surface area

provides more collision sites

IN A SUPPORT MEDIUM maximises surface area and reduces costs

 Specificity
In some cases the choice of catalyst can influence the products

Ethanol undergoes different reactions depending on the metal used as the catalyst.
The distance between active sites and their similarity with the length of bonds
determines the method of adsorption and affects which bonds are weakened.

CLICK HERE FOR

ANIMATION
 Specificity
In some cases the choice of catalyst can influence the products

Ethanol undergoes different reactions depending on the metal used as the catalyst.
The distance between active sites and their similarity with the length of bonds
determines the method of adsorption and affects which bonds are weakened.
 Specificity
In some cases the choice of catalyst can influence the products

Ethanol undergoes different reactions depending on the metal used as the catalyst.
The distance between active sites and their similarity with the length of bonds
determines the method of adsorption and affects which bonds are weakened.

Copper Dehydrogenation (oxidation) Alumina Dehydration

C2H5OH ——> CH3CHO + H2 C2H5OH ——> C2H4 + H2O

 Specificity
Ethanol undergoes two different reactions depending on the metal used as the catalyst.

COPPER Dehydrogenation (oxidation)

C2H5OH ——> CH3CHO + H2

The active sites are the same distance

apart as the length of an O-H bond

It breaks to release hydrogen

ALUMINA Dehydration (removal of water)

C2H5OH ——> C2H4 + H2O

The active sites are the same distance

apart as the length of a C-O bond

It breaks to release an OH group

 Poisoning
Impurities in a reaction mixture can also adsorb onto the surface of a
catalyst thus removing potential sites for gas molecules and decreasing
efficiency.

expensive because... the catalyst has to replaced

the process has to be shut down

examples Sulphur Haber process

Lead catalytic converters in cars
 Catalytic converters
PURPOSE removing the pollutant gases formed in
internal combustion engines

POLLUTANTS CARBON MONOXIDE

NITROGEN OXIDES
UNBURNT HYDROCARBONS
 Catalytic converters
PURPOSE removing the pollutant gases formed
in internal combustion engines

POLLUTANTS CARBON MONOXIDE

NITROGEN OXIDES
UNBURNT HYDROCARBONS

CONSTRUCTION made from alloys of platinum, rhodium and palladium

catalyst is mounted in a support medium to spread it out
honeycomb construction to ensure maximum gas contact
finely divided to increase surface area / get more collisions
involves HETEROGENEOUS CATALYSIS
 Pollutant gases
Carbon monoxide CO
Origin incomplete combustion of hydrocarbons in petrol when not enough
oxygen is present to convert all the carbon to carbon dioxide
C8H18(g) + 8½O2(g) ——> 8CO(g) + 9H2O(l)
 Pollutant gases
Carbon monoxide CO
Origin incomplete combustion of hydrocarbons in petrol when not enough
oxygen is present to convert all the carbon to carbon dioxide
C8H18(g) + 8½O2(g) ——> 8CO(g) + 9H2O(l)

Effect poisonous
combines with haemoglobin in blood
prevents oxygen being carried to cells
 Pollutant gases
Carbon monoxide CO
Origin incomplete combustion of hydrocarbons in petrol when not enough
oxygen is present to convert all the carbon to carbon dioxide
C8H18(g) + 8½O2(g) ——> 8CO(g) + 9H2O(l)

Effect poisonous
combines with haemoglobin in blood
prevents oxygen being carried to cells

Removal 2CO(g) + O2(g) ——> 2CO2(g)

2CO(g) + 2NO(g) ——> N2(g) + 2CO2(g)

 Pollutant gases
Oxides of nitrogen NOx - NO, N2O and NO2
Origin nitrogen and oxygen combine under high temperature conditions
nitrogen combines with oxygen N2(g) + O2(g) ——> 2NO(g)
nitrogen monoxide is oxidised 2NO(g) + O2(g) ——> 2NO2(g)
 Pollutant gases
Oxides of nitrogen NOx - NO, N2O and NO2
Origin nitrogen and oxygen combine under high temperature conditions
nitrogen combines with oxygen N2(g) + O2(g) ——> 2NO(g)
nitrogen monoxide is oxidised 2NO(g) + O2(g) ——> 2NO2(g)

Effect photochemical smog - irritating to eyes, nose and throat

produces low level ozone - affects plant growth
- is irritating to eyes, nose and throat

i) sunlight breaks down NO2 NO2 ——> NO + O

ii) ozone is produced O + O2 ——> O3
 Pollutant gases
Oxides of nitrogen NOx - NO, N2O and NO2
Origin nitrogen and oxygen combine under high temperature conditions
nitrogen combines with oxygen N2(g) + O2(g) ——> 2NO(g)
nitrogen monoxide is oxidised 2NO(g) + O2(g) ——> 2NO2(g)

