Module-V: Catalysis

L-1: Introduction and characteristics of catalyst, types of catalysis (homogenous, heterogeneous

and auto catalysis with example), catalytic poison

L-2: Theories of catalysis, intermediate compound formation and adsorption or contact theory
with examples, advantage and disadvantages.

L3: Acid base catalysis- including kinetics and examples, Enzyme catalysis- Introduction and
characteristic of enzymes

L4: Mechanism and kinetics of enzyme catalyzed reaction, Michaelis-Menten equation,

Lineweaver - Burk Plot.

L5: Important catalysts in industrial processes, Hydrogenation using Wilkinsons catalyst,

Hydroformylation by using Cobalt-catalyst

Class notes- Prepared By

Dr. Rafique Ul Islam

Assistant Professor

Department of Applied Chemistry

Birla Institute of Technology, Mesra, Ranchi-835215

Jharkhand, India

Email: rafiqueisl@gmail.com
L-1: Introduction and characteristics of catalyst, types of catalysis (homogenous,
heterogeneous and auto catalysis with example), catalytic poison

Introduction:

The collision theory of reaction rates: The rate of a reaction depends upon-

(a) Collision between the reactant molecules which increases in increase in the concentration of
the reactant molecules.

(b) Activation of the molecule: For the formation of products, the reactant molecules have to
cross some short of barrier and energy needed for the same. The minimum energy which the
reacting molecules must have posses before the reaction to occur is known as activation energy
and is denoted by Ea.

(c) Proper orientation at the time of the collisions. ( probability or steric factor comes from the
proper orientation of the molecules at the time of collisions.)

Mathematically k = Z11e-Ea/RT. P

Where k = rate constant for the reaction

Z11 = bimolecular collision term
Ea = activation energy
R = Gas constant
T = temperature
P = Probability or steric factor

Effect of temperature on reaction rate:

It is obvious that with increase in temperature, the rate of the reaction also increases. This is due
to the increase in the proportion of the molecules with a given kinetic energy.
The total area under the curve beyond activation energy Ea gives the total number of molecules
having energy greater than or equal to Ea; Only these molecules where collisions determine the
rate of the reactions.

Role of a catalyst:

We can employ catalyst for increase the rate of a reaction because catalyst can provide an
alternative pathway with low activation energy, so more reactant molecules can cross the
activation energy barrier at given concentration and temperature.

ET = threshold energy of the uncatalysed reaction

ET = threshold energy of the catalyzed reaction
ER = Energy of the reactant
Ep = Energy of the product

Advantages of using catalyst instead of using high temperature to promote a chemical reaction

(a) Better to control of the reaction

(b) Low energy cost due to lower temperature (more economical)

(c) Fewer side reactions thereby providing higher yield of the desired products.

:
What is catalyst?

Catalyst is defined as a substance, a small quantity of which alter ( increase or decrease ) the
velocity of a chemical reaction by its mere presence, without itself undergoing any change in
mass and composition at the end of the reaction.

The phenomenon of altering the velocity of a chemical reaction by the presence of a catalyst is
called catalysis.

Types of catalyst:

(a) Positive catalyst: A positive catalyst is a catalyst which accelerates the speed of the reaction
(also known as accelerator)

Examples: (i) In hydrogenation reaction of oil during the manufacture of vegetable ghee by
Nickel (150-3000C)

(ii) MnO2 in the decomposition of KClO3 into KCl and O2

(iii) Platinum black or V2O5 in the oxidation of SO2 by atmospheric oxygen to SO 3 (contact
process)
(b) Negative catalyst: If the catalytic substances retard the chemical reaction, it is called
negative catalyst (also known as inhibitor)

Examples: (i) Alcohol retard the oxidation of chloroform to poisonous phosgene

(ii) Tetraethyl lead acts as anti-knock material in internal combustion engine.

Characteristics of catalysts:

1. A catalyst remains unchanged in mass and composition at the end of the reaction though a
change in physical state, color etc. may occur.

As for example, granular MnO2 (manganese dioxide) used as a catalyst during the decomposition
of Potassium Chlorate (KClO3), is recovered as fine powder after the reaction.

It is believed that MnO2 catalyzed reaction for the preparation of oxygen takes place as follows-

2KClO3 + 2MnO2  2KMnO4 + Cl2 + O2

2KMnO4  K2MnO4 + MnO2 + O2

K2MnO4 + Cl2  2KCl + MnO2 + O2

2. A small amount of catalyst is sufficient to bring an appreciable change in the velocity of the
reaction. Example: The presence of even 1 mg of fine pt powder is enough to catalyze the
combination of 2.5 liters mixtures of H 2 and O2 to form water. Rate also increases in the increase
in the surface area of the catalyst.
3. A catalyst can exert a selective action like a key can open a particular lock. Some catalysts are
very specific in respect of reaction and change of a catalyst may divert the path of the same
reaction to different products.

Examples: (i) water gas ( a mixture of CO and H2) is converted to –

(a) Methanol when passed over ZnO and Cr2O3 at 4000C

(b) Methane when passed over a Nickel catalyst at 4000C

(c) Decomposition of formic acid

Enzymes also have specific catalytic activity.

4. A catalyst can only alter the speed of the reaction but does not affect the final state of
equilibrium since it alters the rate of the forward as well as backward reaction to the same extent,
thereby the composition of the equilibrium remains the same.
5. According to Ostwald, a catalyst cannot initiate the reaction but can only decrease or increase
its rate. Initiations of reactions by catalyst are rather rare but not unknown. Example- Perfectly
dry H2 and O2 does not combine to form water even if they are left in contact for years, but in
presence of little water (catalyst), the reaction proceeds quite rapidly.

6. A catalyst is most active at a particular temperature, called the optimum temperature.

7. The addition of a small amount of foreign substances, which are not themselves catalytically
active, sometimes increase the catalytic activity of the catalyst. Such substances which catalyze
the catalyst are called promoters.

Examples: In the manufacture of ammonia by Habers Process, finely divided Fe acts as a catalyst
while Molybdenum (or a mixture of alumina, Al2O3 and K2O) acts as a promoter.

Similarly, in the manufacture of methanol from CO and H2, the activity of the catalyst ZnO is
greatly enhanced by the presence of Chromium sesquioxide, the promoter.

The properties of promoters are- (i) Selectively enhancement of the reactions; (ii) Increase
catalyst lifetime.

8. The activity of a catalyst is inhibited or completely destroyed by the presence of even minute
traces of certain substances, called catalytic poison or anti-catalyst.

Example: In the manufacture of H 2SO4 by contact process, a trace of As 2O3 destroys the catalytic
activity and efficiency of spongy Platinum.

Types of catalysis (homogenous, heterogeneous and auto catalysis with example)

Generally there are two types of catalysis-

(i) Homogenous and (ii) Heterogeneous catalysis

(A) Homogenous catalysis: In this catalysis, the catalyst is present in the same phase as the
reacting substances (either in gas phase or liquid phase). Examples are given below-

(a) In gas phase:

(i) In the lead chamber process, for the manufacture of H2SO4, nitric oxide (NO) catalyses the
oxidation of the SO2
(ii) Decomposition of acetaldehyde is catalysed by Iodine vapour

(iii) Nitric oxide acts as a catalyst in the combination of CO and O2

(iv) Formation of HCl from H2 and Cl2 using N2O as catalyst.

(b) In Liquid phase: In acid-base catalysis- inversion of cane sugar and hydrolysis of esters.

Acid catalysis:

Base catalysis:

(B) Heterogeneous catalysis:

In such reactions, the catalyst is present in different phase from the reacting substances and the
reaction proceeds at an interface between the two discrete phases. Catalysts are usually solid and
the reactants are in different phase (either liquid or gaseous).

