Duhok Polytechnique University Petrochemical Department Catalyst Science and Technology Lecturer: DR Farhad M. Ali 2020-2021

4th Year Stage Catalyst Science and Technology
Duhok Polytechnique University
Petrochemical Department
Catalyst Science and Technology
Lecturer: Dr Farhad M. Ali
2020-2021
The term catalysis (from the Greek kata-, “down,” and lyein, “loosen”) was
first employed by the great Swedish chemist Jöns Jacob Berzelius in 1835
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DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Chemical Kinetics; Rate of Reaction
Chemical kinetics is the study and discussion of chemical reactions with respect
to reaction rates, effect of various variables, re-arrangement of atoms,
formation of intermediates etc. There are many topics to be discussed, and each of
these topics is a tool for the study of chemical reactions. The study of motion is
called kinetics, from Greek kinesis, meaning movement. The study of chemical
kinetics, therefore, includes the rate of a chemical reaction and also the factors that
influence or alter or control the rate of chemical reactions.
In chemical kinetics we study how molecules react, bond breaking and new bond
formation.
At the macroscopic level, we are interested in amounts reacted, formed, and the rates
of their formation. At the molecular or microscopic level, the following
considerations must also be made in the discussion of chemical reaction
mechanism.
• Molecules or atoms of reactants must collide with each other in chemical

reactions.
• The molecules must have sufficient energy (discussed in terms of activation

energy) to initiate the reaction.
• In some cases, the orientation of the molecules during the collision must also be
considered.
Reaction Rates: how fast the concentration of a reactant or product changes

with time
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The relation between the rate of a reaction and the concentrations of reactants is
expressed by its rate law. For example, the rate of the gas-phase decomposition of
dinitrogen pentoxide
2N2O5 → 4NO2 + O2
has been found to be directly proportional to the concentration of N2O5:
rate = k [N2O5]
k = rate / [N2O5] (k is rate constant)
Be very careful about confusing equilibrium constant expressions with those for
rate laws. The expression for Keq can always be written by inspecting the reaction
equation, and it contains a term for each component (raised to the appropriate power)
whose concentration changes during the reaction. For this reaction it is given by:
Keq = [NO2]4 [ O2] / [N2O5]2 (keq is equilibrium constant)
In contrast, the expression for the rate law generally bears no necessary relation to
the reaction equation and must be determined experimentally.
Since the rate of a reaction has the dimensions of (concentration / time), the
dimensions of the rate constant k will depend on the exponents of the concentration
terms in the rate law.
Chemical reaction rates are the rates of change in concentrations or

amounts of either reactants or products over time.
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 For changes in amounts, the units can be one of mol s -1, g s-1, lb s-1, kg day-1 etc.
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 For changes in concentrations, the units can be one of mol dm -3 s-1, g dm-3 s-1, %
s-1 etc.
With respect to reaction rates, we may deal with average rates, instantaneous
rates, or initial rates depending on the experimental conditions.
The speed of a reaction is called the rate of the reaction. The speed of different
chemical reactions varies hugely. Some reactions are very fast and others are very
slow.
▪ Very fast reaction: explosion

▪ Very short time: precipitation of insoluble salts from their ions in a solution
▪ Takes a little longer: rusting of a nail left in the open air
▪ Takes too long time: formation of stalactites and stalagmites in caves
Measuring Rate of Reactions:
Some rate of reactions has detectable change with respect to time, changes that are
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observable like
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❑ a volume of gas is given off

❑ a change in mass during the reaction
❑ temperature changes
❑ colour changes
❑ a precipitate form
❑ pH changes
❑ change in conductivity
How can rate of reaction be measured?
Measuring the rate of a reaction means measuring the change in the amount of a
reactant or the amount of a product with respect to time.
What can be measured to calculate the rate of reaction between magnesium and
hydrochloric acid?
Mg (s) + HCl (aq) → MgCl2 (aq) + H2 (g)
⚫ The amount of hydrochloric acid used up (cm3 min-1).

⚫ The amount of magnesium chloride produced (g min-1).
⚫ The amount of hydrogen product (cm3 min-1).
Average, Instantaneous, and Initial Reaction Rate:
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1. Average rate of reaction, often denoted by (Δ[conc.] / Δt), The average
rate of reaction is an average rate, obtained by taking the change in
concentration over a time period, for example: - 0.3 M / 15 minutes

Average rate: rate of a chemical reaction computed as the ratio of a

measured change in amount or concentration of substance to the time
interval over which the change occurred.
Math: The formula for the average Rate of Change of y With Respect To x
The Average Rate of change of y with respect to x formula (in general, used in real
world problems such speed, weight loss, etc.)
The "average rate of change" and the "slope" are two different names for the same
formula (y2 - y1) / (x2 - x1). 6
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2. The instantaneous rate of reaction, denoted as dC / dt.
Note: Instantaneous rates are also known as differential rates.
I. Instantaneous rate can be obtained from the experimental data by: first graphing
the concentration of a system as function of time, 7
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II. then finding the slope of the tangent line at a specific point which corresponds to a
time of interest.
Alternatively, experimenters can measure the change in concentration over a very

small time period two or more times to get an average rate close to that of the

instantaneous rate. The reaction rate for that time is determined from the slope of the
tangent lines.
Instantaneous rate: rate of a chemical reaction at any instant in time,

determined by the slope of the line tangential to a graph of
concentration as a function of time.
We determine an instantaneous rate at time t:
• by calculating the negative of the slope of the curve of concentration of a

reactant versus time at time t.
• by calculating the slope of the curve of concentration of a product versus time
at time t.
3. Initial Rate: The initial rate of a reaction is the instantaneous rate at the
start of the reaction (i.e., when t = 0). The initial rate is equal to the negative
of the slope of the curve of reactant concentration versus time at t = 0.
An instantaneous rate is a differential rate: -d[reactant] / dt or d[product] / dt.
Relative Rates of Reaction
The rate of a reaction may be expressed in terms of the change in the amount of any
reactant or product and may be simply derived from the stoichiometry of the
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reaction. Consider the reaction represented by the following equation:
2 NH3 (g) → N2 (g) + 3 H2 (g)

The stoichiometric factors derived from this equation may be used to relate reaction
rates in the same manner that they are used to related reactant and product amounts.

The relation between the reaction rates expressed in terms of nitrogen production and
ammonia consumption, for example, is:
We can express this more simply without showing the stoichiometric factor’s units:
Note that a negative

sign has been added
to account for the
opposite signs of the
two amount changes
(the reactant amount
is decreasing while
the product amount
is increasing). If the
reactants and
products are present
in the same solution, the molar amounts may be replaced by concentrations:
Similarly, the rate of formation of H2 is three times the rate of formation of N2 because 9
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three moles of H2 form during the time required for the formation of one mole of N2:
The figure illustrates the change in concentrations over time for the decomposition of
ammonia into nitrogen and hydrogen at 1100 °C. We can see from the slopes of the

tangents drawn at t = 500 seconds that the instantaneous rates of change in the
concentrations of the reactants and products are related by their stoichiometric factors.
The rate of hydrogen production, for example, is observed to be three times greater
than that for nitrogen production:
Example 1: Consider the reaction that begins immediately after the ions Fe3+ and Sn2+
are simultaneously introduced into an aqueous solution.
2 Fe3+ (aq) + Sn2+ (aq) → 2 Fe2+ (aq) + Sn4+ (aq) (This an oxidation-
reduction reaction)
After 38.5 s of the start of the reaction, [Fe2+] is found to be 1 X 10-3 M.

a. What is the rate of formation of Fe2+?
b. What is the rate of formation of Sn4+?
c. What is the rate of disappearance of Fe3+?
d. What is the rate of disappearance of Sn2+?
Solution:
a. rate of formation of Fe2+:
[ Fe2+] /  t = 1 X 10-3 M / 38.5 s = 2.6 X 10-5 M s-1

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b. rate of formation of Sn4+:
½ X 2.6 X 10-5 M s-1 = 1.3 X 10-5 M s-1
c. rate of disappearance of Fe3+:
[ Fe3+] /  t = [ Fe2+] /  t = - 1 X 10-3 M / 38.5 s = - 2.6 X 10-5 M s-1

d. rate of disappearance of Sn2+:
½ X 2.6 X 10-5 M s-1 = - 1.3 X 10-5 M s-1
Now, the question is:
When refer to the rate of this reaction, which of the four quantities
described here should we use?
The IUPAC recommends that we use a general rate of reaction, which, for the
hypothetical reaction represented by the balanced equation, is
aA + bB → gG + hH
Rate of reaction = - 1/a [A] / t
= - 1/b [B] / t
= 1/g [G] / t
= 1/h [H] / t
In this expression, we take the negative values of rates of disappearance, positive values
of rates of formation, and divided all rates by the appropriate stoichiometric
coefficients from the balanced equation.
The result is a single, positive-valued quantity that we call the rate of reaction.
Thus, the rate for this reaction is
Rate of reaction = - ½ [ Fe3+] /  t 11

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= - [ Sn2+] /  t
= ½ [ Fe2+] /  t
= [ Sn4+] /  t
= 1.3 X 10-5 M s-1

Example 2: Suppose that at some point in the reaction:
A+3B→2C+2D
[B] = 0.9986 mol dm-3, and that 13.20 min later [B] = 0.9746 mol dm-3. What is the
average rate of this reaction during this period?
Average rate = Change in concentration / time or
[B] / t = 0.9746 mol dm-3 - 0.9986 mol dm-3 / 13.20 min - 0 min
= - 0.0240 mol dm-3 / 13.20 min = 0.0018 mol dm-3 min-1 or M min-1 (M
means molar)
Rate of reaction:
1/3 X [B] / t = - 1/3 X (- 0.0240 mol dm-3 / 13.20 min)
= 6.06 X 10-4 mol dm-3 min-1
Example 3: For the oxidation of ammonia
4NH3 + 3O2 → 2N2 + 6H2O
it was found that the rate of formation of N2 was 0.27 mol dm–3 s–1.
a) At what rate was water being formed?
b) At what rate was ammonia being consumed?
Solution:
𝟏 ∆[𝐇𝟐 𝐎] 𝟏 ∆[𝐍𝟐 ] 12
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a) =
𝟔 𝐭 𝟐 𝐭
From the equation stoichiometry, Δ[H2O] = 6/2 Δ[N2], so the rate of formation of
H2O is
3 × (0.27 mol dm–3 s–1) = 0.81 mol dm–3 s–1.

𝟏 ∆[𝐍𝐇𝟑 ] 𝟏 ∆[𝐍𝟐 ] 𝟏 ∆[𝐇𝟐 ]
b) = =
𝟒 𝐭 𝟐 𝐭 𝟔 𝐭

4 moles of NH3 are consumed for every 2 moles of N2 formed, so the rate of
disappearance of ammonia is 2 × (0.27 mol dm–3 s–1) = - 0.54 mol dm–3 s–1.
Comment: Because of the way this question is formulated, it would be acceptable to

express this last value as a negative number.
Factors affect Rate of Reaction; Changing the Rate of a Reaction
A reaction will form products more rapidly if the conditions under which the reaction
occurs are changed so that more molecules have enough energy to reach the peak of
either of the graphs.
There are three ways to increase the size of this set of molecules.
1. Increase the concentration of reactant molecules present
The more molecules present in the reaction vessel, the more likely is a collision. We
can increase the number of molecules by increasing the concentration of the reactants.
If the reactants are both gases, an increase in pressure decreases the volume and brings
the molecules closer together, thus increasing the likelihood of collision.
An increase in concentration produces more collisions. The chances of an effective

collision goes up with the increase in concentration. The exact relationship between
reaction rate and concentration depends on the reaction "mechanism". This is the
process involving elementary reaction steps. The slowest step controls the rate (Rate
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Determinant Step). The nature of the slow step is not obvious from the balanced
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equation. Only experimental observation reveals the link between concentration and
reaction rates.
Changing the concentration or pressure
If the concentration of a dissolved reactant is increased, or the pressure of a reacting

gas is increased:

 the reactant particles become more crowded (more closer each other)
 there is a greater chance of the particles colliding
 the rate of reaction increases
2. Increase the temperature of the reaction
The rate of a reaction will increase if the number of molecules with enough energy to
provide the activation energy of the reaction increases. The below figure shows the
distribution of energies in a collection of
molecules at two different temperatures. Molecules with an energy greater than at

point A are sufficiently energetic to provide the activation energy necessary for
collision. The screened area under each curve represents the number of molecules at
that temperature with an energy greater than A. The screened area is much larger
under the higher-temperature curve. Therefore, at the higher temperature, more
collisions occur and the reaction proceeds faster. At lower temperatures, these results
are reversed and the reaction is slower.
Changing the temperature:
If the temperature is increased:
 the reactant particles move more quickly

 they have more energy (higher kinetic energy) 14
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 the particles collide more often, and more of the collisions result in a reaction
 the rate of reaction increases
As the temperature increases the number of collisions increases as well as the energy
of the collisions.

So, temperature has a big effect on the rate of reaction.
For every 10 oC increase the rate approximately doubles.
Higher temperature → faster reaction
3. Lower the activation energy required for reaction
If the activation energy could be lowered, more molecules would be able to react.
How can the activation energy of a reaction be lowered?
A catalyst can provide such an alternative pathway.
A catalyst is a substance that, when added to a reaction mixture, increases the rate of
the overall reaction yet is recovered unchanged after the reaction is complete.
Suppose a substance C is added to a reaction mixture. If the formation of the product

occurs at a faster rate in the presence of C than in its absence and if C is recovered
unchanged, then C is a catalyst for the reaction. The figure shows that activation
energy is still required, but it is less than that of the uncatalyzed reaction.
There are many examples of catalysts. Since the mid-1970s, many automobile exhaust
systems have been manufactured with catalysts for the reaction
2CO(g) + O2(g) 2CO2(g) (needs high temperature without catalyst)
In the absence of a catalyst, this reaction requires a very high temperature and does not
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occur significantly at normal exhaust temperatures. The well-being of the public

requires that cars stop discharge(eject) large amounts of carbon monoxide. The
introduction of a catalyst to the exhaust system of the car makes possible the oxidation

of carbon monoxide to carbon dioxide at lower exhaust temperatures, with a

considerable improvement in air quality.
A catalyst has the following properties:
Its chemical properties remain unchanged at the end of reaction, although its
physical appearance may change.
1. It is not used up during the reaction, so it has the same mass at the beginning
and at the end of the reaction.
2. Only a small amount of it is needed to speed up the reaction.
3. A catalyst increases the speed but not the yield of a chemical reaction. That is,
the same amount of products is formed whether a catalyst is used or not (mass
balance).
4. Catalysts are very specific to a particular chemical reaction
Catalysts have many uses. For example, iron catalyst (Fe) is used in Haber process
(manufacture of ammonia, NH3) and Epoxyethane is manufactured by reacting
ethene with a limited amount of oxygen in the presence of a silver catalyst,
Some common catalysts used in industry and the reactions they catalysis
Catalyst Reaction catalysed

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Iron making ammonia from nitrogen and hydrogen
Platinum making nitric acid from ammonia
Vanadium(V) oxide making sulphuric acid
Zeolite Catalytic cracking

Platinum on zeoliteIsomerisation for organic compounds
platinum catalyst suspended on aluminium oxide Reforming (a process used to

improve the octane rating of hydrocarbons)
4. Surface area
When a reaction is to take place between reactants in two different physical states,
the reaction rate is increased if we increase the surface area of the more-condensed
reactant. Such reactions include a gas or a liquid with a solid or a gas with a liquid.
The rate of a chemical reaction can be raised by increasing the surface area of a solid
reactant. This is done by cutting the substance into small pieces, or by grinding it
into a powder.
Changing the surface area:
If a solid reactant is broken into small pieces or ground into a powder:
• its surface area increases
• more particles are exposed to the other reactant
• there are more collisions
• the rate of reaction increases
The reaction between a gas and a liquid will take place more rapidly if the liquid is
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sprayed in small drops through which the gas passes than if the gas is passed over the
surface of a large body of liquid.

5. Light
Some reactions, classified as photochemical reactions, are very sensitive to light. A

mixture of the reactants in such a reaction will be stable in the dark indefinitely.
When exposed to light of the correct wavelength, the reaction occurs, often at an
explosive rate. The reaction of hydrogen with chlorine is one such reaction.
H2 (g) + Cl2 (g) → no reaction (dark)
H2 (g) + Cl2 (g) + h → 2 HCl (g) (light)
Light is a form of energy. Hence it provides the necessary activation energy for the
reaction to take place.
The decomposition of nitrogen dioxide into nitrogen monoxide and atomic oxygen
is another photochemical reaction. Small amounts of nitrogen dioxide are found in
the exhaust gases from gasoline engines.
NO2 → NO + O
6. Stirring
In a heterogeneous reaction there are two or more phases of matter interacting, such
as a solid dissolving into a liquid. Stirring or shaking the mixture will speed up the
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reaction rate. This is common sense. When you add sugar to a drink, you stir it
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because you know it will dissolve faster.
Collision theory would predict this because the stirring would increase the number
of collisions between reactant molecules.

Questions:
Q 1: Why the reactants particles move faster when the temperature increases?
Ans.: it is because the particles get higher kinetic energy.
Q 2: How the reaction rate affected by Collision frequency?
Ans.: Collision frequency (the number of collisions in one second): If the number or
frequency of collisions is high, the number of collisions that occur is high. The
frequency of effective collisions also increases; therefore, the rate of reaction becomes
higher.
Q 3: What is the Effect of Increasing the Pressure on the Rate of a Chemical

Reaction?
Ans.: Increasing the pressure of a reaction where the reactant is a gas is similar to
increasing the concentration of a reactant in a solution. The gas particles (usually
molecules) will be closer together when the pressure increases. This means that the
particles will collide more frequently, and the rate of the chemical reaction will
increase.
What is a catalyst?
A catalyst is a substance which enhances the rate of a chemical reaction without itself
getting used up in the reaction. A catalyst offers an alternative, energetically favourable
mechanism to the non-catalytic reaction, thus enabling processes to be carried out 19
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under industrially feasible conditions of pressure and temperature. A catalyst is a

chemical substance that, when added to a chemical reaction, does not affect the
thermodynamics of a reaction but increases the rate of reaction. They increase the
frequency of collisions between reactants but do not change their physical or chemical
properties.

For an active catalyst, the number of molecules transformed per minute by one
molecule of catalyst may be as large as several million. Where a given substance or a
combination of substances undergoes two or more simultaneous reactions that yield
different products, the distribution of products may be influenced by the use of a
catalyst that selectively accelerates one reaction relative to the other(s).
What is meant by catalysis?
The phenomenon using catalyst is known as catalysis. It is the process of using

catalyst.
Catalysis is the key to chemical transformations. Most industrial syntheses and nearly
all biological reactions require catalysts. Furthermore, catalysis is the most important
technology in environmental protection, i. e., the prevention of emissions, a well-
known example is the catalytic converter for automobiles.
Catalytic reactions were already used in antiquity, although the underlying principle
of catalysis was not recognized at the time. For example, the fermentation of sugar to
ethanol and the conversion of ethanol to ethanoic acid are catalyzed by enzymes
(biocatalysts).
However, the systematic scientific development of catalysis only began about 200
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years ago, and its importance has grown up to the present day.
What is the advantage of using catalyst or catalysis?
The main advantages of catalysis are that:
 we get the desired product faster,

 using fewer resources,

 generating less waste,

 using less energy (many important chemical reactions require inputs of energy
to proceed. If a catalyst is present less energy will be required to complete the
reaction).
Does the catalyst lower the activation energy for the reaction?
It provides an alternative reaction pathway of

lower activation energy Ea, compared to the
uncatalysed reaction. A catalyst lowers the
activation energy (Ea) by providing a different
'pathway' or mechanism that makes the bond
breaking processes (or other electronic changes in
the reactants) occur more readily.
Some examples of comparing the activation

energies of uncatalysed and catalysed reactions:
Ea for Ea for Catalyst

Example Uncatalysed Catalysed
KJ mol-1
The decomposition of hydrogen 75 49 colloidal
peroxide: 2H2O2(aq) → 2H2O(l) + O2(g) platinum
23 enzyme
The decomposition of hydrogen iodide: 183 105 Au
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2HI(g) → H2(g) + I2(g) 58 Pt
The synthesis of ammonia: 350 162 W
N2(g) + 3H2(g) → 2NH3(g)

The formation of intermediates
Catalysis also involves the formation of intermediates, not just a matter of an 'activated
complex' or 'transition state'. e.g. for a transition metal the reactant molecules may be
adsorbed and their bonds weakened, or, for a transition metal compound, it may
involve a change in ligand or oxidation state or other bonding re–arrangement, but
will return to its original state often via a 2–3 stage 'catalytic cycle'.
What is reaction intermediate (Transition State)?
A reaction intermediate or an intermediate is a molecular entity that is formed from

the reactants (or preceding intermediates) and reacts further to give the directly
observed products of a chemical reaction. Most chemical reactions are stepwise, that
is they take more than one elementary step to complete. Transition states may involve
transition metals when they use as catalyst.
The exact mechanism for the action of catalysts is not completely understood in all
cases. However, catalysts provide an alternate path or series of steps by which the
reaction can take place.
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What is Activation Energy?
Activation energy is the minimum amount of energy that must be available for a
chemical reaction to occur. In order for reactions to proceed we must provide energy
to break bonds. This energy is known as the activation energy for a particular reaction.
Based on Maxwell -
Boltzmann distribution
description, shows how
reducing the activation
energy considerably
increases the proportion
of particles with
sufficient kinetic energy
to overcome the barrier
of the activation energy.
Transition metals are very good catalysts…Why?
The most important reason transition metals are good catalysts is that they can lend
electrons or withdraw electrons from the reagent, depending on the nature of the
reaction.
1- The ability of transition metals to be in a variety of oxidation states, the

ability to interchange between the oxidation states and the ability to form 23
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complexes with the reagents and be a good source for electrons make transition
metals good catalysts.
2- They provide a surface for reactions to occur. The metal forms weak
bonds to the reacting species holding them in place.

What change(s) could happen to the catalyst?
A catalyst can be changed physically e.g. the granules can end up more powdery or
the surface become roughened. This may be due to a heat effect from exothermic
reactions or just side effect of regeneration in the catalytic cycle.
For example, in the laboratory preparation of oxygen from the MnO 2(s) catalysed
decomposition of hydrogen peroxide solution, the residual water seems stained brown
due to very fine particles of MnO2(s)
Do we always need to use catalyst?
For some reactions it is not really necessary to use catalyst. For example, when the
reaction is with low activation energy. The following shows the necessity to use a
catalyst for reactions:
Comments related to the reaction activation energy

Reaction Profile Diagram
and use of a catalyst
An exothermic reaction with a small activation energy
The reaction may go very well without a catalyst at a
practical temperature, perhaps even at room
temperature
An exothermic reaction with a moderately high

activation energy.
This reaction might benefit from using a catalyst if a
suitable one is available
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An endothermic reaction with a big activation energy

This reaction would benefit from using a catalyst e.g.
to avoid using an excessively high temperature,
catalysts used to crack crude oil into useful fractions

Does the catalyst affect the chemical equilibrium position?
The catalyst for a given reaction accelerates the reaction in both directions equally.
Therefore, a catalyst does not affect the position of equilibrium of a chemical reaction;
it affects only the rate at which equilibrium is attained. Apparent exceptions to this
generalization are those reactions in which one of the products is also a catalyst for the
reaction. Such reactions are termed autocatalytic.
a catalyst does not shift the position of equilibrium in a chemical reaction

- its action only increases the rate at which equilibrium is approached.
Types of Catalysis:
(a) Homogeneous catalysis:
Homogeneous catalysis refers to reactions where the catalyst is in the same phase
as the reactants, principally in solution. Homogeneous catalysts occupy the same
phase as the reaction mixture.
Enzymatic catalysis is a good example of homogeneous catalysis.
Homogeneous catalysts allow for greater interaction with the reaction mixture than
heterogeneous catalysts.
 The catalyst and reactants are in the same phase (usually a solution), and
so the catalysed reaction can happen throughout the bulk of the reaction
medium. 25
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 Catalysis can be due to temporary changes in the oxidation state and
ligand(s) of a transition metal ion and results in a 'catalytic cycle'. In other
words, the reaction occurs via some intermediate species and the original
catalyst is reformed.

What is a phase?
If you look at a mixture and can see a boundary between two of the components,
those substances are in different phases. A mixture containing a solid and a liquid
consists of two phases. A mixture of various chemicals in a single solution consists of
only one phase, because you can't see any boundary between them.
Examples of homogeneous catalysis:
Acid catalysis, organometallic catalysis, and enzymatic catalysis are examples of

homogeneous catalysis. Most often, homogeneous catalysis involves the introduction
of an aqueous phase catalyst into an aqueous solution of reactants. In such cases, acids
and bases are often very effective catalysts, as they can speed up reactions by affecting
bond polarization.
An advantage of homogeneous catalysis is that the catalyst mixes into the reaction 26
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mixture, allowing a very high degree of interaction between catalyst and reactant
molecules. However, unlike with heterogeneous catalysis, the homogeneous catalyst
is often irrecoverable after the reaction has run to completion.
Homogeneous catalysts are used in variety of industrial applications, as they allow for
an increase in reaction rate without an increase in temperature.

1. Co(II) as catalyst: The reaction of tartrate ions with hydrogen peroxide is an

example of an oxidation–reduction reaction. Hydrogen peroxide is a strong oxidizing
agent, resulting in the complete oxidation of tartrate ions to give carbon dioxide and
water.
The extent of this oxidative decomposition reaction is evident by the production of

carbon dioxide gas. Hydrogen peroxide initially oxidises the cobalt(II), Co 2+, to
cobalt(lll), Co3+. The cobalt(III) bonds to the tartrate ion, allowing the oxidation to
take place. The Co3+ is then reduced back to Co2+.
NaKC4H4O6 + 5H2O2 → 4CO2 + 6H2O + 2OH- (aq) + Na+(aq) + K+(aq)

C4H4O62- + 5H2O2 → 4CO2 + 6H2O + 2OH- (aq) (ionic form)
In the absence of a catalyst, the decomposition reaction, although thermodynamically

favourable, is kinetically very slow. Thus, even at 75 °C, the reaction occurs at a barely
noticeable rate.
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2. Acid catalysis: The reactant molecule may be protonated (for example using
sulphuric acid) to form some 'active' protonated intermediate e.g. a carbocation in the
case of adding water to alkenes to form alcohols.
Step 1: Alkene undergoes protonation to form carbocation by electrophilic attack
of H3O+. CH2=CHCH3 + H2SO4 → CH3-CH(OSO2OH)CH3
Step 2: Water, being a nucleophile, attacks on the carbocation.
CH3-CH(OSO2OH)CH3 + 2H2O → CH3-CH(OH)CH3 + H3O+ + HSO4-
Step 3: Deprotonation occurs to form an alcohol.
H3O+ (H+)(the electrophile from the acid) protonates the alkene to form the
carbocation).
3. Oxidation of iodide ions by peroxodisulphate:
The uncatalysed reaction overall is: (a) S2O82–(aq) + 2I– (aq) → 2SO42–(aq) + I2(aq)
This 'direct' uncatalysed reaction involves the collision of two highly repelling negative
ions and so has a very high activation energy (Ea3 in the diagram below).
BUT, the collision of an

Fe3+ ion and an I– ion
involves a positive ion–
negative ion attraction, 28
Page
reducing repulsion, so
this interaction which has
a much lower activation
energy.

Initially, the 1st step overall for the catalysed reaction is ... (Ea1 in diagram)
(b) 2Fe3+(aq) + 2I–(aq) → 2Fe2+(aq) + I2(aq)
Fe2+ is the 'intermediate', and in the 2nd step overall, it is oxidised to Fe3+ and the
peroxodisulphate ion is reduced to sulphate ion ... (Ea2 in diagram above)
(c) 2Fe2+(aq) + S2O82–(aq) → 2SO42–(aq) + 2Fe3+(aq)
So, the Fe3+ is regenerated in the cycle, showing the Fe3+/Fe2+ ions act in a genuine
catalytic cycle but remember it cannot be simply two steps, the above must represent
the summations of at least four steps.
Note 1: It doesn't matter whether you start with the Fe3+ or Fe2+ ion, catalysis will
occur because the peroxodisulphate would oxidise some Fe2+ to Fe3+ (reaction b) and
the Fe3+ then oxidises the iodide.
Note 2: If you added up the two equations (b + c) of the cycle you get equation (a)
showing the overall reaction change.
(b) 2Fe3+(aq) + 2I–(aq) → 2Fe2+(aq) + I2(aq)
(c) 2Fe2+(aq) + S2O82–(aq) → 2SO42–(aq) + 2Fe3+(aq)
(a) S2O82–(aq) + 2I– (aq) → 2SO42–(aq) + I2(aq)
Note 3: The full mechanism must be quite complex e.g. at least 4 steps because the
chances of three particles colliding in the right way (a termolecular collision) and with 29
Page
sufficient frequency is unlikely. Most mechanisms proceed by bimolecular collisions,

whatever the overall order of the reaction!
4. Esterification: Acids, proton donors (H+), catalyse the formation of an ester

from a carboxylic acid and alcohol, they also catalyse the reverse reaction of hydrolysis.

The reaction is actually an equilibrium; it’s common to see just “H+”, although H2SO4
(sulfuric acid) are also often used.
5. Friedel–Craft reactions: The alkylation and acylation of aromatic

hydrocarbons is catalysed by aluminium chloride or FeCl3.
6. Sulphur dioxide oxidation:
SO2 (g) + O2 (g) → SO3 (g) catalyst: NO (g)
In the presence of nitrogen monoxide, the overall reaction rate speeds up

dramatically
NO(g) + ½ O2 → NO2(g) NO as a catalyst
NO2(g) + SO2 → NO(g) + SO3( g) NO2 acts as intermediate
7. The 'catalytic cycle' of ozone destruction by chlorine atoms from

30
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CFC's
Ozone is destroyed by reactions with chlorine, bromine, nitrogen, hydrogen, and
oxygen gases. Reactions with these gases typically occurs through catalytic processes.
A catalytic reaction cycle is a set of chemical reactions which result in the destruction
of many ozone molecules while the molecule that started the reaction is reformed to
continue the process. Because of catalytic reactions, an individual chlorine atom can

on average destroy nearly a thousand ozone molecules before it is converted into a

form harmless to ozone.
(b) Heterogeneous catalysis: In heterogeneous catalysis, catalyst is present in a

different phase than that of reactants.
 A heterogeneous catalyst exists in a different phase from the reactant

molecules - often as a solid in contact with either a gaseous or liquid reactant
 Many important industrial reactions are catalyzed by the surfaces of special
solid materials
 Heterogeneous catalysts are often composed of metals or metal oxides
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 The greater the surface area of a heterogeneous catalyst, the more reactions
can take place. Thus, in manufacturing heterogeneous catalysts techniques are used
to maximize the surface area (e.g. using highly porous structures)
 The initial step in heterogeneous catalysis is the adsorption of reactants onto
the surface of a catalyst
 The surface of metal catalysts are highly reactive in comparison to interior atoms

The reaction occurs on the catalyst surface which may be the transition metal or
one of its compounds, Ni for example. The reactants must be adsorbed onto the
catalyst surface at the 'active sites'.
This can be physical adsorbed or 'weakly' chemically bonded to the catalyst surface.
Either way, it has the effect of concentrating the reactants close to each other
and weakening the original intra–molecular bonds within the reactant molecules
and so allows a greater chance of successful collision.
The diagram below illustrates a typical heterogeneous catalysis e.g. hydrogenation of
alkenes with hydrogen and a nickel catalyst.
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33
Strength of adsorption / catalyst:
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The strength of adsorption is crucial to having a productive catalyst surface:

The bonding to the catalyst surface (chemisorption/adsorption) must be strong
enough to weaken reactant molecule bonds but weak enough to allow new bonds to
form and the products to 'escape' from the catalyst surface (desorption).
Typical examples to illustrate this idea ....

▪ If the catalyst–reactant bonding is too strong, most reactant/product molecules will

be too strongly 'chemisorped' inhibiting reaction progress e.g. tungsten (W),
▪ If the catalyst–reactant bonding is too weak, many reactants are not chemisorbed
strongly enough to allow the initial bond breaking processes to happen.
(Au) and (Ag) tend to be more limited catalysts, but even silver, can act as a catalyst for
some reactions.
just right: (Cu), (Ni), (Pt), (Rh), (Pd) catalyse many reactions such as hydrogenation,
redox reactions involving CO and NO etc. Palladium can catalyse the spontaneous
combustion/combination of hydrogen and oxygen at room temperature!
Examples of Heterogeneous catalysis
1) Potassium chlorate decomposition:

When solid potassium chlorate is heated, potassium chloride and oxygen are 34
Page
produced.
2 KClO3 (s) → 2 KCl (s) + 3 O2 (g)
Catalyst: MnO2 (s), faster and lower temperature
2) Hydrogen peroxide decomposition:

2H2O2(aq) → 2H2O(l) + O2(g)

Catalyst: MnO2(s)
3) Iron, Fe(s), catalyses the combination of nitrogen and hydrogen gases in the
important industrial Haber synthesis of ammonia, important in the manufacture of
nitric acid and artificial fertiliser salts such as ammonium sulphate and ammonium
nitrate.
N2(g) + 3H2(g) 2 NH3(g) ∆H = -92 KJ mol-1
Fe used as catalyst. The catalyst is
actually slightly more complicated
than pure iron.
The Haber process is used by the
chemical industry to manufacture
ammonia which is used to make nitric
acid and fertilisers. The raw materials
for the Haber process are nitrogen from
air and hydrogen is usually obtained
from natural gas. The purified gases are
passed over a catalyst of iron at a high
temperature (typically 450°C) and a
very high pressure (typically 200
35
atmospheres). Some of the hydrogen
Page
reacts with nitrogen reacts to form
ammonia.
A set of optimum conditions to get the most efficient yield of ammonia and this
involves getting a low % yield (e.g. 8% - 15% conversion) but fast using an iron
catalyst.

Optimum conditions for Haber Process:

High pressure: (typically 200 atmospheres) because you are going from 4 to 2 gas
molecules, so high pressure favours the forward reaction to give fewer gas molecules.
But, the higher pressure means more dangerous and more costly engineering, so a
compromise needed.
High temperature: (typically 450°C) because the reaction is exothermic so, the low
temperature favours the yield of the ammonia, but the problem is the reaction is very
slow at low temperature and that is why the high temperature is.
So, high temperature and high pressure with using a catalyst we can get an optimum
condition.
4) Platinum: Manufacture of Nitric acid:

Nitric acid production involves two stages:
(a) Oxidation of ammonia
Most plants operate with: an alloy of platinum and rhodium as catalyst: a series
of 90% platinum/10% rhodium catalyst gauzes in parallel at 975-1225 K
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(b) Absorption of the nitrogen oxides
Air is added and the gases compressed again (7-12 atm typically). The gases (NO2 &
N2O4) are then passed through one or more towers to meet a stream of water with the
formation of nitric acid:
Rhodium is added to the platinum to give the gauze strength and to reduce the loss
of platinum. Recently, it has been found that knitted gauze increases the efficiency
of conversion and prolongs the life of the catalyst.
5) Platinum/rhodium/palladium metals, Pt(s)/Rh(s)/Pd(s),on a ceramic

support, catalyse the following reactions in car exhausts inside the catalytic
converter.
CO(g) + O2 → CO2(g)
NO(g) → N2(g) + O2(g)
The overall reaction is:
2NO(g) + 2CO(g) → N2(g) + 2CO2(g)

Catalytic converters change harmful substances in a car’s exhaust gasses, such as carbon
monoxide, nitric oxide, nitrogen dioxide and hydrocarbons, into less harmful 37
Page
substances like carbon dioxide and water vapour by means of chemical reactions.
Source of carbon monoxide: The CO is from the inefficient combustion of the

hydrocarbon fuel,
CxHy + (x/2 + y/4)O2 􀃆 xCO + y/2H2O

Source of nitrogen(II) Oxide: The nitrogen(II) oxide is 'naturally' formed at high

temperature in the engine (as it is in lightning strikes!).
N2(g) + O2(g) → 2NO(g)
The NO and CO are adsorbed onto the catalyst surface, bonds broken and reformed
prior to the products nitrogen and carbon dioxide leaving the catalyst surface leaving
the exhaust as N2 and CO2
These transition metal catalysts can also oxidise unburned hydrocarbons from
inefficient combustion.
CxHy + (x + y/4)O2 → xCO2 + y/2H2O
Catalytic converters need to work at high temperatures of up to 400 oC to maximise
their efficiency. To achieve this optimum operating temperature the unit were
positioned down the exhaust system, away from the engine’s heat source.
Types of catalytic converters

There are various types of catalytic converter. A simple ‘two-way’ oxidation cat works
to turn carbon monoxide (CO) to carbon dioxide (CO2) and hydrocarbons, which are
basically particles of unburnt fuel, to carbon dioxide and water. More advanced
‘three-way’ catalytic converters are fitted to modern cars and these do the above while
also reducing emissions of nitric oxide (NO) and nitrogen dioxide (NO 2) which
together are more commonly known as NOx, a major cause of localised air pollution.
Note: Pt, Rh and Pd are very expensive metals and copper and nickel are cheaper 38
Page
alternatives but they are vulnerable to catalytic poisoning by traces of sulphur dioxide
in the exhaust gases. Once poisoned, the catalyst in a converter cannot be regenerated,
so, its a new costly converter!

6) Nickel, Ni(s), catalyses the addition of hydrogen to an alkene double bond, e.g.
in the hydrogenation of unsaturated vegetable oils to make more saturated
margarine.
–CH=CH– + H2 → Ni catalyst → –CH2–CH2–
7) Solid heterogeneous catalysts are really important in the petrochemical
industry:
i- Isomerisation: These reactions convert linear alkane vapours into branched
alkanes of the same carbon number over a platinum–aluminium oxide (Pt/Al2O3)
catalyst at 150 oC.
Branched alkanes have a higher-octane rating than linear alkanes, so a better petrol
fuel components.
e.g. hexane → methylpentanes or dimethylbutanes
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ii- Reforming: Converting straight chain alkane vapour into cyclic alkanes and
aromatic hydrocarbons can be achieved by using a Pt/Al 2O3 catalyst at 500 oC.
Aromatic hydrocarbons are important chemical feedstock to make many useful
aromatic compounds.
Example:
iii- Cracking: Catalytic cracking of vapourised hydrocarbons at e.g. 500 oC using

zeolites to make more lower alkanes for petrol or alkenes. Alkenes are important
intermediates in making many useful compounds from antifreeze to plastics.
e.g. higher alkanes → lower alkanes and alkenes
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Note: Zeolites tend to become 'poisoned' with carbon–soot deposits in the high
temperature cracking reactions and this blocks the adsorption of the hydrocarbons.
However, in this case, the catalyst can be regenerated in a separate container through
which very hot air is passed to burn off the carbon–soot deposits.

Catalytic Cracking Catalytic Reforming

Is the breakdown of large compounds Is the process of converting low octane
into smaller hydrocarbons in the naphtha into high-octane reformate
presence of a catalyst products
Most commonly used catalyst is Zeolite Most commonly used catalysts are
Platinum or Rhenium on a silica base
Includes the breakdown of larger Includes the rearrangement of
hydrocarbons into smaller hydrocarbons hydrocarbons in order to form different
products
Feed is distillates obtained from crude Feed is naphtha feedstock
oil distillation
Mainly gives small alkanes and alkenes Mainly gives isomerised and aromatic
products
8) Vanadium(V) oxide, V2O5, is used as a catalyst in the 'Contact Process'

in the production of sulphur trioxide for the manufacture of sulphuric acid.
The catalysing of the conversion of sulphur dioxide into sulphur trioxide is explained
via change in oxidation state changes.
2SO2(g) + O2(g) → 2SO3(g) (S4+ → S6+; change in oxidation number)
The mechanism, somewhat simplified, it goes via the catalytic cycle ...
(i) SO2 + V2O5 → SO3 + V2O4, then
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(ii) V2O4 + 1/2O2 → V2O5

(The vanadium changes its oxidation state from +5 to +4 and back to +5 in the cycle.)
The following comparing the advantages and disadvantages of homo- and

heterogeneous catalysis:

Advantages Disadvantages
Catalyst needs to be separated

after reaction
Homogeneous
Good contact with reactants
catalysis Catalyst recovery may be difficult
because the temperature for the
distillation can destroy the
catalyst
There is a lower effective

There is little difficulty in
Heterogeneous concentration of catalyst since the
separating and recycling the
catalysis reaction occurs only on the
catalyst.
exposed active surface.
Reaction Rate and catalyst:

If a catalyst is to increase the reaction rate, k, it would appear to be able to do so by
one of two ways:
1. Increase the frequency factor, A, ( 𝑘 = 𝐴𝑒 −𝐸𝑎/𝑅𝑇 ) or ln K = ln A – Ea / RT
The Arrhenius equation states that the rate constant, k, of a reaction is
I. directly proportional to the frequency factor (A),
II. inversely proportional to the activation energy Ea, and
III. directly proportional to the temperature). (i.e. in some way increase the rate
of successful molecular collisions)
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2. Decrease the activation energy, Ea

In generally, a catalyst typically increases reaction rates by lowering the activation
energy, Ea. This is related to the energy required to stretch and break a bond; thus,
catalysts must facilitate this process in some way.

Also, a catalyst often lowers the overall activation energy for a reaction by providing a
completely different reaction mechanism for the reaction. In other words, a different
set of underlying elementary reaction steps.
Catalyst (Catalytic) Cycle:

A catalytic cycle in chemistry is a term for a multistep reaction mechanism that involves
a catalyst. The catalytic cycle is the main method for describing the role of catalysts in
chemistry. Since catalysts are regenerated, catalytic cycles are usually written as a
sequence of chemical reactions in the form of a loop. In such loops, the initial step
entails binding of one or more reactants by the catalyst, and the final step is the release
of the product and regeneration of the catalyst.
Autocatalysis:
When one of the products of a reaction acts as catalyst, the process is called
autocatalysis.
Examples of autocatalysis include:
1. The reaction of permanganate with oxalic acid,
One of the simplest examples of this is in the oxidation of a solution of ethanedioic
acid (oxalic acid) by an acidified solution of potassium manganate(VII) (potassium
permanganate).
43
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The reaction is very slow at room temperature. The reaction is catalysed by

manganese(II) ions. The manganese(II) ions amongst the products. More and more
catalyst is produced as the reaction proceeds and so the reaction speeds up.
2. The acid-catalyzed hydrolysis of ethyl acetate into ethanoic acid and ethanol
CH3CH2CO2CH3 + H2O = CH3CH2OH + CH3CO2H
3. Spontaneous degradation of aspirin into salicylic and ethanoic acid (causing old
aspirin containers to smell mildly of vinegar).
The ethanoic acid released from the aspirin will cause some accelerated degradation of
our ibuprofen (act as auto catalyst) 44
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Characteristics of Catalysts
1. The catalyst remains unchanged in mass and chemical composition.
2. In case of reversible reactions, the catalyst does not influence the composition of
reaction mixture at equilibrium. It only helps to attain the equilibrium quickly.
3. The catalyst changes the chemical kinetics of a reaction but not the chemical
thermodynamics.
4. A catalyst does not lower the activation energy for a reaction, instead it provides an
alternative path for the reaction that has a lower activation energy.
5. The reaction equilibrium constant (which is a function of the Gibbs free energies of
reactants and products only) is not affected by the catalyst.
Promoters (activators)
Promoters are chemical substances that enhance the activity of a catalyst. Substances
which themselves are not catalysts, but when mixed in small quantities with the
catalysts increase their efficiency are called as promoters or activators.
Examples,
1. In Haber’s process for the synthesis of ammonia, traces of molybdenum (act as
Promoters) increases the activity of finely divided iron which acts as a catalyst.
45
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N2 (g) + 3 H2 (g) → 2 NH3 (g) (Fe as catalyst with Mo as promoter)
2. In the manufacture of methyl alcohol from water gas, chromic oxide is used as a
promoter with the catalyst zinc oxide.
CO (g) + 2 H2 (g) → CH3-OH (l) (ZnO as catalyst with Cr2O3 as promoter)

Catalytic poisons
Decreases the activity of a catalyst. Substances which destroy the activity of the catalyst
by their presence are known as catalytic poisons. For example:
i The presence of traces of arsenic(III) oxide (As2O3) in the reacting gases reduces the
activity of platinized asbestos which is used as catalyst in contact process for the
manufacture of sulphuric acid.
ii The activity of iron catalyst is destroyed by the presence of hydrogen sulphide, H2S,
or carbon monoxide, CO, in the synthesis of ammonia by Haber’s process.
iii The platinum catalyst used in the oxidation of hydrogen is poisoned by carbon
monoxide, CO.
Effect of temperature on catalyst activity:

Change of temperature alters the rate of catalytic reaction as it does for the same
reaction in absence of catalyst. By increasing the temperature, there is an increase in
the catalytic power of a catalyst but after a certain temperature its power begins to
decrease. A catalyst has thus, a particular temperature at which its catalytic activity is
maximum. This temperature is termed as optimum temperature.
Negative Catalyst (Inhibitor or Retarder)

A catalyst may be positive (i.e., increases rate of reaction) or negative (i.e., decreases
rate of reaction).
Chemical reactions are retarded by the presence of foreign substances and these
substances are negative catalysts. A few examples of negative catalysts are: 46
Page
• Phosphoric acid labours as a negative catalyst for the decomposition of H202

• Alcohol acts as a negative catalyst in the oxidation of Na2SO3
Mechanism of Heterogeneous Catalysis

1. Diffusion of reactants to the surface of the catalyst.

2. Adsorption of reactant molecules on the surface of the catalyst.

3. Chemical reaction on the surface through the formation of the intermediate.
4. Desorption of the products from the catalyst surface.
5. Diffusion of the products away from the catalyst's surface
The suitability of a catalyst

The suitability of a catalyst for an industrial process depends mainly on the following
three properties:
– Activity – Selectivity – Stability (deactivation behaviour)
The question which of these functions is the most important is generally difficult to
answer because the demands made on the catalyst are different for each process.
i. Activity: Activity is the ability of catalysts to accelerate chemical reaction, the

degree of acceleration can be as high as times in certain reactions
Activity of given catalyst is a measure of how fast reaction (or reactions)
proceeds in the presence of the catalyst. The activity of a catalyst depends upon the
strength of chemisorption to a large extent. The adsorption should be reasonably
strong but not so strong that they become immobile and no space is available for other
reactants to get adsorbed.
ii. Selectivity: The selectivity of a catalyst is its ability to direct a reaction to yield a
particular product, e.g., starting with H2 and CO using different catalysts, we get
different products. 47
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Reactants Products Catalyst used

CO (g) + 3 H2 (g) → CH4 (g) + H2O (g) Ni
CO (g) + 2 H2 (g) → CH3-OH (l) Cu, ZnO-Cr2O3
CO (g) + H2 (g) → HCHO (g) Cu

As seen from these examples, different catalysts might give different products for the
same reactants
The selectivity of a reaction is the fraction of the starting material that is converted to
the desired product. It is expressed by the ratio of the amount of desired product to
the reacted quantity of a reactant and therefore gives information about the course of
the reaction. It is the ability of the catalyst to direct a reaction to yield a particular
product
𝐀𝐦𝐨𝐮𝐧𝐭 𝐨𝐟 𝐝𝐞𝐬𝐢𝐫𝐞𝐝 𝐩𝐫𝐨𝐝𝐮𝐜𝐭
Selectivity of catalyst =
𝐐𝐮𝐚𝐧𝐭𝐢𝐭𝐲 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 𝐨𝐟 𝐭𝐡𝐞 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭
There are various kinds of product selectivity:
 Chemical selectivity, or chemo-selectivity, denotes a situation where two

different chemical reactions can occur, giving two different products.
Similarly, regio-selectivity occurs when the same chemical reaction in different
regions of the molecule leads to different products. When a reaction gives two (or
more) diastereomers, the selectivity to each of these is called diastereo-
selectivity.
A diastereomer is a stereoisomer with two or more stereo-centres and the
isomers are not mirror images of each other.
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Distereo isomers formed, cis and trans, This reaction is distereo selective reaction

In the special case when two products are mirror-image

diastereomers, or enantiomers, we talk about enantio-
selectivity
One enantiomer is an optical stereoisomer of another
enantiomer. The two molecules are mirror images of each
other, which are not superimposable - much like your left
and right hand.
 Shape–selective catalysis: The catalytic reaction that depends upon the pore
structure of the catalyst and the size of the reactant and product molecules is called
shape-selective catalysis.
Example: Cracking Isomerization of hydrocarbons in the presence of zeolites is an
example of shape-selective catalysis.
An important zeolite catalyst used in the petroleum industry is ZSM-S. lt converts
alcohols directly into gasoline.
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iii. Catalytic activity (Stability)

Is usually denoted by the symbol (z) and measured in mol s-1, a unit which was called
katal and defined the SI unit for catalytic activity.
Catalytic activity is not a kind of reaction rate, but a property of the catalyst under
certain conditions, in relation to a specific chemical reaction.
Catalytic activity of one katal (Symbol 1 kat = 1 mol s-1) of a catalyst means
an amount of that catalyst (substance, in mol) that leads to a net reaction of
one mol per second of the reactants to the resulting reagents or other
outcome which was intended for this chemical reaction.
A catalyst may and usually will have different catalytic activity for distinct reactions.
Catalysts that lose activity during a process can often be regenerated before they
ultimately have to be replaced. The total catalyst lifetime is of crucial importance for
the economics of a process.
Deactivation of catalyst
Catalyst deactivation, the loss over time of catalytic activity and/or selectivity, is a
problem of great and continuing concern in the practice of industrial catalytic
processes. Typically, the loss of activity in a well-controlled process occurs slowly.
However, process upsets or poorly designed hardware can bring about catastrophic
failure. For example, in steam reforming of methane or naphtha great care must be
taken to avoid reactor operation at excessively high temperatures or at steam to 50
Page
hydrocarbon ratios below a critical value. Indeed, these conditions can cause
formation of large quantities of carbon filaments which plug catalyst pores and voids,
pulverize catalyst pellets, and bring about process shut down all within a few hours.

The mechanisms of catalyst deactivation are many; nevertheless, they can be

grouped into six intrinsic mechanisms of catalyst decay: (i) poisoning, (ii) fouling,
(iii) thermal degradation, (iv) vapor compound formation accompanied by
transport, (v) vapor–solid and/or solid–solid reactions, and (vi)
attrition/crushing.
Causes of solid (heterogeneous) catalyst deactivation are basically threefold:

(1) Chemical, (2) Mechanical, and (3) Thermal
The reversibly poisoned or fouled catalysts are relatively easily regenerated. On the
other hand, chemical, mechanical, and thermal forms of catalyst degradation are rarely
reversible.
Mechanisms of catalyst deactivation
Mechanism Type Brief definition/description
Strong chemisorption of species on catalytic

Poisoning Chemical sites, thereby blocking sites for catalytic
reaction
Physical deposition of species from fluid phase

Fouling Mechanical
onto the catalytic surface and in catalyst pores
Thermally induced loss of catalytic surface

Thermal degradation Thermal area, support area, and active phase–support
reactions
Reaction of gas with catalyst phase to produce 51

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Vapor formation Chemical
volatile compound
Vapor–solid and solid– Reaction of fluid, support, or promoter with

Chemical
solid reactions catalytic phase to produce inactive phase
Attrition/crushing Mechanical Loss of catalytic material due to abrasion

Loss of internal surface area due to

mechanical-induced crushing of the catalyst
particle
 Poisoning:
Poisoning occurs when there is a strong chemical interaction of reactants, products, or
impurities with active sites on the catalyst surface. Sulphur Poisoning being the most
widely cited example. Thus, poisoning has operational meaning; that is, whether a
species acts as a poison depends upon its adsorption strength relative to the other
species competing for catalytic sites. For example, oxygen can be a reactant in partial
oxidation of ethylene to ethylene oxide on a silver catalyst and a poison in
hydrogenation of ethylene on nickel. In addition to physically blocking adsorption
sites, adsorbed poisons may induce changes in the electronic or geometric structure of
the surface. Catalyst can be poisoned by reactants, products, and impurities.
Many poisons affect reforming catalysts including sulphur, metals, halides and
phosphates. Sulphur is a particular problem because:
 nickel is a very good sulphur adsorbent
 only a small amount of sulphur can cause problems
 sulphur can totally deactivate a reforming catalyst
 sulphur- and arsenic-containing compounds are typical poisons for metals in
hydrogenation, dehydrogenation and steam reforming reactions.
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The good news is that sulphur poisoning is reversible. Steam can be used to slowly
strip off the sulphur over a period of 24 hours. The less good news is that the catalyst
may lose some of its activity permanently. The effective answer is to remove sulphur
from the feedstock gases before they enter the reformer tube.
Some other examples of poisoning

◼ Organic bases (e.g. amines) and ammonia are common poisons for acidic solids
such as silica-alumina and zeolites in cracking and hydrocracking reactions.
◼ Metal compounds (e.g. Ni, Pb, V and Zn) are poisons in automotive emissions
control, catalytic cracking and hydrotreating.
◼ Acetylene is a poison for ethylene oxidation, while asphaltenes are poisons in
hydrotreating of petroleum residual.
Selective poisoning: A chemical directly reacts with the active site or the carrier,
rendering it less or completely inactive. “Selective” poisoning involves preferential
adsorption of the poison on the most active sites at low concentrations.
An example of selective poisoning is the deactivation of platinum by CO for the

para-H2 conversion
Nonselective poisoning: Deposition of fouling agents onto or into the catalyst

carrier, masking sites and pores, resulting in a loss in performance. If the activity loss
is proportional to the concentration of adsorbed poison, the poisoning is “non-
selective”.
Arsenic poisoning of cyclopropane hydrogenation on Pt is non-selective

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 Fouling (coking and carbon deposition)

(very common for reactions involving hydrocarbons). The deposit of unwanted
materials on a surface is defined as fouling and affects how a chemical process proceeds.
Fouling adds a layer of organic, inorganic or even living organisms to the surface which 54
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affects the properties of the catalyst and the mechanism of the process.
Coke formation is one of the most prominent types of catalytic fouling and is chiefly
involved in the deactivation of a catalyst. This coke formation forms a fouled layer on
the surface of a catalyst which reduces how much of the surface area of the catalyst is

available to the surroundings. With less surface area exposed, a catalyst is less effective.
secondary reactions of reactants or products, coke formation.
✓ Coking can be reduced by running at high pressure & hydrogen-rich feeds

✓ Catalyst deactivated by coking is often regenerated by burning off the carbon
Carbon is typically a product of CO disproportionation while coke is produced by

decomposition or condensation of hydrocarbons on catalyst surfaces and typically
consists of polymerized heavy hydrocarbons.
Possible effects of fouling by carbon (or coke) on the functioning of a

supported metal catalyst:
Carbon may (1) chemisorb strongly as a

monolayer or physically adsorb in
multilayers and in either case block access 55
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of reactants to metal surface sites,
(2) totally encapsulate a metal particle and

thereby completely deactivate that
particle, and

(3) plug micro- and mesopores such that access of reactants is denied to many
crystallites inside these pores.
Finally, in extreme cases, strong carbon filaments may build-up in pores to the extent
that they stress and fracture the support material, ultimately causing disintegration of
catalyst pellets and plugging of reactor voids.
 Thermal degradation and sintering
For a catalyst to be effective it must have an effective interface with the reactants, thus
heterogeneous catalysts are prepared with high surface areas. Large surface areas are
thermodynamically unstable, thus given suitable conditions such as high temperatures
the catalysts will rearrange to form the most favourable lower surface area
agglomerates. These rearrangements are often accelerated by particular chemical
environments. For example, moist atmospheres accelerate structural changes in oxide
catalyst supports. This agglomeration of catalysts is known as sintering, which causes
a decrease in the availability of active sites on a catalyst
 Attrition (crushing) (Mechanical failure of catalysts)

➢ Loss of catalytic material due to abrasion.
➢ Loss of internal surface area due to mechanical-induced crushing of the
catalyst particle.
Loss of catalytic material due to abrasion; loss of internal surface area due to
mechanical-induced crushing of the catalyst particle. Mechanical failure of catalysts is
observed in several different forms that depend on the type of reactor, including: 56
Page
(1) crushing of granular, pellet, or monolithic catalyst forms due to a load in fixed
beds;
(2) attrition, the size reduction, and/or breakup of catalyst granules or pellets to
produce fines, especially in fluid or slurry beds; and

(3) erosion of catalyst particles or monolith coatings at high fluid velocities in any
reactor design.
The main consequence of attrition is the generation of fines and the resulting loss of
valuable material.
Attrition is evident by a reduction in the particle size or a rounding or smoothing of

the catalyst particle easily observed under an optical or electron microscope.
 Corrosion / leaching
The active sites of a catalyst may become inactive by the adsorption of impurities in
the feed stream.
57
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Turnover Number (TON)
In catalysis, the term turnover number, TON, has two meanings:
 the number of moles of substrate that a mole of catalyst can convert before
becoming inactivated ( mol of substrate / 1 mol of catalyst) and
 is the amount of substrate converted per the amount of catalyst used.

In other words, the turnover number is defined as the absolute number of passes
through the catalytic cycle before the catalyst becomes deactivated. (TON has no unit)
In theory, the Ideal catalyst would have an infinite turnover number and would never
be consumed. In practice, turnover numbers begin at 100 and can go up to a million,
more so in some cases.
The lifetime of the catalyst, and therefore its stability, are measured in terms of its
TON
In general, industrial chemists are interested in both TON and turnover frequency
(TOF) (see the next section). A large TON (e.g., 106–1010) indicates a stable, very
long-lived catalyst. The TON can be calculated by dividing the amount of reactant
(moles) by the amount of catalyst (moles):
This assumes a yield of the product of 100%, which is most often not the case. To
calculate the true number of turnovers, the yield obtained needs to be considered.
For example, if 10 mol of reactant and 2.5 mol of catalyst are used, then the TON
becomes
If the yield of the product is 94%, then the actual number of turnovers is
58
𝐦𝐨𝐥 𝐬𝐮𝐛𝐬𝐭𝐫𝐚𝐭𝐞
𝐓𝐎𝐍 = %𝐜𝐨𝐧𝐯 𝐱 Page
𝐦𝐨𝐥 𝐜𝐚𝐭𝐚𝐥𝐲𝐬𝐭
𝟏𝟎
𝐀𝐜𝐭𝐮𝐚𝐥 𝐓𝐎𝐍 = 𝟎. 𝟗𝟒 𝐱 = 𝟑. 𝟕𝟔
𝟐. 𝟓
Turnover Frequency (TOF):
Turnover frequency is defined as the number of passes through the catalytic cycle
per unit time (typically seconds, minutes or hours).

