Introduction to catalysis

Lecture-1
Four major sectors of world economy that involve catalytic
processes
History
• Catalyst technology has been used for many centuries. It ranged from inorganic
catalyst to make soaps to enzyme catalysts for producing wines, cheese and other
food and beverages.
• The industrial catalyst technology started with the large-scale production of sulfuric
acid on platinum catalyst in 1875. In subsequent years, various major catalytic
processes were invented. In 1903, ammonia oxidation on Pt gauge was developed by
Ostwald for nitric acid production.
• Another major breakthrough was ammonia synthesis with promoted iron in 1908-
1914 by Mittasch, Bosch and Haber.
• Conversion of synthesis gas to liquid hydrocarbons by hydrogenation of CO, which was
developed in 1920-1940, was a major development in the energy sector. In petroleum
industry, the development of catalytic cracking process during 1935- 1940 changed
the energy scenario. This process used a solid catalyst in the petroleum industry for
the first time. Subsequent decades saw the development of various catalytic
hydrocarbon processes such as catalytic naphtha reforming (1950) and hydrotreating
for removal of sulphur, nitrogen, metals from petroleum feed stock (1960). With the
discovery of Ziegler-Natta catalyst in 1955, the polymer industry grew significantly.
• The first large scale industrial homogeneous catalytic process came up in 1960 in the
form of Walker process for making acetaldehyde from ethylene.
• The development of shape selective catalysts such as molecular sieves or zeolites for
cracking (1964) resulted in the production of exclusively shape selective products.
• The other major development in catalysis was in 1970-1980 for environmental
pollution control. Noble metal catalysts were developed for emission control of CO,
NOx and hydrocarbons from automobiles. Vanadia-titania and zeolite catalysts were
developed for selective reduction of NOx. Catalysis is a continuously growing area
and discovery of new catalysts and their applications has led to major
development in the chemical industry.
• The economic significance of the catalyst industry is enormous. The catalytic
processes contribute greater than 35% of global GDP. The world catalyst industry
amounts to US $ 12 billion. It is expected to grow annually by 6 % to US $16 billion
US$ in 2012. Polymerization catalysts are expected to grow most rapidly due to
significant expansion in polymer industry. Enzyme and organometallic catalysts will
also grow. Reduction of sulphur levels in fuels and ongoing shifts towards heavy
grade crude oil with high sulphur content is expected to contribute to the growth of
catalytic hydrocarbon industry.
Classification of catalysts
Catalytic processes that take place in a uniform gas or liquid
phase are classifiedas homogeneous catalysis.

Homogeneous catalysts are generally well-defined chemical

compounds or coordination complexes, which, together with
the reactants, are molecularly dispersed in the reaction medium.

Examples of homogeneous catalysts include mineral acids and

transition metal compounds (e. g., rhodium carbonyl complexes
in oxo synthesis).
Heterogeneous catalysis takes place between several
phases. Generally the catalyst is a solid, and the reactants are
gases or liquids.
An interesting intermediate between homogeneous and heterogeneous
catalysts are the metal cluster catalysts. In many reactions that require
several active centers of the catalyst, it is found that heterogeneous
catalysts are active, while homogeneous catalysts give zero conversion.
The reason is that crystallites on a metal surface exhibit several active
centers, while conventional soluble catalysts generally contain only one
metal center.

In contrast, metal clusters have several active centers or can form multi-
electron systems. Metal clusters such as Rh6(CO)16, Rh4(CO)12,
Ir4(CO)12, Ru3(CO)12, and more complex structures have been successfully
tested in carbonylation reactions. Rhodium clusters catalyze the conversion
of synthesis gas to ethylene glycol, albeit at very high pressures up to now.

With increasing size, the clusters become less soluble, and the
precipitation of extremely small particles from solution is possible, that
is, a transition from homogeneous to heterogeneous catalysis.
Catalytic reactions
In a thermodynamically feasible
chemical reaction, when addition of
a small amount a chemical
substance increases the rate of
attainment of chemical equilibrium
but the substance itself does not
undergo any chemical change, then
the reaction is called a catalytic
reaction.
The substance that enhances the
reaction rate is called a catalyst.
Catalysts work by providing
alternative mechanism involving a
different transition state of lower
energy. Thereby, the activation
energy of the catalytic reaction is
lowered compared to the
uncatalyzed reaction
A catalyst accelerates both the rates of the forward and reverse reaction.
Equilibrium of a reversible reaction is not altered by the presence of the
catalyst.
For example, when oxidation of SO2 is carried out in the presence of three
different catalysts, namely Pt, Fe2O3 and V2O5 , the equilibrium
composition is the same in all three cases.