(a) In contact Process for the manufacture of H2SO4, sulfur dioxide is directly oxidized to sulfur
trioxide by atmospheric oxygen in the presence of Pt or vanadium pentoxide V2O5 as catalyst.
(b) In Haber’s process, for the manufacture of NH3, nitrogen and hydrogen gases in the volume
ratio 1:3 are passed over heated iron catalyst which contains a promoter, molybdenum.

(c) Oxidation of ammonia to nitric oxide in presence of Pt-gause as catalyst

(d) Hydrogenation of unsaturated hydrogen in presence of nickel as a catalyst.

Auto-catalysis:

When a product formed in the course of the reaction enhances the velocity of the reaction (or
acts as a catalyst), the phenomenon is called autocatalysis. In other words, if one of the product
of a reaction is capable of catalyzing the same reaction in which it is produced this is called
autocatalysis.

Examples: when an oxalate reacts with acidified KMnO4 solution, the Mn(II) ions (resulting
from the reduction of permanganate) catalyze the reaction. When oxalic acid is added to an
acidified solution of Potassium permanganate, no appreciable de-colorization occurs for a
comparatively long period of time but once the de-colorization occurs, it proceeds rapidly.

Many hydrolysis reactions are catalysed by acids. When esters are hydrolysed since one of the
products is an acid, the reaction is autocatalytic.

Mn(II) ions are not present before the reaction starts and so it starts off extremely slowly at room
temperature. However, once the Mn(II) is produced, the reaction proceeds rapidly.
L-2: Theories of catalysis, intermediate compound formation and adsorption or contact
theory with examples, advantage and disadvantages.

Theories of Catalysis: (Mechanism of catalysis):

1. Intermediate compound formation theory:

This theory explains the mechanism of homogenous catalysis. The theory states “The catalyst
forms a very reactive and unstable intermediate compound with reactant which immediately
reacts with the other reactants yielding the products of the reaction and liberating the catalyst in
its original chemical composition.”

A reaction of the type is shown below where A and B are the reactant and formed product AB.

A + B  AB

Which takes place in the presence of a catalyst C may occur as-

A + C [AC]

Reactant Catalyst Intermediate compound

[AC] + B AB + C

Intermediate compound Reactant Product Catalyst

Many catalytic reactions can be explained on the basis of this theory. The main advantage of this
theory is that it explains various homogenous reactions.

Explaination of various homogenous reaction on the basis of intermediate compound

formation theory:

1. Catalytic action of NO in the manufacture of H2SO4 by chambers Process

2. Preparation of O2 from KClO3 by heating in presence of MnO2 probably takes place as-

2KClO3 + 2MnO2  2KMnO4 + Cl2 + O2

Catalyst Intermediate

2KMnO4  K2MnO4 + MnO2 + O2

K2MnO4 + Cl2  2KCl + MnO2 + O2

3. In Friedel-Craft reaction, action of anhydrous AlCl3 (catalyst) is explained as-

4. Williamson’s etherification process in presence of H2SO4 as a catalyst.

Limitations: This theory fails to explain-

(i) The action of promoters and catalytic poisons.

(ii) The function of a catalyst in heterogeneous reaction, e.g. combination of SO 2 and O2 in

presence of platinised asbestos where catalyst is solid and reactant are gases.
2. Adsorption or Contact Theory:

It explains the action of heterogenous catalysis.

According to the theory:

(i) The surface of a solid catalyst possess some isolated active spots (or centers) having residual
affinity or free unsatisfied valency forces.

(ii) Due to this free unsatisfied valency forces on the catalyst surface, the molecule of the
gaseous reactant get adsorbed in unimolecular thick layer.

(iii) The adsorbed molecule reacts due to their proximity, forming products. The latter then fly
off leaving the surface for the fresh action.

(iv) The chemical action is accelerated on account of increased concentration of the reacting
substances on the surface of the solid catalyst and no definite intermediate compound formation
takes place.

(v) The forces which keeps the molecules of reactant intact which catalyst also attracts the
reacting molecules. These distorted molecules of a catalyst being under more strain and more
reactive.

Graphical representation of the theory:

Illustrative example:

Reactions of ethane and hydrogen gas in presence of nickel as a catalyst to give saturated alkenes
is one of the examples which can be explained by the help of contact theory.

One of the industrial applications is the hydrogenation of vegetable oils to make ghee which
involves a carbon-carbon bond in the vegetable oil with hydrogen in the presence of Ni-catalyst.

With the help of contact theory, the hydrogenation process can be described as follows-

Figure: Hydrogenation of ethane to ethane in presence of Nickel catalyst

Both the molecules are absorbed by weak attractive forces. Activation occurs when the bonding
electrons in the molecules rearranges to form bonds to metal atoms, following the reaction of the
activated atoms, the weakly adsorbed ethane (C2H6) molecule escape from the surface.
This theory successfully explains the following facts-

(a) The catalysts are more efficient in finely divided state. With the increase of disintegrations,
the free surface area is also increased, thereby free valencies or active spots which are
responsible for adsorption of reactant molecules increase in number and consequently the
activity of the catalyst is also increases.

(b) Enhanced activity of a rough surfaced catalyst compared to the smooth surface: Rough
surface possesses cracks; peaks corners etc. and consequently have larger number of active spots
which in turn explain enhanced activity as compared to a smooth surface.

(c) Action of promoters is explained by assuming that loose compound is formed between the
catalyst and promoters which possess an increased adsorption capacity than pure catalyst only.

(d) Action of catalytic poisons is probably due to the preferential adsorption of poison on the
active spots of the catalysts and thus reducing the number of free active spots available for
adsorption of the reacting molecules.

Example:

(e) Specific action of catalyst: The affinity of the catalyst for the reactant molecules is solely
responsible for adsorption and adsorption occurs only when the intensity of affinity of catalyst
for the reactants are quite high, otherwise not. The action of catalyst is also specific.
L3: Acid base catalysis- including kinetics and examples, Enzyme catalysis- Introduction and
characteristic of enzymes

Acid-Base catalysis:

Acid-base catalysis is an example of homogenous catalysis which is catalyzed by Bronsted acid

or base or both.

(i) Specific proton catalyzed reaction (H+ ion catalysis): A reaction which is catalyzed by H + or
H3O+ ions but not by other proton donors (Bronsted Acids)e.g. solvolysis of esters, inversion of
cane sugar, keto-enol tautomerism.

The term specific acid catalysis is used when the reaction rate is dependent on the equilibrium
for protonation of the reactant and is governed by concentration of H+ ion, not other Bronsted
acids.

(ii) General acid Catalysis: These are the reactions which are not only catalyzed by H+ ions but
also acids including water. E.g. iodination of acetone

(iii) Specific OH- ion catalysis: A reaction which is catalyzed by OH- ion only. E.g. conversion of
acetone to diacetone alcohol which is catalyzed by OH- ion.

(iv) Generalized base catalysis: These are the reactions which are not only catalyzed by OH - ions
but also by other bases eg. OAc-

(v) Reaction catalyzed by both H+ and OH- ions: Hydrolysis of ester is an example where both
H+ ion and OH- ion can catalyze the hydrolysis process.
Kinetics of acid catalyzed reaction:

Mechanism 1:

We assume that a proton is transferred from an acid AH + to the substrate S. The acid form the
substrate SH+ then reacts with water molecule to form the product P.

Applying steady state approximation for SH+, we have,

Rate of formation of SH+ = rate of consumption of SH+

K1[S][AH+] = K-1[A] [SH+] + K2[SH+][H2O]

For very dilute solution, concentration of [H2O] almost remain constant, so

K1[SH][AH+] = K-1[A][SH+] + K2[SH+]

Solving for [SH+]. We have

The rate of formation of product is given by,

Let us discuss two limiting cases,

Case I: If K2  K-1[A]. so there is always only a small [SH+].

As the rate depends on [AH+], hence the reaction is generalized acid catalysis.

Case II: If K2  K-1[A], SH+ may be considered to be in equilibrium with reactant.

Where K is the ionization constant of [AH+]

From the equation the rate is proportional to the [H +], it is an example of specifically acid
catalyzed reaction.

Mechanism 2:

We assume that in the second step, the acid form of the substrate reacts with a base instead of
water molecule.

Applying steady state approximation,

K1[S][AH+] = K-1[A] [SH+] + K2[SH+][A]

The rate of the reaction is.

From the above equation, it is obvious that the rate of the reaction is proportional to [AH +], it is
an example of general acid catalysis.
Examples:

(i) Hydrolysis of esters: This is a specific acid catalyzed reaction when the reaction rate is
dependent on the equilibrium for the protonation of reaction.

Base catalyzed hydrolysis of esters.

(ii) Halogention of acetone:

Rate determining step is the enolisation of acetone followed by a rapid addition of halogen to the
enol. The enolisation of acetone is catalyzed by acids or bases.

Base catalyzed enolisation of acetone and halogenation:

Modern concept of acid base catalysis:

(i) A reaction which is catalysed by an acid is also catalysed by all substances which have a
tendency to loose proton.

(ii) A reaction which is catalysed be base is also catalysed by all substances which have a
tendency to gain proton.

Enzymes or biological catalyst:

Enzymes are highly complex, non-living nitrogenous organic substances produced by living
animals and plants. They possess the incredible capacity in bringing about many complex
chemical reactions like hydrolysis, oxidation, reduction etc. They are highly specific and each
enzymes can catalyze a specific reaction. It also lowers the activation energy for a particular
reaction. Examples:

(i) Starch is catalyzed by diastage to form maltose in turn by maltase into glucose.
(ii) Invertage converts cane sugar into a mixture of glucose and fructose while zyamase converts
glucose and fructose into alcohol.

(iii) The enzymes urease (present in Soyabeans) converts urea quantitatively into ammonia and
CO2 or (NH4)2CO3.

The enzymes ptyalin present in human mouth (saliva) converts starch into glucose.

Characteristics of Enzymes:

(i) enzymes are protein that can acts as enormously effective catalyst and can speed up the
reaction by high factors of upto 1012.

(ii) They are highly specific and each enzymes catalyze a particular reaction. (Key and Lock).

(iii) All enzyme reaction exhibits maximum efficiency at optimum temperature. Above this
temperature the enzymes gets denatured, thereby losing its activity.

For most enzymes, the reaction rates increases upto 450C and above 450C, thermal denaturation
take place. Above 550C, rapid thermal denaturation destroys completely the catalytic activity of
the enzyme protein. Enzyme decreases the activation energy of a reaction at a given temperature.

(iv) Enzyme catalyzed reactions are much more sensitive to catalytic poison such as HCN, CS2,
H2S etc. the inhibitors (or poisons) interact with the functional groups present on the enzyme
surface and often reduce or completely destroy the catalytic activity of the enzyme.

(v) Activity of certain enzymes depends upon certain non-protien substances called co-enzymes.
For each enzyme, there is only one co-enzymes.

(vi) Enzymes loose their activity when exposed to UV radiation or in presence of electrolyte.

(vii) The effect of PH on the rate of enzyme catalysed reaction is of complex nature. Usually the
rate possess through a maximum as the PH increased. (PH 5-7)
(viii) Even a small amount of an enzyme can be highly efficient in bringing about a particular
biological reaction.

(ix) Enzyme does not disturb the final state of equilibrium.

L4: Mechanism and kinetics of enzyme catalyzed reaction, Michaelis-Menten equation,

Lineweaver - Burk Plot.

Mechanism and kinetic of enzyme catalysed reaction:

L. Michaelis and Mary Menten proposed a mechanism for the kinetics of enzyme catalysed
reactions which involves the following steps-

Step 1: Formation of enzyme-substrate complex

Step 2: Decomposition of the enzyme-substrate complex to give the products.

