Concepts of Heterogeneous

Catalysis
Catalysts & Adsorbents (CH3113)

Course Outcomes
1. Identify the mechanism of heterogeneous catalytic reactions.
2. Synthesize various solid catalyst.
3. Characterize different properties of solid catalyst.
4. Apply various adsorption isotherms.
5. Evaluate the performance of non-isothermal catalytic reactors.
6. Design of catalytic reactors.
Catalysis Types
Classification of
Catalytic Systems

Heterogeneous Homogeneous Enzymatic

No phase Phase Boundary Complex organic

boundary exists separates catalyst molecules,
from the usually protein,
reactants which form
a lyophilic colloid
Homogeneous Catalysis
Action • catalyst and reactants are in the same phase
• reaction proceeds through an intermediate species with lower energy
• there is usually more than one reaction step
• transition metal ions are often involved - oxidation state changes

Example
Acids Esterificaton
Conc. sulphuric acid 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 with lower energy
• there is usually more than one reaction step
• transition metal ions are often involved - oxidation state changes

In homogeneous catalysis - Catalysts are present in the same phase as the substances which are going
into the reaction phase.
• The most widely used industrial unit operation - homogeneous or heterogeneous catalysts as
these are better suited for the industrial operations.
• Heterogeneous or homogeneous forms of catalysts the catalysts does not undergo chemical
changes
• Physical states of these substances undergo substantial changes in the size of the particles or the
changes in colors.
• For homogenous catalytic reactions, the rate of catalytic reactions are proportional to the
concentration of catalysts .
Homogeneous Catalysis
Action • catalyst and reactants are in the same phase
• reaction proceeds through an intermediate species with lower 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.
 Homogeneous vs Heterogeneous
Homogeneous catalysis Heterogeneous catalysis
These types of catalysts usually are common in either These are found in liquid phase, gas phase and solid
liquid phase or gas phase phase

Operative temperature for homogeneous catalysis is Operative temperature for heterogeneous catalysis is
generally low except only when under high pressure harsh as compared to homogeneous process

As the reactants and catalysts are in same phase the The heterogeneous catalysis process diffusivity is low as
diffusion in homogeneous catalysis process is very high the absorbance surface is low

The heat transfer in homogeneous catalysis is very high The heat transfer is relatively low as compared to
as all the molecules of reactants and catalysts are in homogeneous catalysis as the reactant molecules
same phase and catalysts are in different phase

The active site is not very well defined as different

The active site is very well defined phase sites might have different catalytic properties
for the same particle
 Homogeneous catalysis Heterogeneous catalysis

Recycling methods are not very cost effective as

These catalysts although require reactivating
it’s a long drawn process and as it’s a difficult
treatment process but still quite cost effective
treatment method for spent catalysts

The modification of heterogeneous catalysts is

Modification of homogenous catalysts is very
relatively difficult as the controlling methods of
easy as it depends upon the tuning of electronic
particle site as well as the active size at molecular
and steric properties on metal
level is really difficult

Reaction mechanism is difficult to fins as the

Reaction mechanism easier to find as varied
techniques utilised as the product is scrutinised
techniques are available
and not the catalysts

Selectivity of homogeneous catalysts are very

Selectivity of heterogeneous catalysts is low
high
Introduction to Heterogeneous Catalyst
• Catalyst used by mankind for over 2000 years
• Wine, Cheeze and bread making industry
• Catalyst – components accelerating rate of chemical reaction without
being consumed
• Majority of catalysts are used in petroleum industry & production of
chemicals.
• Changes a reaction rate by promoting a different molecular path
("mechanism") for the reaction
• H2 and O2 are virtually inert at room temperature
• Components react instantaneously in presence of platinum
 • Catalysis – Occurrence, study, use of catalysts & catalytic
process
• Catalyst development is important in raw material &
finished product.
• Increase in product yield and selectivity in Chemical
Reactions
• A different product can be obtained by adopting an
alternate pathway having lower energy barrier, affecting
yield and selectivity.
• Catalyst can neither accelerate or slow • Heterogeneous Catalysts – Reactants,
formation of product species product and Catalysts are in the different
phases.
• Catalyst change rate of reaction – N2 + 3H2 → 2NH
doesn’t affect equilibrium 3

• At low temperature, reaction rate is very

• Homogeneous Catalysts – Reactants, low.
product and Catalysts are in the same • At high temperature reaction becomes fast,
phase. where dissociation to N and H are
2 2
2SO + O → 2SO favoured, if product is not at all removed.
 Catalysts
• Catalysts increase reaction rate without themselves being changed
• Can accelerate a reaction in both directions
• Do not affect the state of equilibrium of reaction
• simply allow equilibrium to be reached faster
 Effect of Activation Energy on a
reaction
Catalyst lowers the activation energy for both forward and reverse
reactions.

12
 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
Significance of Activation Energy
• Activation Energy is minimum amount of energy that must be possessed by reacting
molecules so that they can get converted into products.
• Reactant molecules must pass through energy rich activated state before they can react.
• Quantity of energy required by the reactants to overcome this activated state or energy
barrier is called as Activation energy.
• Difference between energies of reactants and products is called as heat of reaction.
• Energy of activation for any reaction is the difference in energy of activated complex and
energy of reactants.
Diffusion of Gases in Catalysts
 Heterogeneous Catalysis

Most important steps in a heterogeneous catalytic reaction are mentioned below

Adsorption: 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
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
There is a re-arrangement of electrons and the products are then released from the active sites