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Catalysis Notes PDF
Catalysis Notes PDF
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
∆H
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UNIT IV: CATALYSIS 2014
Although a catalyst lowers the activation energy E a for a reaction, it does not affect the
energy difference ∆H between the products and reactants. It is clear from Arrhenius
equation, lower the value of activation energy (E a) faster will be the rate of a reaction.
(Note: Arrhenius equation is K = A e-Ea/RT, where A is the Arrhenius factor or the
frequency factor, R is gas constant, Ea is activation energy.)
CHARACTERISTICS OF CATALYSIS:
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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UNIT IV: CATALYSIS 2014
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UNIT IV: CATALYSIS 2014
b) Heterogeneous catalysis:
The catalytic process in which the reactants and the catalyst are in different
phases is known as heterogeneous catalysis.
The catalyst is usually a solid, and the reactants are either gases or liquids.
Heterogeneous catalysis is the most important type of catalysis in industrial
chemistry. It is also used in catalytic converters in automobiles.
Examples of heterogeneous catalysis with gaseous reactants:
i) Oxidation of SO2(g) to SO3(g) in the presence of Pt.
iii) Oxidation of ammonia into nitric oxide in the presence of platinum gauze in
Ostwald’s process.
Ni(s)
vegetable oils (l) + H 2(g) vegetable ghee(s)
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UNIT IV: CATALYSIS 2014
a. Promoters or activators:
Promoters are substances that enhance the activity of a catalyst. Such
substances act as catalyst for the catalyst.
For example, In Haber’s process for manufacture of ammonia, molybdenum acts
as a promoter for iron which is used as a catalyst.
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UNIT IV: CATALYSIS 2014
H ---------- H
H ----- H Fe Fe Fe
Fe Fe Fe Fe Mo Mo
Fe 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.
O O O
C C C
Pt Pt Pt Pt Pt Pt
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UNIT IV: CATALYSIS 2014
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:
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UNIT IV: CATALYSIS 2014
c. Numerous reactions that occur in the bodies of animals and plants to maintain
the life process are catalysed by enzymes. The enzymes are, thus, termed as
biochemical catalysts and the phenomenon is known as biochemical catalysis.
d. The first enzyme was synthesised in the laboratory in 1969.
The following are some of the examples of enzyme-catalysed reactions:
1. Inversion of cane sugar into glucose and fructose by invertase enzyme.
2. Conversion of glucose into ethyl alcohol and carbon dioxide by zymase enzyme.
diastase
2(C6H10O5)n(aq) + nH2O(aq) nC12H22O11(aq)
starch 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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UNIT IV: CATALYSIS 2014
1. One molecule of an enzyme may transform one million molecules of the reactant per
minute.
2. Each enzyme is specific for a given reaction, i.e., one catalyst cannot catalyse more
than one reaction. For example, the enzyme urease catalyses the hydrolysis of urea
only.
3. The rate of an enzyme reaction become maximum at a definite temperature, called
the optimum temperature. On either side of the optimum temperature, the enzyme
activity decreases. The optimum temperature range for enzymatic activity is 298-310
K. Human body temperature being 310 K is suited for enzyme-catalysed reactions.
4. The rate of an enzyme-catalysed reaction is maximum at a particular pH called
optimum pH, which is between pH values 5-7.
5. The enzymatic activity is increased in the presence of certain substances, known as
co-enzymes.
6. The inhibitors interact with the active functional groups on the enzyme surface and
often reduce or completely destroy the catalytic activity of the enzymes.
There are a number of cavities present on the surface of enzymes. These cavities
are of characteristic shape and possess active groups like -NH2, -COOH, -SH, -OH, etc.
These are actually the active centres on the surface of enzyme particles. Molecules of
the substrate, which have complementary shape, fit into these cavities just like a key fits
into a lock.
Thus, the enzyme-catalysed reaction proceeds in two steps.
Step 1: Binding of enzyme (E) to substrate (S) forms enzyme substrate complex
(ES)
Step 2: Decomposition of the enzyme substrate (ES) complex to form product (P)
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UNIT IV: CATALYSIS 2014
In 1913, Michaelis and Menten proposed a mechanism for the kinetics of enzyme
catalyzed reaction. It involves two steps
Step I: The enzyme (E) reacts with the substrate (S) to form enzyme-substrate complex
(ES). This is a reversible process and equilibrium is established rapidly.
Step II: The ES complex undergoes dissociates to give product (P) and enzyme (E).
K2
ES P + E .....(2)
enzyme-substrate complex product enzyme
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UNIT IV: CATALYSIS 2014
Instead of solving for [ES] in terms of Free enzyme [E], solve for [ES] in terms of Total
enzyme [E]0.
Where, Km = K -1 + K2
K1
[ES] = [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
Equation (8) is known as Michaelis-Menten equation.
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UNIT IV: CATALYSIS 2014
Rate of product formation = K2 [E]0 [S] = K2 [E]0 [S] = 1 K2 [E]0 half maximal rate
Definition of Michaelis constant (Km) = concentration of [S] for which the rate is
half-maximal.
..………………………………..Chapter completed……………………………………….
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