This number is usually determined by dividing the TON by the time required to
produce the given amount of product.
𝐓𝐎𝐍
𝐓𝐎𝐅 =
𝐓𝐢𝐦𝐞
However, as with the TON, the actual yield of the product also needs to be
considered. Continuing the example above, if the reaction in question was run for 7
hours to obtain the 94% yield, the TOF is
A catalyst’s turnover frequency number, or turnover number per time unit,

characterizes its level of activity. So, the TOF is the total number of moles transformed
into the desired product by one mole of active site per hour. The larger the TOF, the
more active the catalyst.
In theory, the Ideal catalyst would have an infinite turnover number and would never
be consumed. In practice, turnover numbers begin at 100 and can go up to a million,
more so in some cases.
Example: 10 mmols of substrate are converted to product using a catalyst

loading of 0.2 mmols in 2 hours. .
TON = 10 / 0.2 = 50 TOF = 50 / 2 h = 25 h-1
Note that the TON is always a pure number (unitless), while the TOF has units of
time–1.
59
Page
Number of turnovers performed – more is better; TOF (turnover frequency) – faster
is better
Q: Why technologists are interested in TOF and TON?
A: because both give idea about the activity and stability of the catalyst. Number of
turnovers performed – more is better; TOF (turnover frequency) – faster is better. The

catalyst turnover number (TON) and the turnover frequency (TOF) are two
important quantities used for comparing catalyst efficiency.
Enzymes as catalyst
Enzymes are biological catalysts and will only catalyze one reaction involving one
molecule or pairs of molecules. This is known as specificity. The enzyme has an
active site which is a specific location that a molecule called a substrate fits into. This
is known as the "lock and key model".
Enzymes work best at their optimum temperature. This is why homeostasis is

important - to keep our body temperature at a constant 37°C.
As the temperature increases, so does the rate of chemical reaction. This is because
heat energy causes more collisions,
with more energy, between the
enzyme molecules and other 60
Page
molecules. However, if the

temperature gets too high, the
enzyme is denatured and stops
working.

Only molecules with the correct shape can fit into the enzyme. Just like only one
key can open a lock, only one type of enzyme can speed up a specific reaction
Enzyme Catalyst Kinetic:
In a mathematical description of enzyme action developed by Leonor Michaelis and

Maud Menten in 1913, two constants, Vmax and Km, play an important role.
These constants are important to know, both to understand enzyme activity on the
macroscale and to understand the effects of different types of enzyme inhibitors.
Maximal Velocity (Vmax): Increasing the substrate concentration indefinitely does

not increase the rate of an enzyme-catalyzed reaction beyond a certain point. This
point is reached when there are enough substrate molecules to completely fill
(saturate) the enzyme's active sites. The maximal velocity, or Vmax, is the rate of the
reaction under these conditions. Vmax reflects how fast the enzyme can catalyze the
reaction.
Michaelis Constant (Km): Enzymes have varying tendencies to bind their

substrates (affinities). An enzyme's Km describes the substrate concentration at which
half the enzyme's active sites are occupied by substrate. A high Km means a lot of
substrate must be present to saturate the enzyme, meaning the enzyme has low
affinity for the substrate. On the other hand, a low Km means only a small amount
of substrate is needed to saturate the enzyme, indicating a high affinity for substrate.
Click on the image at right to see how high Km and low Km enzymes compare.
Graphically, the Km is the substrate concentration that gives the enzyme one-half of
61
Page
its Vmax. Although it may look like the Vmax drops, if the graph is extended along
the x-axis, the Vmax stays constant for the two enzymes described here.
A lower Km value indicates that an enzyme has a higher affinity for a substrate.

Questions and Answers
1. Why a adsorption process is always exothermic
Ans.: Adsorption is spontaneous process, therefore change in free energy (ΔG) is

negative. ΔG = ΔH – TΔS, For the negative value of ΔG, in a system, in which
randomness decreases, ΔH must be negative. Hence, adsorption is always
exothermic.
2. What are catalysts?
Ans.: Catalysts are substances that reduce the activation energy of a chemical reaction,
facilitating it or making it energetically viable. The catalyst increases the speed of the
chemical reaction
3. What is meant by saturation of the enzyme?

Ans.: Saturation of the enzyme means that all of the Enzyme (E) is bound to
Substrate (S) and no free E exists. The enzyme has bound to as much substrate as
possible. This situation occurs at high levels of S.
62
Page
4. What is the chemical basis of enzyme specificity?
Ans.: The chemical basis of enzyme specificity is the complimentary relationship

between the enzyme active site and the substrate that binds in that site. This
complementarity involves a structural fit of the S into the E active site (a "lock and
key" kind of fit) and a chemical complementarity. For example if the E has H-bond

donating groups, the S will have H-bond accepting groups and vice versa, or that
there will be an opposite charge relationship between groups on the E and S. In
addition of there are nonpolar groups on the S, the E will have a nonpolar region
into which these groups will fit.
5. Identify the correct statement regarding enzymes:

A. Enzymes are specific biological catalysts that cannot be poisoned.
B. Enzymes are normally heterogeneous catalysts that are very specific in action
C. Enzymes are specific biological catalysts that can normally function at very high
temperature (T - 1000K).
D. Enzymes are specific biological catalysts that possess well defined active sites
6. According to adsorption theory of catalysis, the speed of the reaction

increases because:
A. adsorption produces heat which increases the speed of the reaction.
B. in the process of adsorption, the activation energy of the molecules becomes large.
C. the concentration of the reactant molecules at the active centres of the catalyst
becomes high due to adsorption.
D. adsorption lowers the activation energy of the reaction
63
Page

Duhok Polytechnique University Petrochemical Department Catalyst Science and Technology Lecturer: DR Farhad M. Ali 2020-2021

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4th Year Stage Catalyst Science and Technology

Duhok Polytechnique University

Catalyst Science and Technology

Lecturer: Dr Farhad M. Ali

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Chemical Kinetics; Rate of Reaction

• Molecules or atoms of reactants must collide with each other in chemical

• The molecules must have sufficient energy (discussed in terms of activation

Reaction Rates: how fast the concentration of a reactant or product changes

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

has been found to be directly proportional to the concentration of N2O5:

k = rate / [N2O5] (k is rate constant)

Keq = [NO2]4 [ O2] / [N2O5]2 (keq is equilibrium constant)

Chemical reaction rates are the rates of change in concentrations or

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

▪ Very fast reaction: explosion

Measuring Rate of Reactions:

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

❑ a volume of gas is given off

How can rate of reaction be measured?

Mg (s) + HCl (aq) → MgCl2 (aq) + H2 (g)

⚫ The amount of hydrochloric acid used up (cm3 min-1).

Average, Instantaneous, and Initial Reaction Rate:

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Average rate: rate of a chemical reaction computed as the ratio of a

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

2. The instantaneous rate of reaction, denoted as dC / dt.

Note: Instantaneous rates are also known as differential rates.

Alternatively, experimenters can measure the change in concentration over a very

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Instantaneous rate: rate of a chemical reaction at any instant in time,

We determine an instantaneous rate at time t:

• by calculating the negative of the slope of the curve of concentration of a

An instantaneous rate is a differential rate: -d[reactant] / dt or d[product] / dt.

Relative Rates of Reaction

2 NH3 (g) → N2 (g) + 3 H2 (g)

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Note that a negative

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

After 38.5 s of the start of the reaction, [Fe2+] is found to be 1 X 10-3 M.

a. rate of formation of Fe2+:

[ Fe2+] /  t = 1 X 10-3 M / 38.5 s = 2.6 X 10-5 M s-1

½ X 2.6 X 10-5 M s-1 = 1.3 X 10-5 M s-1

c. rate of disappearance of Fe3+:

[ Fe3+] /  t = [ Fe2+] /  t = - 1 X 10-3 M / 38.5 s = - 2.6 X 10-5 M s-1

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

d. rate of disappearance of Sn2+:

½ X 2.6 X 10-5 M s-1 = - 1.3 X 10-5 M s-1

Now, the question is:

Rate of reaction = - 1/a [A] / t

Thus, the rate for this reaction is

Rate of reaction = - ½ [ Fe3+] /  t 11

= 1.3 X 10-5 M s-1

DR FARHAD M. ALI CATALYST SCIENCE and TECHNOLOGY-2020-2021

Example 2: Suppose that at some point in the reaction:

Average rate = Change in concentration / time or

1/3 X [B] / t = - 1/3 X (- 0.0240 mol dm-3 / 13.20 min)

= 6.06 X 10-4 mol dm-3 min-1

Example 3: For the oxidation of ammonia