Effect photochemical smog - irritating to eyes, nose and throat

produces low level ozone - affects plant growth
- is irritating to eyes, nose and throat

i) sunlight breaks down NO2 NO2 ——> NO + O

ii) ozone is produced O + O2 ——> O3

Removal 2CO(g) + 2NO(g) ——> N2(g) + 2CO2(g)

 Pollutant gases
Unburnt hydrocarbons CxHy
Origin insufficient oxygen for complete combustion

Effect toxic and carcinogenic (causes cancer)

Removal catalyst aids complete combustion

C8H18(g) + 12½O2(g) ——> 8CO2(g) + 9H2O(l)
 Homogeneous Catalysis
Action • catalyst and reactants are in the same phase
• reaction proceeds through an intermediate species of lower energy
• there is usually more than one reaction step
• transition metal ions are often involved - oxidation state changes

Example
Acids Esterificaton
Conc. H2SO4 catalyses the reaction between acids and alcohols
CH3COOH + C2H5OH CH3COOC2H5 + H2O

NB Catalysts have NO EFFECT ON THE POSITION OF EQUILIBRIUM

but they do affect the rate at which equilibrium is reached
 Homogeneous Catalysis
Action • catalyst and reactants are in the same phase
• reaction proceeds through an intermediate species of lower energy
• there is usually more than one reaction step
• transition metal ions are often involved - oxidation state changes
 Homogeneous Catalysis
Action • catalyst and reactants are in the same phase
• reaction proceeds through an intermediate species with of energy
• there is usually more than one reaction step
• transition metal ions are often involved - oxidation state changes

Examples
Gases Atmospheric OZONE breaks down naturally O3 ——> O• + O2
- it breaks down more easily in the presence of chlorofluorocarbons (CFC's).

There is a series of complex reactions but the basic process is :-

CFC's break down in the presence of
UV light to form chlorine radicals CCl2F2 ——> Cl• + • CClF2

chlorine radicals then react with ozone O3 + Cl• ——> ClO• + O2

chlorine radicals are regenerated ClO• + O ——> O2 + Cl•

Overall, chlorine radicals are not used up so a small amount of CFC's can
destroy thousands of ozone molecules before the termination stage.
 Transition metal compounds
These work because of their ability to change oxidation state

1. Reaction between iron(III) and vanadium(III)

The reaction is catalysed by Cu2+

step 1 Cu2+ + V3+ ——> Cu+ + V4+

step 2 Fe3+ + Cu+ ——> Fe2+ + Cu2+
overall Fe3+ + V3+ ——> Fe2+ + V4+
 Transition metal compounds
These work because of their ability to change oxidation state

2. Reaction between I¯ and S2O82-

A slow reaction because REACTANTS ARE NEGATIVE IONS ∴ REPULSION

Addition of iron(II) catalyses the reaction

step 1 S2O82- + 2Fe2+ ——> 2SO42- + 2Fe3+

step 2 2Fe3+ + 2I¯ ——> 2Fe2+ + I2

overall S2O82- + 2I¯ ——> 2SO42- + I2

 Auto-catalysis
Occurs when a product of the reaction catalyses the reaction itself

It is found in the reactions of manganate(VII) with ethandioate

2MnO4¯ + 16H+ + 5C2O42- ——> 2Mn2+ + 8H2O + 10CO2

The titration needs to be carried out at 70°C because the reaction is slow as Mn2+ is
formed the reaction speeds up; the Mn2+ formed acts as the catalyst
 ENZYMES
Action enzymes are extremely effective biologically active catalysts
they are homogeneous catalysts, reacting in solution with body fluids
only one type of molecule will fit the active site “lock and key” mechanism
makes enzymes very specific as to what they catalyse.

Activity is affected by ...

temperature - it increases until the protein is denatured
substrate concentration - reaches a maximum when all sites are blocked
pH - many catalysts are amino acids which can be protonated
being poisoned - when the active sites become “clogged” with unwanted
 ENZYMES
Action enzymes are extremely effective biologically active catalysts
they are homogeneous catalysts, reacting in solution with body fluids
only one type of molecule will fit the active site “lock and key” mechanism
makes enzymes very specific as to what they catalyse.

A B C

A Only species with the correct shape can enter the active site in the enzyme
B Once in position, the substrate can react with a lower activation energy
C The new products do not have the correct shape to fit so the complex breaks up
 ENZYMES
ANIMATED ACTION

A Only species with the correct shape can enter the active site in the enzyme
B Once in position, the substrate can react with a lower activation energy
C The new products do not have the correct shape to fit so the complex breaks up
 REVISION CHECK
What should you be able to do?

Recall the definition of a catalyst

Explain qualitatively how a catalyst works
Understand the difference between homogeneous and heterogeneous catalysis
Explain how heterogeneous catalysts work
Understand the importance of active sites, poisoning and specificity
Recall and understand the importance of catalytic converters
Explain how homogeneous catalysts work
Work out possible steps in simple reactions involving homogeneous catalysis
Recall and understand how enzymes work

CAN YOU DO ALL OF THESE? YES NO

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CAT AL YSI
S
The End

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING