Design, Synthesis, Characterization and

Applications of Catalyst

Chamila Gunathilake
Department of Chemical & Process Engineering
University of Peradeniya
 Overview
➢Chemical Kinetics-Rate of reaction
➢Introduction to Catalyst
➢Principles of homogeneous and heterogeneous catalysis
➢Parameters important in determining catalytic activity
➢Synthesis & Designing of new catalyst
➢Modern techniques for characterization of catalyst
➢Industrial applications of catalyst
Recommended Texts:
Industrial Catalysis A Practical Approach: Jens Hagen, WILEY-VCH Verlag
GmbH & Co. KGaA, 2006
Catalysis Concepts and Green Applications: Gadi Rothenberg,, WILEY-VCH
Verlag GmbH & Co. KGaA, 2008.
• Basis and Applications of Heterogeneous Catalysis: Mike Bowker, Oxford
Primer, (1998).
• Catalytic Chemistry: B.C.Gates, Wiley (1992).

3
What does rate of reaction mean?
The speed of different chemical reactions varies hugely.
Some reactions are very fast and others are very slow.
The speed of a reaction is called the rate of the reaction.
What is the rate of these reactions?
rusting baking explosion

slow fast very fast

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Chemical Kinetics
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 Reaction Rate
• The rate of a reaction is expressed as the change in reactant
concentration with time.
• Consider the stoichiometrically simple reaction
➢The rate can be expressed also in terms of the appearance of a product
➢In this case, we have [P]2>[P]1.
➢ In practice, it finds that the quantity of interest is not the rate over a certain
time interval because this is only an average quantity whose value depends
on the particular value of Δt;
➢Rather, it is interested in the instantaneous rate. In the language of calculus,
as Δt becomes smaller and eventually approaches zero, the rate of the
foregoing reaction at a specific time t is given by
 Reaction Order
➢The relationship between the rate of a chemical reaction and the
concentrations of the reactants is a complex one that must be determined
experimentally
➢The reaction is x order with respect to A and y order with respect to B.
➢Thus, the reaction has an overall order of x+y.
➢ It is important to understand that, in general, there is no connection between
the order of a reactant in the rate expression and its stoichiometric
coefficient in the balanced chemical equation.
 Zero-Order Reactions
• The rate law for a zero-order reaction of the type
First-Order Reactions
 Half-Life of a Reaction
• The half-life of a reaction is defined as the time it takes for the concentration
of the reactant to decrease by half of its original value
Half-Life of a First Order Reaction
• In contrast to first-order reactions, the half-lives of other types of
reaction all depend on the initial concentration
 Second-Order Reactions
Two types of second-order reactions here.
➢In one type, there is just one reactant.
➢The second type involves two different reactants.
The first type is represented by the general reaction
• The second type of second-order reaction is represented by
 Pseudo-First-Order Reactions
➢An interesting special case of second-order reactions occurs when one of the
reactants is present in great excess
➢Because the concentration of water in the acetyl chloride solution is quite high
about 55.5 M, the concentration of pure water and the concentration of acetyl
chloride is of the order of 1 M or less, the amount of water consumed is
negligible compared with the amount of water originally present.
 Determination of Reaction Order
1. Integration Method
2 Differential Method
• This method was developed by van’t Hoff in 1884.
3. Half-Life Method.
4. Isolation Method
 Molecularity of a Reaction
• Typically, the overall reaction is the sum of several steps
• The sequence of steps by which a reaction occurs is called
the mechanism of the reaction.
• To know the mechanism of a reaction is to know how
molecules approach one another during a collision, how
chemical bonds are broken and formed, how charges are
transferred, and so on when the reactant molecules are in
close proximity.
• When this reaction is catalyzed by iodide ions, the rate law is found to
be

• Each of these so-called elementary steps describes what actually happens

at the molecular level.
➢How do we account for the observed rate
dependence in terms of these two steps?
➢Simply assume that the rate for the first step is much
slower than that for the Second step, that is, k1 << k2.
➢ The overall rate of decomposition, then, is
completely controlled by the rate of the first step,
which is aptly called the rate-determining step, and
we have:
 Intermediate
➢Note that the sum of steps 1 and 2 gives us the overall reaction, because
the species IO− cancels out.
➢Such a species is called an intermediate because it appears in the
mechanism of the reaction but is not in the overall balanced chemical
equation.
➢An intermediate is always formed in an early elementary step and
consumed in a later elementary step.
➢On the other hand, a catalyst, I− in this case appears as a reactant in the
initial elementary step.
➢It invariably forms an intermediate and is regenerated at the end of the
reaction.
➢Unlike the order of a reaction, molecularity cannot be zero or a
noninteger.
 Unimolecular Reactions
➢Involve only one reactant molecule in the elementary
step.
 Frederick Alexander Lindemann (1886–1957)
➢Unimolecular reactions often follow a first-order rate law.
➢ Because these reactions presumably occur as the result of a
binary collision
➢we would expect them to be bimolecular processes and
hence second-order reactions.
 Steady-State Approximation
➢A* is an energetically excited species
➢It has little stability and a short lifetime.
➢Its concentration in the gas phase is not only low but probably fairly
constant as well.
➢Using this assumption, we can apply the steady-state approximation as
follows.
➢The rate of change of [A*] is given by the steps leading to the formation
of A* minus the steps leading to the removal of A*
The steps leading to A* is an energetically excited species, it has little
stability and a short lifetime.
According to the steady-state approximation, however, this rate of
change must be zero.
 Bimolecular Reactions
• Any elementary step that involves two reactant molecules
is a bimolecular reaction.
 Termolecular Reactions
➢An elementary step that involves the simultaneous encounter of three
reactant molecules is called a termolecular reaction.
➢The probability of a three-body collision is usually quite small and only a few
such reactions are known

