5.11 Catalysis

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College Board AP Chemistry Your notes
5.11 Catalysis
Contents
Catalysts & Reaction Rate
Catalysts in Action
Page 1 of 13
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Your notes
Catalysis describes the process by which the rate of a reaction is increased by the addition of a
substance known as a catalyst
A catalyst is a substance that increases the rate of a reaction without being consumed by it
The effect of a catalyst is seen in its ability to reduce the activation energy required for a reaction
How Does a Catalyst Work?
Considering the general form of rate laws, rate = k[A]x[B]y, we can conclude that a catalyst affects the
numerical value of k, the rate constant
According to the Arrhenius equation, k = Ae-Ea/RT, the rate constant, k, is determined by the frequency
factor, A, and the activation energy, Ea
Hence a catalyst may affect the rate of a reaction by altering the value of A or Ea
A catalyst provides an alternative mechanism with a lower Ea compared to the uncatalysed
reaction
It could also help with the orientation of the reacting molecules, thereby increasing the frequency
factor, A
The more dramatic effect of the catalyst involves the provision of an alternative reaction mechanism
with lower activation energy
Effect of Catalyst on Activation Energy
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Your notes
The diagram shows that a catalyst allows the reaction to take place through a different mechanism,
which has a lower activation energy than the original reaction
It is important to note that a catalyst has no effect on:

The overall energy change of the reaction
The kinetic energy of the reacting molecules
The yield of the products
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Worked example
Your notes
The following graph shows two different reaction pathways, X and Y, for the same overall reaction at
the same temperature.
a. Identify which pathway is slower with reason(s)

b. How can there be two different reaction pathways for the same reaction at the same
temperature?
Answers:
Answer a)
Pathway Y is slower because it has a higher activation energy
Answer b)
The difference in the reaction pathway indicates the presence of a catalyst
The catalyst speeds up the rate of the reaction by providing an alternative pathway X with lower
activation energy
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Catalysts & Rate-Determining Steps

Catalysts speed up reaction rates by providing an alternative mechanism with lower activation energy Your notes
In some instances, the catalyzed mechanism may include an additional reaction step
Consider a simple, one-step, bimolecular reaction:
A + B → AB
A possible mechanism for the catalyzed reaction is shown below:
A + catalyst → A—catalyst (step 1)
A—catalyst + B → AB + catalyst (step 2)
Overall reaction: A + B → AB
From this proposed mechanism, we can see that:
The chemical species A—catalyst is an intermediate
It is produced in step 1 and consumed in step 2
The catalyst is regenerated in the reaction
It appears as a reactant in step 1 and as a product in step 2
Hence in a reaction mechanism, the overall concentration of the catalyst is constant
The catalyst may change during the overall reaction
It is typically involved in the rate-determining step
It is regenerated unchanged at the end of the overall reaction
The effect of a catalyst can be shown on an energy profile diagram as follows:
Catalyst and Reaction Mechanisms
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Your notes
A catalyst lowers the activation energy of a reaction by providing an alternative mechanism. A catalyst
also increases the rate of the reverse reaction
Note that a catalyst decreases the activation energy for both the forward and the reverse reactions
Hence, it speeds up the rate of both reactions and consequently allows the system to reach
equilibrium quickly
Therefore, a catalyst has no effect on the position of equilibrium for a reaction
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Catalysts in Action
Your notes
Catalysts & Binding
Catalysts are classified into two categories depending on whether they are in the same phase as the
reactants or not
Homogeneous
Heterogeneous
Heterogeneous catalysts are in a different phase to the reaction
For example, the use of platinum or palladium metals (solid) in organic reactions such as
hydrogenation reactions
Homogeneous catalysts exist in the same phase as the reactants
Homogeneous catalysts most often catalyze gaseous and aqueous reactions
For example, aqueous zinc chloride, ZnCl2, is used to catalyze the organic reaction between
hydrogen chloride and alcohol
Enzyme Catalysis
Enzymes are examples of biological catalysts that can speed up the rate of biological reactions in living
organisms
Most enzymes are large protein molecules with molecular weights ranging from about 10,000 to
about 1 million amu
Enzymes are very selective in the reactions they catalyze
Some are absolutely specific, operating for only one substance in only one reaction
Enzyme molecules possess an active site
This is part of the molecule with a shape that allows a specific reactant molecule (substrate) to
bind
The binding between the substrate and active site involves dipole-dipole attractions, hydrogen
bonds, and dispersion forces
Two models currently exist to explain how an enzyme and its substrate interact
Model 1:
The substrate molecule fits into the active site on the enzyme molecule, somewhat in the way a
key fits into a lock
This results in the formation of an enzyme-substrate complex as a reaction intermediate
On binding to the enzyme, the substrate may have bonds weakened or new bonds formed
that help yield the products
Model 2:
This is often called the induced fit model
This suggests that the active site of an enzyme changes its shape to fit its substrate
Enzyme Catalysis Models
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Your notes
Diagram A shows the lock and key model relationship between the enzyme’s active site and the
reactant molecules (substrate) while diagram B shows the enzyme’s active site changing shape to allow
the substrates to bind.
Page 8 of 13
Catalysts & Covalent Bonding

