Mechanisms of Catalytic Reactions and Characterization of Catalysts

What is a Catalyst ?
Catalyst is a substance that increases the rate
of the reaction at which a chemical system approaches equilibrium , without being substantially consumed in the process.

Catalyst affects only the rate of the

reaction,i.e.Kinetics.
It changes neither the thermodynamics of the reaction nor the equilibrium composition.
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Chemical Reaction
Thermodynamics says NOTHING about the rate of a reaction. Thermodynamics : Will a reaction occur ? Kinetics : If so, how fast ?

Kinetic Vs. Thermodynamic

A reaction may have a large, negative DGrxn, but the rate may be so slow that there is no evidence of it occurring.

Conversion of graphite to diamonds is a thermodynamic favor process (DG -ve ).

C (graphite) C (diamond)
Kinetics makes this reaction nearly impossible
(Requires a very high pressure and temperature over long time)

Kinetic Vs. Thermodynamic

Reaction path for conversion of A + B into AB

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Activation Energy
Activation Energy : The energy required to overcome the reaction barrier. Usually given a symbol Ea or G
The Activation Energy (Ea) determines how fast a reaction occurs, the higher Activation barrier, the slower the reaction rate. The lower the Activation barrier, the faster the reaction

Activation Energy
Catalyst lowers the activation energy for both forward and reverse reactions.

Activation Energy

This means , the catalyst changes the reaction path by lowering its activation energy and consequently the catalyst increases the rate of reaction.
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How a Heterogeneous Catalyst works ?

Substrate has to be adsorbed on the active sites of the catalyst

Absorption and Adsorption

H H H H H H H H H H H H H H H H H H

H H HH H H H H H H H H H H H H H H

H2 adsorption on palladium

H2 absorption palladium hydride

Surface process

bulk process

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Adsorption
In physisorption

1. The bond is a van der Waals interaction 2. adsorption energy is typically 5-10 kJ/mol. ( much weaker than a typical chemical bond )
3. many layers of adsorbed molecules may be formed.

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Adsorption
For Chemisorption

1. The adsorption energy is comparable to the energy of a chemical bond. 2. The molecule may chemisorp intact (left) or it may dissociate (right). 3. The chemisorption energy is 30-70 kJ/mol for molecules and 100-400 kJ/mol for atoms.

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Characteristics of Chemi- and Physisorptions

DE(ads)
E(d)
Physisorption

<

DE(ads)
Chemisorption

small minima weak Van der Waal attraction forces

large minima formation of surface chemical bonds

CO
physisorption

physisorption/ desorption chemisorption

atomic chemisorption

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Adsorption and Catalysis

Adsorbent: surface onto which adsorption can occur.
example: catalyst surface, activated carbon, alumina Adsorbate: molecules or atoms that adsorb onto the substrate. example: nitrogen, hydrogen, carbon monoxide, water Adsorption: the process by which a molecule or atom adsorb onto a surface of substrate. Coverage: a measure of the extent of adsorption of a specie onto a surface
H H H H H H H H

adsorbate

coverage q = fraction of surface sites occupied

H H H H

adsorbent

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Adsorption Mechanisms
Langmuir-Hinshelwood mechanisms:
1. Adsorption from the gas-phase 2. Desorption to the gas-phase 3. Dissociation of molecules at the surface 4. Reactions between adsorbed molecules Two Questions:

Is the reaction has a Langmuir-Hinshelwood mechanism? What is the precise nature of the reaction steps? Cannot be solved
without experimental or computational studies
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Langmuir-Hinshelwood mechanisms
Example The Reaction A2 + 2B = 2AB

may have the following mechanism

A2 + * = A2* A2* + * = 2A* B + * = B* A* + B* = AB* + * AB* = AB + *

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Adsorption Mechanisms
Eley-Rideal mechanism:

1. Adsorption from the gas-phase 2. Desorption to the gas-phase

3. Dissociation of molecules at the surface 4. Reactions between adsorbed molecules 5. Reactions between gas and adsorbed molecules The last step cannot occur in a Langmuir-Hinshelwood mechanism

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Eley-Rideal mechanism
Example
The reaction A2 + 2B = 2AB may have the following Eley-Rideal mechanism A2 + * = A2* A2* + * = 2A* A* + B = AB + * where the last step is the direct reaction between the adsorbed molecule A* and the gas-molecule B.

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Eley-Rideal or Langmuir-Hinshelwood?
For the Eley-Rideal mechanism:
the rate will increase with increasing coverage until the surface is completely covered by A*. For the Langmuir-Hinshelwood mechanism:

the rate will go through a maximum and end up at zero, when the surface is completely covered by A*.
This happens because the step B + * = B*

cannot proceed when A* blocks all sites. The trick is that the step B + * = B*
requires a free site.
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Catalyst Preparation
(1) Unsupported Catalyst Usually very active catalyst that do not require high surface area e.g., Iron catalyst for ammonia production (Haber process)

(2) Supported Catalyst requires a high surface area support to disperse the primary catalyst the support may also act as a co-catalyst (bi-functional) or secondary catalyst for the reaction (promoter)

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Supported Catalyst
Highly dispersed metal on metal oxide
Nickel clusters

SiO2
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End of the Catalysis and Catalysts

THANK YOU
References

1. 2.
3.

A.Corma,Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem. Rev.1995, 95, 559-614. Bruce C. gates, Catalytic Chemistry.1992.
Zaki Seddigi, Characterization of the acidic properties of zeolite and their catalytic behavior in the synthesis of MTBE. 1994.

4. 5.

Ali El-Rayyes, Study of the photochemical properties of some aromatic compound on molecular sieves using a picosecond pulse laser system. 2001. Keith Laidler, Chemical Kinetics, 1987.
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