Another important characteristic of catalyst is its effect on selectivity.

The presence of different catalysts can result in different product distribution
from the same starting material.
For example, decomposition of ethanol in the presence of different catalysts
results in different products as shown below.
Types of catalytic reactions
Heterogeneous
• The catalyst and the reactants are in different phases.
Homogeneous
• The catalyst is in the same phase as the reactants.
• Most homogeneous reactions are carried out in liquid
phase
• Have high selectivity and hence preferred
Heterogeneous catalytic theory
It is believed that the entire surface of the solid catalyst is not responsible for catalyzing any
reaction.
Only certain sites on the catalyst surface actually participate in the reaction and these sites are
called active sites on the catalysts.
These sites may be the unsaturated atoms resulting from surface irregularities or atoms with
chemical properties that enable the interaction with the adsorbed reactant atoms or molecules.
Activity of the catalyst is directly proportional to the number of these active sites available on the
surface and is often expressed in terms of turnover frequency. Turnover frequency is defined as
the number of molecules reacting per active site per second at the condition of experiments.
A solid catalytic reaction A→ B goes through the following steps

1. Transportation of reactant (A) from bulk fluid to pore mouth on the

external surface of catalysts pellets
2. Diffusion of the reactant (A) from the pore mouth through the catalyst
pores to the immediate vicinity of internal catalytic surface
3. Adsorption of reactant (A) onto the catalyst surface
4. Reaction of (A) on the catalyst surface
producing product (B)
5. Desorption of the product (B) from
the surface
6. Diffusion of the product (B) from
interior part of the pores to the pore
mouth on the external surface
7. Transfer of the product (B) from pore
mouth on the external surface to the
bulk fluid
The overall rate of reaction is equal to the rate of slowest step in the
mechanism.
When the mass transfer and diffusion steps [1,2,6,7] are very fast
compared to adsorption and reaction steps [3,4,5], concentration
in the immediate vicinity of the active sites is the same or
indistinguishable from that in the bulk fluid. Consequently, the
transport or diffusion steps do not affect the overall rate of the
reaction.
Alternatively, if reaction and diffusion steps are fast compared to the
mass transfer steps, then mass transfer does affect the rate of
reaction.
When mass transfer from the bulk phase to the pore mouth is slow
and affects the reaction rate, then changing the flow conditions
past the catalyst should change the overall reaction rate.
In case of porous catalysts, diffusion within the catalyst pores may
limit the reaction rate. Under this condition external flow does not
affect the reaction rate but internal diffusion does affect.
Adsorption on solid surfaces
Heterogeneous solid catalysis is strongly associated with adsorption phenomenon.
In solid catalysis, at least one of the reactant needs to be adsorbed on the
surface of the catalyst.

The surfaces include both external surface and internal surface due to the pores.
For highly porous material, the internal surface area due to the pores is much
higher than the external surface area. The pores in a solid material can be of
different dimensions. Pores with diameter less than 2nm (20 A0) are called
micropores, pores in the range of 2- 50 nm (20 – 500 A0) are called mesopores,
whereas pores greater than 50 nm are called macropores.

The pore size distribution of a catalyst is affected by preparation condition and

amount of loading of active component. Usually a wide pore size distribution
exists in a catalyst. The active sites are dispersed throughout the porous matrix.
Under suitable conditions of temperature and pressure, a gas can gradually
adsorb on the solid surface and finally lead to its complete coverage.
Why adsorption takes place on solid surface
In the bulk of the adsorbent, the molecules are
associated with their neighbours equally in all direction
and the molecular forces are therefore balanced.
However on the adsorbent surface, the molecules are
bounded to the inner molecules at one side leaving
unbalanced molecular forces on the other side. These
unbalanced molecular forces on adsorbent surfaces
create the attractive force for the adsorbate molecules
approaching the surface. These molecular forces are
weak in nature and called van der Waals attraction
forces.
Types of adsorption
Depending on the nature of interaction, the adsorption can be of two
types:
Physisorption: The phenomenon of adsorbate molecules attaching
themselves to adsorbent surface under the influence of van der
Waals forces is called physisorption or physical adsorption. The van
der Waals forces mainly consist of dipole –dipole interactions. This
is an exothermic process with a low enthalpy change known as
heat of adsorption. This process resembles liquefaction and heat of
adsorption for physisorption is also known as heat of liquefaction.

Chemisorption : At higher temperature, the adsorbed molecules can

undergo electronic rearrangement with the surface molecules.
This phenomenon is called chemisorption. The electronic
rearrangement may include formation and breaking of chemical
bonds. The electronic rearrangement occurs only when there is
significant interaction between adsorbate and the adsorbent
molecules. Hence all adsorbate will not be chemisorbed on all
adsorbent surfaces. Chemisorption process is selective and an
adsorbate molecule will chemisorbed only on selected adsorbent
Physisorption versus Chemisorption
• Physisorption involves only weak molecular interaction, the associated enthalpy changes are
small (in the range of 10 to 40 kJ /mol) . On the other hand, in case of chemisorption,
enthalpy change is large and can range from 80-400 kJ /mol.
• The Figure compares the volume of gas adsorbed as a function of temperature under
physisorbed and chemisorbed conditions. In physisorption, the molecules are adsorbed on
surface by weak interaction. With increase in temperature, adsorbed molecules gain excess
energy and their tendency to escape from the surface increases. Hence volume of gas
adsorbed on the surface decreases with temperature.

However, the chemisorption involves higher

interaction energy between adsorbate and
adsorbent molecules and hence is favored by
temperature rise. Hence at low temperature
range volume of adsorbed gas increases with
temperature. However, at higher temperature
range as the adsorbed molecules gains excess
energy, rate of desorption becomes higher
resulting in decrease in adsorbed gas volume.
• In case of chemisorption, since there is electronic interaction between adsorbate and
adsorbent molecules, only a monolayer of adsorbate can be formed on the adsorbent
surface. In case of physisorption, the first monolayer formed on the surface of the
adsorbent can act as adsorbing surface for formation of next layer of adsorbate and so
on. This phenomenon is called multilayer adsorption For the physisorption, volume of
gas adsorbed increases with pressure due to increase in concentration of adsorbate and
formation of multilayers. However for chemisorption process which corresponds to
monolayer formation, the effect of pressure is not significant.
• Chemisorption is specific for adsorbate and adsorbent pair. Specific solid adsorbent can
undergo electronic interaction only with specific adsorbate gas molecule.
• Physisorption is highly reversible while chemisorption can be irreversible.
• Physisorption is important for estimating the total surface area. It also provides a basis
for estimating the pore volume and pore size distributions. On the other hand,
chemisorption is important in estimation of area of catalytic active sites as well as its
dispersion.
Adsorption kinetics
Rate of adsorption :
Then the rate of adsorption is

sp
ra = rc s =
(2mk B T )1 / 2
From kinetic theory the rate of collision, rc, is the rate at which molecules of a gas strike a
bare surface per cm2 per sec at pressure p. The rc is given as

p
rc =
(2mk B T )constant,
molecules /cm2 .sec, where ‘kB’ is Boltzmanns 1/ 2 ‘m’ is mass and ‘T’ is temperature.

The ‘s’ is known as the sticking coefficient and defined as fraction of molecules bombarding
or impinging on the catalyst surface that stick to the surface on impact. The ‘s’ is also
called the sticking probability.
Whether a molecule will be adsorbed (chemisorbed) depends on two main
parameters: activation energy and configuration.
Only those molecules possessing the required activation energy can be
chemisorbed. Even if the molecules possess the necessary energy they may
not be chemisorbed if the configuration of the molecule and surface site do
not allow the activated complex to be traversed.

The fraction of molecules possessing the required energy is

where Ea is the activation energy for chemisorption.  − Ea 

exp   is
The configuration probability that a molecule will occupy a single site
 fraction
RT 
proportional to the fraction of unoccupied surface, 1-θ, where θ is the
of surface covered.

is the proportionality constant often known as ‘condensation coefficient’. It is

the fraction of those molecules with energy greater than Ea that is adsorbed.
 − Ea 
s = (1 − ) exp  
 RT 
 p  − Ea  For non- dissociative adsorption, f(θ) =
ra =  (1 − ) exp  
(2mk BT )1/ 2  RT  fraction of surface uncovered = (1-θ).
p  − Ea 
ra =  exp  f ()
(2mk BT )1/ 2  RT 
The type of adsorption depends on extent on interaction between adsorbate and
adsorbent surface molecules.

In actual adsorption, the observed rate decreases rapidly with increasing surface
coverage which implies that the activation energy increases with the surface
coverage, θ.
The condensation coefficient α also varies with θ. These variations are caused by
surface heterogeneity, that is the activity of the adsorbent sites varies and
different sites posses different values of α and Ea . The most active sites are
associated with lowest activation energy. Hence probability of occupation of these
sites by adsorbate molecules is higher. Further, the interaction between occupied
and unoccupied site also affects the rate of adsorption. Hence α and Ea should be
represented as function of θ.

p  − E a () 
ra =  ( ) exp  (1 − )
(2mk B T )1/ 2
 RT 
Rates of Desorption
The rate of desorption is given by Polanyi –Wigner equation as

dN a − Ed 
rd = − = N a exp 
m

dt  RT 
where, Ed is activation energy for desorption, ν is the pre-exponential factor of the
desorption rate coefficient, Na is the number of binding sites for the adsorbed molecules
and m is kinetic order for desorption process.
Kinetic order suggests the nature of elementary steps that governs the desorption.