Some heterogeneous catalysts can speed up the reaction rate through the formation of weak covalent Your notes
bonds with the reactant molecules
One example is the decomposition of N2O on gold, the solid catalyst
N2O (g) → N2 (g) + ½ O2 (g)
In the catalyzed decomposition, N2O is chemically adsorbed on the surface of the solid gold
A weak covalent bond is formed between the oxygen atom of an N2O molecule and a gold atom on
the surface
This weakens the bond joining nitrogen to oxygen, making it easier for the N2O molecule to break
apart
The process can be represented as follows:
Decomposition of N2O with Gold Catalyst
Diagram showing the catalytic action of gold in the decomposition of dinitrogen oxide, N2O. A weak
covalent bond represented by the broken lines is formed between oxygen and the solid gold catalyst
Another example of catalysis involving covalent bond formation between a catalyst and the reactants
is acid-base catalysis
In such reactions, the catalyst donates protons to the reactant molecules (usually a base), a
process known as protonation
This leads to the formation of an intermediate which is more reactive than the original reactant
The conversion of esters into alcohol and water in the presence of a hydrochloric acid catalyst is a
good example of such reactions
Acid Catalysed Hydrolysis of Esters
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Your notes
Reaction mechanism showing acid-catalyzed hydrolysis of esters. The H3O+ acid catalyst pronates the
ester, forming a protonated intermediate. This intermediate is then easily hydrolysed
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Surface Catalysis
In industry, many reactions are catalyzed by the surfaces of solids Your notes
These reactions often involve gaseous reactants being adsorbed on the surface of a solid catalyst
Adsorption refers to the collection of one substance on the surface of another substance
Examples of surface catalysis
Some of the more important examples of surface catalysis include:
The Contact Process - a multistep reaction for making sulfuric acid
V 2 O 5 ( s)
2SO2 (g) + O2 (g) ⎯⎯⎯⎯⎯⎯⎯⎯ 2SO3 (g)
The Haber Process - for making ammonia
Fe ( s)
N2 (g) + 3H2 (g) ⎯⎯⎯⎯⎯⎯ 2NH3 (g)
Catalytic converters - for the removal of toxic / poisonous gases from car exhausts
Pt/Pd /Rh (s)
2CO (g) + 2NO (g) ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ 2CO2 + N2
Hydrogenation - for the hardening of vegetable oils
Ni/Pt/Pd (s)
C2H2 (g) + H2 (g) ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ C2H4 (g)
How surface catalysis works

The mode of action of a heterogeneous catalyst consists of 2 main steps:
Adsorption of the reactants on the catalyst surface
The reactants diffuse to the surface of the catalyst
The reactant is physically adsorbed onto the surface by weak forces
The reactant is chemically adsorbed onto the surface by covalent bonds
This causes bond weakening between the atoms of the reactants
Desorption of the products
The bonds between the products and catalyst weaken so much that the products break away from
the surface
Exam Tip
The specification states that:
in surface catalysis, a reactant or intermediate binds to, or forms a covalent bond with, the surface
This suggests that the focus of the reaction is on the initial adsorption of reactants and their
subsequent reactions more than desorption
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Surface catalysis in hydrogenation

Hydrogenation is an important industrial process that is used to convert Unsaturated fats, occurring as Your notes
oils, to Saturated fats
Hydrogenation involves the use of a heterogeneous catalyst
The hydrogenation process involves the addition of hydrogen across the carbon=carbon double bond
/ C=C which converts them into carbon-carbon single bonds / C-C
A simple example of hydrogenation involves ethylene and hydrogen gas:
C2H2 (g) + H2 (g) → C2H4 (g)
Without a catalyst, this reaction is very slow
However, when the reaction is catalyzed by a metal such as nickel, palladium or platinum, the rate
increases dramatically
The role of the catalyst is to allow the formation of metal–hydrogen interactions that weaken the H‒
H bond, making the reaction easier
How hydrogenation happens
Using the ethylene and hydrogen example, hydrogen and ethylene adsorb onto the catalyst surface,
where the reaction occurs
This causes weakening of the hydrogen bond / H-H, ultimately breaking the bond
This leaves two H atoms loosely bonded to the metal surface but relatively free to move
When a hydrogen atom encounters an adsorbed ethylene molecule, it forms a single covalent bond
with one of the carbon atoms
Effectively, the C‒C pi bond is destroyed
This leaves an ethyl group, C2H5, bonded to the surface via a metal-to-carbon sigma bond
This sigma bond is relatively weak
So, when the other carbon atom also encounters a hydrogen atom, a bond is readily formed
This forms an ethane molecule, C2H6, which is released from the metal surface
Surface Catalytic Hydrogenation of Ethylene
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Your notes
Diagram showing the reaction mechanism between ethylene and hydrogen on the surface of platinum
metal catalyst
In general, it is important to note that for solid catalysts, an increase in surface area makes them more
effective
Page 13 of 13

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College Board AP Chemistry Your notes

Catalysts & Reaction Rate

It is important to note that a catalyst has no effect on:

a. Identify which pathway is slower with reason(s)

Catalysts & Rate-Determining Steps

Catalysts & Covalent Bonding

How surface catalysis works

Surface catalysis in hydrogenation

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