CATALYSIS

Catalysis
Catalysis is an action by a catalyst that takes part in a chemical reaction
process and can alter the rate of reactions, and yet itself will return to its
original form without being consumed or destroyed at the end of the
reactions.
Three key aspects of catalyst action
Taking part in the reaction
• it will change itself during the process by interacting with other reactant/product molecules
Altering the rates of reactions
• in most cases, the rates of reactions are increased by the action of catalysts; however, in some
situations, the rates of undesired reactions are selectively suppressed
Returning to its original form
• After reaction cycles, a catalyst with exactly the same nature is ‘reborn’
• In practice, a catalyst has its lifespan - it deactivates gradually during use

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 Catalyst
A catalyst is defined as a substance that alters the rate of a chemical
reaction, itself remaining chemically unchanged at the end of the reaction.

Characteristic features of catalysts are –

1.Catalyst may undergo physical changes but not chemical
2.Small quantities of catalyst are sufficient for catalysis
3.Catalyst alters the rate of reaction but cannot initiate it
4.Catalytic activity is maximum at optimum temperature and pH
5.Catalyst lowers the activation energy of forward and backward reaction and also lowers
threshold energy
6.It provides a new mechanism for the reaction

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• Positive catalysts are those catalysts which increase the rate of the reaction.
The activation energy of the reaction is lowered, and the speed of the reaction
also increases.
• An example of positive catalysis is the decomposition 0of potassium chlorate.
Without a catalyst, decomposition takes0 place at 700 C, and with an MnO
catalyst, decomposition takes place at 300 C.

MnO
KClO3 KCl + O2

• Chemical reactions are sometimes retarded by the presence of a foreign

substance. This substance is known as a negative catalyst.
• Examples: Phosphoric acid serves as a negative catalyst for the decomposition
of H2O2.
• Alcohol acts as a negative catalyst in the oxidation of Sodium sulfide Na2SO3.
• The decomposition of hydrogen peroxide is retarded by the presence of dilute
acids or glycerol.

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 Types of Catalysts & Catalytic Reactions
• The types of catalysts
• Classification based on the its physical state, a catalyst can be
• Gas CH3CHO + (I2) ⎯⎯→ CH4 + CO
H2SO4
• Liquid C12H22O11 + H2O ⎯⎯⎯⎯→ C6H12O6 + C6H12O6 + [H2SO4]
• Solid N2 + 3H2 + [Fe] ⎯⎯→ 2NH3 + [Fe]
• Classification based on the substances from which a catalyst is made
• Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
• Organic (organic acids, enzymes etc.)
• Classification based on the ways catalysts work
• Homogeneous - both catalyst and all reactants/products are in the same phase (gas or liq)
• Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)
• Classification based on the catalysts’ action
• Acid-base catalysts
• Enzymatic
• Photocatalysis
• Electrocatalysis, etc.
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 PROMOTERS
•A substance which, though itself not a catalyst, promotes the
activity of a catalyst is called a promoter.
Example: Molybdenum (Mo) promotes the activity of iron
catalyst in the Haber synthesis for the manufacture of ammonia
Fe
N2 + 3H2 → +Mo 2NH3

POISON
A substance which destroys the activity of the catalyst to
accelerate a reaction, is called a poison.
Example: The iron catalyst used in the synthesis of ammonia
(Haber Process) is poisoned by H2S.
Fe
N2 + 3H2 → H 2NHS 3
2

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AUTOCATALYSIS
• When one of the products of reaction itself acts as a catalyst for that
reaction the phenomenon is called Autocatalysis.
• In autocatalysis the initial rate of the reaction rises as the catalytic
product is formed, instead of decreasing steadily.
• The curve plotted between reaction rate and time shows a maximum
when the reaction is complete.
Example: The hydrolysis of ethyl acetate forms
acetic acid (CH3COOH) and ethanol. Then, acetic
acid acts as a catalyst for the reaction.

CH3COOC2H5 + H2O ⎯⎯→ CH3COOH + C2H5OH

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 Action of Catalysts
• Catalysis action - Reaction kinetics and mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to non-catalytic reaction)
• Forming complex with reactants/products, controlling the rate of elementary steps in the
process. This is evidenced by the facts that
• The reaction activation energy is altered uncatalytic

• The intermediates formed are different from catalytic

energy
those formed in non-catalytic reaction reactant
• The rates of reactions are altered (both
product
desired and undesired ones)
reaction process
• Reactions proceed under less demanding conditions
• Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat
sensitive materials

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 How catalysts increase the reaction rate
and the selectivity of chemical reactions?

