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CATALYSIS
INTRODUCTION:
The systematic study of the effect of various foreign substances on the rates of chemical
reactions was first made by Berzelius in 1835. He suggested the term catalyst for such
substances. In Greek, kata = wholly, lein = to loosen.
CATALYST:
Substances, which accelerate the rate of a chemical reaction and themselves remain
chemically and quantitatively unchanged after the reaction, are known as catalysts.
For example, MnO2 acts as a catalyst for the following reaction
The phenomenon of increase in the rate of a reaction that results from the addition of a
catalyst is known as catalysis.
The action of the catalyst can be explained on the basis of intermediate complex theory.
According to this theory, a catalyst participates in a chemical reaction by forming temporary
bonds with the reactant resulting in an intermediate complex which decomposes to yield
product and the catalyst.
It is believed that the catalyst provides an alternative pathway or reaction mechanism by
reducing the activation energy between reactants and products and hence lowering the
potential energy barrier, and the reaction rate is increased as shown below
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CHARACTERISTICS OF CATALYSIS:
1. Catalyst remains chemically and quantitatively unchanged after the reaction.
However, it may undergo a physical change.
2. A small amount of the catalyst can catalyse a large amount of reactants. For
example, 1 g of metallic platinum is sufficient to decompose 108 liters of H2O2.
while, some catalysts are required in relatively large amount to be effective. For
example, In Friedel-Crafts reaction, anhydrous aluminium chloride catalyst is
required to the extent of 30% of the mass of benzene.
3. The activity of a solid catalyst is enhanced with increase in its surface area.Thus,
finely divided nickel is a better catalyst than lumps of nickel.
4. Catalyst is specific in its action.while a particular catalyst can be used for one
reaction, it will not necessarily work for another reaction. For example,
decomposition of KClO3 is catalyzed by MnO2 but not by platinum.
Sometimes, for the same substrate different catalyst yield different products.
5. Catalyst cannot initiate a reaction. In most cases, it accelerates the reaction already
in progress.
6. Catalyst does not change the equilibrium constant of a reaction. It helps in attaining
the equilibrium faster, that is, it catalyses the forward as well the backward reactions
to the same extent so that the equilibrium state remains same but is reached earlier.
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iii) Oxidation of ammonia into nitric oxide in the presence of platinum gauze in
Ostwalds process.
H 2(g)
Ni(s)
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vegetable ghee(s)
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Fe
Fe
Fe
Fe
Fe
Mo
Fe
Fe
Mo
Fe
Fe
ii) Increase of active sites: The number of peaks and cracks on the catalyst
surface is increased on the addition of promoter to the catalyst. This increases
the concentration of reactants and rate of the reaction.
b. Inhibitors or catalytic poisons:
Inhibitors are substances that decrease the activity of a catalyst or make the
catalyst inactive.
Arsenius oxide and HCN are two of the most powerful catalytic poisons.
Some examples of catalytic poisons
1. Arsenius oxide poisons the catalytic activity of platinized asbestos in the
manufacture of H2SO4 by contact process.
2. Platinum catalyst used in the oxidation of H2 is poisoned by CO.
O
C
Pt
O
C
Pt
Pt
O
C
Pt
Pt
Pt
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AUTO CATALYSIS:
When one of the products formed during the course of reaction itself act as a
catalyst for that reaction the phenomenon is called as autocatalysis.
In normal reaction, the rate of reaction decreases with the passage of time. However,
in autocatalysis, as the reaction proceeds, concentration of catalytic product increases
and so the rate of reaction increases.
Examples:
1) Hydrolysis of methyl acetate is catalysed by H+ ions furnished by acid. As the
reaction proceeds, concentration of catalyst (H+) increases and hence, the rate of
reaction increases.
ENZYME CATALYSIS:
a. Enzymes are complex nitrogenous organic compounds produced by living
plants and animals which facilitate the reactions, but unlike other catalysts
are not consumed in reactions.
b. They are typically proteins or RNA.
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2. Conversion of glucose into ethyl alcohol and carbon dioxide by zymase enzyme.
nC12H22O11(aq)
maltose
6. In stomach, the pepsin enzyme converts proteins into peptides while in intestine, the
pancreatic trypsin converts proteins into amino acids by hydrolysis.
7. Conversion of milk into curd: It is an enzymatic reaction brought about by lacto bacilli
enzyme present in curd.
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Step 2: Decomposition of the enzyme substrate (ES) complex to form product (P)
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Step II: The ES complex undergoes dissociates to give product (P) and enzyme (E).
K2
ES
enzyme-substrate complex
product
..(4)
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10
E
enzyme
.....(2)
[ES]
K1 [E]0 [S]
..(6)
K-1 + K2 + K1[S]
Dividing the numerator and denominator by K1
[ES] =
K1 [E]0 [S] K1
{ K -1 + K2 + K1 [S]} K1
[ES] =
K1 [E]0 [S]
K1 [E]0 [S]
K1 { K-1 + K 2 + K1 [S]} K1
=
K 1 { K-1 + K2 + K1 [S]}
[E]0 [S]
..(7)
K1
K1
K1
[E]0 [S]
..(8)
(Since, K-1 + K 2 = Km )
[S] + Km
K1
Substitute [ES] into equation (3)
Rate of product formation = d[P] = K2[ES] = K2 [E]0 [S] ..(8)
dt
[S] + Km
2[S]
Definition of Michaelis constant (Km) = concentration of [S] for which the rate is
half-maximal.
....Chapter completed.
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