A zero-order kinetics indicates that desorption occurs from multilayer where desorption
is independent of coverage.
A first order kinetics indicates the presence of single surface species whereas
second order kinetics indicates recombination of adsorbate atoms leading to production
of a diatomic molecule that is then desorbed.
Adsorption Isotherms and Isobars
• When an adsorbate molecule in the gas phase comes in contact with the surface of
the adsorbent, an equilibrium distribution of the adsorbate molecules takes place
between the adsorbent surface and the gas phase. This equilibrium distribution
depends upon various factors including partial pressure of adsorbate,
temperature, nature of adsorbate, and the surface area and nature of adsorbent.
Adsorption isotherm shows the amount of molecules adsorbed on the solid surface
as a function of the equilibrium partial pressure at constant temperature.
• Adsorption isobar shows the variation of adsorbed species with temperature at
constant pressure.

• The adsorption-desorption isotherm characterize the adsorbent. It depicts the

nature of adsorption - desorption process occurring on the surface and also reveals
the pore structure of the adsorbent. Often the isotherm is expressed as standard
volume adsorbed as a function of relative pressure.
• Relative pressure is defined as the ratio of actual gas partial pressure over the
saturated vapor pressure of adsorbate (P0) under constant temperature.
• Type I isotherm is for very small pores or microporous adsorbents. Adsorption
occurs by filling of the micropores. The adsorbate uptake rate depends on the
accessible micropore volume rather than total internal surface area.
• Type II and Type IV isotherms are observed for non-porous or macroporous
adsorbents with unrestricted monolayer-multilayer adsorption. At first the
adsorption volume rapidly increases at low relative pressures of less than 0.01 due
to interaction of the adsorbate molecules with the higher energetic region followed
by the interaction with less energetic region. When the monolayer formation of the
adsorbed molecules is complete, multilayer formation starts to take place
corresponding to the ‘sharp knee’ of the isotherms. As the relative pressure
approaches unity an abrupt rise indicates the bulk condensation of adsorbate gas to
liquid.
• Type III and Type V isotherms do not have the ‘sharp knee’ shape implying stronger
adsorbate – adsorbate interactions than adsorbate-adsorbent interaction.
Hysteresis Loop
• In case of isotherms for nonporous material, the desorption curve traces the
adsorption curve.
• However, for the mesoporous and macroporous materials, desorption curve do not
retrace the adsorption curve resulting in a wide loop. This is known as hysteresis
loop and corresponds to the capillary condensation of adsorbate in the multilayer
region, pore filling and emptying mechanism.
• Type A hysteresis is attributed to cylindrical or tubular type pores of adsorbent with
a narrow distribution of uniform pores. It is characterized by steep and narrow
parallel adsorption and desorption curves. Type B has a long flat plateau adsorption
with a steep desorption curve. This is a complex structure of pores with
interconnected networks or ink bottle shaped pores.

Type C represents aggregates of

adsorbent that contain parallel
plates, slit- shape pores or wide
capillaries (> 500 A0). Type D is
associated with slit- shape pores
that are mainly in the
micropore region.
Plotting concentration against position in the pore provides
information about the ratio of the reaction rate to the transport rate

a) Film diffusion region: the reaction is fast compared to

diffusion in the film layer and to diffusion in the pores.
b) Pore diffusion region: the reaction is fast compared to
diffusion in the pores, but slow compared to film diffusion.
c) Kinetic region: the reaction is slow compared to diffusion in
the pores and through the gas film.
Effect of temperature: Changing the temperature changes the ratio of
reaction to transport rate. In the kinetic region, the reaction rate
increases rapidly with increasing temperature, as in a homogeneous
reaction obeying the Arrhenius law.

In the pore diffusion region, the reaction rate also increases according
to the Arrhenius law, but at the same time the concentration profile
becomes steeper, so that an ever decreasing fraction of the catalyst is
active. This results in a less rapid increase of the reaction rate than in the
kinetic region.

In the film diffusion region, reff

increases slowly with increasing
temperature because the diffusion has
only a slight temperature dependence.
There is practically no
reaction resistance, and the gas already
undergoes complete conversion on the
outer surface of the catalyst.