• The presence of a catalyst lower Ea, the

reaction rate of a catalyzed reaction is
faster than the reaction rate of the
uncatalyzed reaction at the same
temperature.
• Because a catalyst decreases the height
of the energy barrier, its presence
increases the reaction rates of both the
forward and the reverse reactions by
the same amount.

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 THEORIES OF CATALYSIS
There are two main theories of catalysis :
•Intermediate Compound Formation theory
•The Adsorption theory
Intermediate Compound Formation theory

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The Adsorption theory
Four steps of adsorption –

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 Enzyme as Biocatalyst
Catalysis brought about by enzymes is known as Enzyme Catalysis.
Conversion of glucose into ethanol by Zymase present in yeast,
C6H12O6 ⎯⎯→ 2C2H5OH + 2CO2

• In the enzyme catalysed reaction, the substrate is changed to the product via a high
energy transition state.

• The state has a very short life cycle and it is stabilized by the enzyme. For an
enzyme catalyzing a simple reaction from substrate to product the overall reaction
can be written in two steps:
E+S ES
ES E+P
• An example of this type of reaction is decomposition of hydrogen peroxide into
water and oxygen. Although the reaction is strongly favored thermodynamically, it
is very slow unless catalyzed.

• Catalase increases the uncatalyzed rate of H2O82 decomposition. In the presence of

catalase, the decomposition of H2O2 occurs 10 times faster than in the absence of
catalase.
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 Why enzymes?
• Speed
• Catalase has the highest turnover number value of 40,000,000 (per
second per molecule of enzyme),
• Carbonic anhydrase 400,000 (per second per molecule of enzyme),
• Specificity
• Reaction condition
• Cleanliness

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 Chemical Catalyst Enzyme

Function Catalysts are substances that increase or Enzymes are proteins that increase rate of
decrease the rate of a chemical reaction chemical reactions converting substrate into
but remain unchanged. product.

Molecular weight Low molecular weight compounds. High molecular weight globular proteins.

Types There are two types of catalysts – There are two types of enzymes - activation
positive and negative catalysts. enzymes and inhibitory enzymes.

Nature Catalysts are simple inorganic Enzymes are complex proteins.

molecules.
Alternate terms Inorganic catalyst. Organic catalyst or bio catalyst.
Reaction rates Typically slower Several times faster
Specificity They are not specific and therefore end Enzymes are highly specific producing large
up producing residues with errors amount of good residues

Conditions High temp, pressure Mild conditions, physiological pH and

temperature
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 Factors Affecting Enzyme Activity

• Enzyme Concentration
• Substrate Concentration
• pH Value (Pepsin – 2, Trypsin – 7.8)
• Temperature (Taq polymerase – ~75, Proteases – 37, RE – 37 )
• Effector (DNAse – Mg2+)
• Inhibitor
• Reversible (acetylcholinesterase inhibitor – rivastigmine)
• Irreversible (Peptidase inhibitor – penicillin)

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 Applications of Catalysis
• Industrial applications
Almost all chemical industries have one or more steps employing
catalysts
• Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals …

Advantages of catalytic processes

• Achieving better process economics and productivity
• Increase reaction rates - fast
• Simplify the reaction steps - low investment cost
• Carry out reaction under mild conditions (e.g. low T, P) - low energy consumption
• Reducing wastes
• Improving selectivity toward desired products - less raw materials required, less unwanted wastes
• Replacing harmful/toxic materials with readily available ones
• Producing certain products that may not be possible without catalysts
• Having better control of process (safety, flexible etc.)
• Encouraging application and advancement of new technologies and materials
• And many more …
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 Applications of Catalysis
• Environmental applications
• Pollution controls in combination with industrial processes
• Pre-treatment - reduce the amount waste/change the composition of emissions
• Post-treatments - once formed, reduce and convert emissions
• Using alternative materials
• Pollution reduction
• gas - converting harmful gases to non-harmful ones
• liquid - de-pollution, de-odder, de-colour etc
• solid - landfill, factory wastes

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 Biocatalysts in
green chemistry

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