Chapter 5

CATALYSIS

1. THE BASIC CONCEPTS

2. CHARACTERISTICS OF CATALYST

3. HOMOGENEOUS CATALYSIS

4. HETEROGENEOUS CATALYSIS

5. ENZYME CATALYSIS
THE BASIC CONCEPTS 1
 THE BASIC CONCEPTS 2

 Catalysis
 A substance that alters the reaction rate of a particular
chemical reaction.
 Chemically unchanged at the end of the reaction
 Positive catalyst → increase the rate
 Negative catalyst (inhibitor) → decrease the rate
 By providing an alternative pathway (or mechanism)
lower/higher activated energy
 A small quantity of the catalyst is required
 The catalyst remains unchanged (in mass or chemical composition) in the reaction (Activities of catalyst).
 The catalyst does not change the equilibrium constant. But equilibrium approaches earlier
 The catalyst can not make the impossible reaction occur and does not initiate reaction
 CHARACTERISTICS OF CATALYST 3

 NEGATIVE CATALYST
 The catalyst which decreases the rate of reaction is called negative catalyst and
phenomenon is called inhibition.
 Ex:
Acetanilide
H2 O 2 H2 O + O
 CHARACTERISTICS OF CATALYST 4

 AUTO CATALYSIS

 The product in the reaction be the catalyst of the reaction

 This product is called auto catalyst
 CHARACTERISTICS OF CATALYST 5

 PROMOTERS CATALYST
 Those substances which are added with catalysts in a chemical reaction to increase the
efficiency or activity of catalyst.
 CHARACTERISTICS OF CATALYST 6

 CATALYST POISIONS
 Substances that destroy or reduce the strength of the catalyst when present in a small
amount with a catalyst are called poisons catalyst or anti catalyst.
Catalyst
poisions
 CHARACTERISTICS OF CATALYST 7

 Homogeneous catalysis: The reactants and  Heterogeneous catalysis: In a chemical

catalysts are in the same physical state in this reaction, when the physical states of the
reaction. This reaction is also an example reactants and catalysts differ, the catalyst
of Homogeneous catalysis is called heterogeneous catalysis

There is no homogeneous catalyst in the solid phase

 HOMOGENEOUS CATALYSIS 8

 KINETICS OF ACID – BASE CATALYSED REACTION

 For the reaction:

 Acidity catalyst:

 Base catalyst:

 Non-catalyst:

 Rate of reaction: v = 𝐇 + 𝐎𝐇 + 𝐨 = k.[S]

 HOMOGENEOUS CATALYSIS 9

 KINETICS OF ACID – BASE CATALYSED REACTION

 Catalyst is a strong acid

• k2 >> k1, k3

And = const = A
 HOMOGENEOUS CATALYSIS 10

 KINETICS OF ACID – BASE CATALYSED REACTION

 Catalyst is strong base:

 k3 >> k1, k2

 =

 B=
 HOMOGENEOUS CATALYSIS 11

 KINETICS OF ACID – BASE CATALYSED REACTION

 Summaries

1. Acid – Base catalyst

2. Acid catalyst

3. Base catalyst

4. Acid – Base catalyst and non-catalyst

HETEROGENEOUS CATALYSIS 12
 HETEROGENEOUS CATALYSIS 13

 PHASE DIVISION IN HETEROGENEOUS CATALYSIS

1. Transport of reactants A, … from the main

stream to the catalyst surface
2. Transport of reactants in the catalyst pores
3. Adsorption of reactants on the catalytic sites
4. Chemical reaction between adsorbed atoms
or molecules
5. Desorption of products B, …
6. Transport of products in the catalyst pores
back to particle surface
7. Transport of products from the particle
surface back to the main fluid stream.
 HETEROGENEOUS CATALYSIS 14

 RATE LAW
 For the monomolecular reaction S → P
 Diffusion velocity
 Kinematic rate

 Diffusion velocity:  Kinematic rate:

 Fick’s law: the rate of mass transfer through a
 From rate law: vk = kk .CSn
surface area is related to the concentration
- kk: rate constant
gradient
- CS: conc of reactants on surface area
dq/dt = -D.σ.dC/dl
- n: order of reaction
D: diffusion coefficient (m2/sec) ; dq/dt (g/cm2.sec)
σ: surface area
dC/dl: concentration gradient ; l (cm)
 HETEROGENEOUS CATALYSIS 15

 Fick’s law: σ

 Assume for units volume, V: σ.

as: dC = dq/V

 Rate of diffusion through units volume, V:

 HETEROGENEOUS CATALYSIS 16

 Rate of diffusion: vdif = kdif(CS - CX)

 In the area between diffusion and kinetic:

 HETEROGENEOUS CATALYSIS 17

 When kk >> kdif (kinetic area)

 Vdif << Vk

 Rate constant of reaction, kc:

HETEROGENEOUS CATALYSIS 18

 When kk << kdif (diffusion area)

 Vdif >> Vk

and ∆C ≈ 0
 HETEROGENEOUS CATALYSIS IN INDUSTRY

 Reforming methanol reaction with Pd/Zn/ZnO

 HETEROGENEOUS CATALYSIS IN INDUSTRY
 HETEROGENEOUS CATALYSIS IN INDUSTRY
 HETEROGENEOUS CATALYSIS IN INDUSTRY
 ENZYME CATALYSIS 19

 STRUCTURE OF ENZYMES

 Enzymes also called as biocatalyst

are protein
 The sequence of amino acids
determine the protein shape and
therefore its function
 The shape of active site is
different for each enzyme. This is
where the reaction occurs
 ENZYME CATALYSIS 20

 STRUCTURE OF ENZYMES
 ENZYME CATALYSIS 21

 STRUCTURE OF ENZYMES
 Secondary structure
 ENZYME CATALYSIS 22

 STRUCTURE OF ENZYMES
 Tertiary structure
 ENZYME CATALYSIS 23

 STRUCTURE OF ENZYMES
 Quaternary structure
 ENZYME CATALYSIS 24

 PROPERTIES OF ENZYME

 Reaction specific
 Each enzyme works with a specific substrate
• Chemical fits between active sites and
substrate
- H bonds and ionic bonds
 Not consumed in reaction
 Single molecule enzyme can catalyzed
thousands or more reactions per second
• Enzyme unaffected by the reaction
 ENZYME CATALYSIS 25

 PROPERTIES OF ENZYME

 Affected by cellular conditions

 Any conditions affected the protein structure: temperature, pH, salinity …
 ENZYME CATALYSIS 26

 APPLICATIONS OF ENZYME