Overall reaction,

Now the enzyme is consumed in step 1 and but regenerated in backward step. Since step 2 is
slow (rate determining) so the rate of the reaction is given by,

Using the steady state approximation with respect to ES,

Rate of formation of ES = Rate of consumption of ES

The equilibrium between the free and bound enzyme E and ES is given by the equation,

[E]o = [E] + [ES]

[E] = [E]o - [ES]

Where, [E]o = total enzyme concentration which can be measured

[E] = free enzyme concentration which cannot be measured

[ES] = Reacted or bound enzyme concentration

Dividing by K1, we get,

This equation is known as Michaelis-Menten equation and Km is known as Michaelis constant.

When all the enzymes has reacted with the substrate at high concentration, the rate of the
reaction will be maximum. Under this condition, no free enzyme will be remain and hence,

[E]o = [ES]

Maximum rate = Vmax = K2[ES] = K2[E]o

Where K2 is called turn over number of the enzyme. The number of molecules converted
in unit time by one molecule of enzyme is called turn over number and its value ranges from
100-1000s-1 but can be 105-106 s-1.

Now the rate is given by,

Case I: If, Km  [S], then we get, neglecting S in the denominator,

Thus, the enzyme catalyzed reaction is of first order, when the substrate concentration is low.

Case II: If Km  [S], so that we can neglect Km, then,

Enzyme catalyzed reaction is zero order when substrate concentration is high.

Case III: If, Km = [S], then,

i.e. Michaelis constant is that concentration of the substrate at which rate of formation of
products is equal to half the maximum rate of formation of products at high concentration of the
substrate.
This above equation is a equation of straight line, Y = mx + C
L5: Important catalysts in industrial processes, Hydrogenation using Wilkinsons catalyst,
Hydroformylation by using Cobalt-catalyst

Applications of Catalysts for industrially important Processes:

Sl Process Catalyst Temperature Reaction Remarks

No

1 Haber’s Fe 4500C N2 + 3H2  2NH3 It is used for the

Process manufacture of ammonia;
Al2O3 + K2O or Mo is
also used as Promoters

2 Contact V2O5 or 4500C 2SO2 + O2  2SO3 It is used for the

Process Platinised manufacture of sulfuric
asbestos acid

3 Chamber NO 2SO2 + O2  2SO3 It is used for the

Process manufacture of sulfuric
acid

4 Bosch’s Fe2O3 400-4500C (CO + H2) + H2O It is used for the

Process CO2 + 2H2 manufacture of H2. Cr2O3
is used as promoter.

5 Ostowald Platinised 3000C 4NH3 + 5O2  4NO Excess of air (as promoter)
s Process Asbestos + 6H2O; is also required.

2NO + O2  2NO2

4NO2 + 2H2O + O2
 4HNO3

6 Bergius Tin or 4500C Coal  Gasoline Heavy oil is also required

Process Nickel for making paste of coal
oleate with catalyst.
7 Hardenin Nickel 150-3000C Oils  Fats It is used for the
g of oil manufacture of vegetable
ghee from vegetable oil.

Hydrogeneation reaction by Wilkinson’s Catalyst: (PPh3P)3RhCl

Tris-triphenyl phosphine Rhodium Chloride,(PPh3P)3RhCl which is generally known as

Wilkinson’s Catalyst acts as a homogenous catalyst for the hydrogenation of alkenes and
alkynes. The catalyst is not able to reduce other functional groups although it is very reactive
compound. The mechanism of the reaction is given below:
Figure: Mechanism of hydrogenation reaction using Wilkinson’s Catalyst

Hydroformylation reaction by Cobalt carbonyl:

The reaction of an alkene with synthesis gases i.e. mixture of carbon monoxide and
hydrogen(CO + H2) to produce an aldehyde is known as hydroformylation. The reaction takes
place inpresence of a catalyst. Industrially Cobalt carbonyl is used as a catalyst at 130-170 0C and
under 200-300 atmospheric pressure.

The mechanism of hydroformylation using cobalt carbonyl as catalyst is shown below;

Figure: Mechanism of Hydroformylation reaction using Cobalt catalyst

Suggested Readings:

1.

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