• where X = Cl, Br, or I.

➢ (a) Fast and slow steps in a catalytic cycle are analogous to the falling of sand grains through an
hourglass with narrow and wide openings.

➢ (b) The thermal cis/trans isomerization of stilbene, the Diels–Alder cycloaddition of butadiene to
ethene, and the fluorination of gaseous BF3 in the presence of methane are examples of
unimolecular, bimolecular, and termolecular reactions, respectively.
 Reversible Reactions
➢Most reactions are reversible to a certain extent, and we must consider both the
forward and reverse rates. For the reversible reaction that proceeds by two
elementary steps.

➢The principle of microscopic reversibility states that at equilibrium, the rates of

the forward and reverse processes are equal for every elementary reaction
occurring.
➢It means that the process A → B is exactly balanced by B → A so that equilibrium
cannot be maintained by a cyclic process in which the forward reaction is A → B
and the reverse reaction is B → C → A:
• Instead, for every elementary reaction we must write
a reverse reaction as follows:
 Consecutive Reactions
➢A consecutive reaction is one in which the product from the first step
becomes the reactant for the second step, and so on.
The thermal decomposition of acetone in the gas phase is an example
 Parallel Reactions
• Catalytic reaction will yield several products, because one of the
catalytic intermediates can react via two different pathways. The
general scheme for two parallel reactions is shown in
 Chain Reactions
• One of the best-known gas-phase chain reactions involves the formation of
hydrogen bromide from molecular hydrogen and bromine between 230°C and
300°C:
We assume that a chain of reactions proceeds as
follows
Rates of reaction
Why are some reactions faster than others?

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Changing the rate of reactions
Anything that increases the number of successful collisions
between reactant particles will speed up a reaction.

What factors affect the rate of reactions?

⚫ increased temperature

⚫ increased concentration of
dissolved reactants, and increased
pressure of gaseous reactants

⚫ increased surface area of solid

reactants

⚫ use of a catalyst.

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Slower and slower!
Reactions do not proceed at a steady rate. They start off at a
certain speed, then get slower and slower until they stop.
As the reaction progresses, the concentration of reactants
decreases.
This reduces the frequency of collisions between particles
and so the reaction slows down.

0% 25% 50% 75% 100%

reactants
percentage completion of reaction
product
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Graphing rates of reaction

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Reactant–product mix

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The reactant/product mix

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Temperature and particle collisions

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Effect of concentration on rate of reaction
➢ The higher the concentration of a dissolved reactant,
the faster the rate of a reaction.
Why does increased concentration increase the rate of
reaction?
➢ At a higher concentration, there are more particles in the
same amount of space. This means that the particles are
more likely to collide and therefore more likely to react.

lower concentration higher concentration

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Concentration and particle collisions

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Effect of pressure on rate of reaction
➢ Why does increasing the pressure of gaseous reactants
increase the rate of reaction?
As the pressure increases, the space in which the gas
particles are moving becomes smaller.
The gas particles become closer together, increasing the
frequency of collisions. This means that the particles are more
likely to react.

lower pressure higher pressure

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Effect of surface area on rate of reaction
Any reaction involving a solid can only take place at the
surface of the solid.
If the solid is split into several pieces, the surface area
increases. What effect will this have on rate of reaction?

low surface area high surface area

This means that there is an increased area for the reactant
particles to collide with.
The smaller the pieces, the larger the surface area. This
means more collisions and a greater chance of reaction.

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Surface area and particle collisions

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Reaction between a carbonate and acid
Marble chips are made of calcium carbonate. They react
with hydrochloric acid to produce carbon dioxide.

calcium hydrochloric calcium carbon

carbonate + acid chloride + water + dioxide

CaCO3 2HCl CaCl2 H2O CO2

(aq)
+ (aq) (aq)
+ (aq)
+ (g)

The effect of increasing surface area on the rate of reaction

can be measured by comparing how quickly the mass of the
reactants decreases using marble chips of different sizes.

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The effect of surface area on rate

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 Activation Energy
• Molecules must be activated
before they can undergo a
reaction
– Reactants must absorb enough
energy from surroundings to
destabilize chemical bonds (energy
of activation)
• Transition state
– Intermediate stage in reaction
where the reactant molecule is
strained or distorted but the reaction
has not yet occurred

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 Collision Model

• Molecules must collide to react.

• Main Factors:
▪ Activation energy, Ea
▪ Temperature
▪ Molecular orientations

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Reactions, particles and collisions
➢ Reactions take place when particles collide with a certain
amount of energy.
➢ The minimum amount of energy needed for the
particles to react is called the activation energy, and
is different for each reaction.

➢ The rate of a reaction depends on two things:

⚫ the frequency of collisions between particles

⚫ the energy with which particles collide.

➢ If particles collide with less energy than the activation

energy, they will not react. The particles will just
bounce off each other.

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 A Reaction Profile
➢A reaction profile shows potential energy plotted as a function of a
parameter called the progress of the reaction.
CO(g) + NO2(g) CO2(g) + NO(g)

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry Chapter Thirteen
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 Change in Potential Energy
A Model for Chemical Kinetics

➢The configuration of the atoms of the colliding species at the time of the
collision is called the transition state.
➢The transitory species having this configuration is called the activated
complex.
➢Reactant molecules must have enough energy to surmount the energy
“hill”Copyright
separating products from reactants
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 Distribution of Kinetic Energies

At higher temperature
(red), more molecules
have the necessary
activation energy.

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry Chapter Thirteen
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 Effect of Temperature on the Rates of Reactions
➢In 1889, Svante Arrhenius proposed the following
expression for the effect of temperature on the rate
constant, k:
k = Ae–Ea/RT
➢The constant A, called the frequency factor, is an
expression of collision frequency and orientation; it
represents the number of collisions per unit time that are
capable of leading to reaction.
➢The term e–Ea/RT represents the fraction of molecular
collisions sufficiently energetic to produce a reaction.
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 Arrhenius
A Model for Equation
Chemical Kinetics

• A = frequency factor
• Ea = activation energy
• R = gas constant (8.3145 J/K·mol)
• T = temperature (in K)

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 The Arrhenius Equation

• In 1889, Arrhenius discovered that the temperature

dependence of many reactions could be described by the
equation, because the frequency factor A is related to
molecular collisions,
• it is temperature dependent.
• For a limited temperature range about 50 K, however, the
predominant temperature variation is contained in the
exponential term

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 Collision Theory

• The collision theory of reaction rates is based on the

kinetic theory of gases
• In its simplest form, it applies only to bimolecular
reactions in the gas phase.
• Consider the bimolecular elementary reaction

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• the number of binary collisions per cubic meter per
second between “hard-sphere” A molecules is given by

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• For a bimolecular reaction of the type

• the binary collision number is

• where dAB is the collision diameter between A and B, and

μ, the reduced mass, is given by
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➢Thus, the frequency factor, A, is temperature dependent.
➢In practice, we usually treat it as a temperature-
independent quantity in the calculation of Ea values.
➢Doing so does not introduce any serious error, however,
because the exponential term i.e., Exp (-Ea/RT) depends
much more on temperature than the square-root term
does on temperature

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➢ The activation energy Ea is an extremely important parameter in catalysis.
➢ It gives the height of the energy barrier that the system must overcome for the
reaction to proceed.
➢ The higher the activation energy, the higher the sensitivity of k to temperature.
➢ Typical values for Ea range from 2 kcal mol-1 to tens of kilocalories/mole.
➢ A useful rule of thumb states that the reaction rate roughly doubles for every 10 C
increase in temperature.
➢ Furthermore, when Ea is less than 5 kcal mol-1, we say that the reaction is
diffusion-controlled. This means that the reaction rate is limited by how fast the
molecules move toward one another.
➢ Conversely, when Ea is greater than 5 kcal mol-1, we say that the reaction is
chemically controlled.
➢ Typical values for A range from 1011 to 1014 s-1 for first-order reactions. As the
exponent in the Arrhenius equation is a pure number, the units of A are the same as
those of k.
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 Importance of Orientation
One hydrogen atom can Effective collision; the I
approach another from atom can bond to the C
any direction … atom to form CH3I

… and reaction will still occur; the

Ineffective collision;
spherical symmetry of the atoms means
orientation is important
that orientation does not matter.
in this reaction.
Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry Chapter Thirteen
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Summary
For Reactants to Form Products
➢ Collision must involve enough energy to produce the
reaction (must equal or exceed the activation energy).
➢ Relative orientation of the reactants must allow formation of
any new bonds necessary to produce products.

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