Problem 1.

Define catalyst and catalysis. Mention

the types and classification of catalysis.
Discuss the characteristics of catalytic
reactions.

Prepared by: Atta Subhan 364704

[I] Catalyst and Catalysis
 Berzelius (1835) found that the speed of a number of reactions is
increased due to the presence of a small quantity of a foreign
substance.
 He also found that these substances remain chemically unchanged
at the end of the reaction.
 He termed these substances as catalysts and the phenomenon itself
is known as catalysis.
 A familiar example is that of the decomposition of KCI 3.
 The decomposition of KClO3 is very slow even at high
temperature, but a small quantity of MnO2 increases the rate of
decomposition to a very great extent and MnO2 remains
chemically unchanged at the end of the reaction.
 Butlater on it was observed that there are certain substances
which can retard the rate of a chemical reaction.
 Hence. Ostwald defined that,
 “A catalystis a substance which influences the speed of a
chemical reaction without itself undergoing any chemical
change at the end of the reaction.”
 Catalysis is mainly divided into two types, viz., homogeneous
catalysis and heterogeneous catalysis.
[A] Homogeneous Catalysis
 When the catalyst is present in the same phase as that of the reactants,
the phenomenon is known as homogeneous catalysis.
 (a) Examples of homogeneous catalysis in gas phase
 (i) Oxidation of sulphur dioxide (SO2) to sulphur trioxide (SO3) with nitric
oxide (NO) as catalyst,
2SO2 + O2 + [NO] 2SO3 + [NO]
Gas Gas Gas Gas
 (ii) Decomposition of acetaldehyde (CH3CHO) with iodine (I2) as catalyst,
CH3CHO + [I2] CH4 +
CO + [I2]
Vapour Vapour Gas Gas
 (b) Examples of homogeneous catalysis in solution phase
 Many reactions in solutions are catalysed by acids (H+) and bases (OH-).
 Decomposition of hydrogen peroxide (H2O2) in the presence of iodide ion
(I-) as catalyst,
2H2O2 2H2O + O2
 (ii) I -
Hydrolysis of cane sugar in aqueous solution in the presence of mineral
acid as catalyst,
C12H22O11 + H2O C6H12O6 + C6H12O6
Cane sugar Glucose
H2SO4
Fructose
 (iii) Hydrolysis of an ester in the presence of acid or alkali.
CH3COOC2H5 + H2O CH3COOH +
C2H5OH H+/OH-
Ethyl acetate Acetic acid
Ethanol
[B] Heterogeneous Catalysis
 When the catalyst is in a different phase than that of
reactants, the phenomenon is known as heterogeneous
catalysis.
 Some examples of heterogeneous catalysis with reactants in the
gas, liquid or the solid phase are given below.
 (a)Heterogeneous catalysis with gaseous reactants (contact
catalysis)
 (i)Oxidation of ammonia to nitric oxide (NO) in the presence
of a platinum gauze (a stage in the manufacture of nitric acid),
4NH3 + 5O2 + [Pt] 4NO + 6H2O
+ [Pt]
Gas Gas Solid
 (ii)
Combination of sulphur dioxide (SO2) and oxygen in the
presence of finely divided platinum or vanadium pentoxide, V 2O5,
(contact process for sulphuric acid).
2SO2 + O2 + [Pt] 2SO3 + [Pt]
Gas Gas Solid
 (iii)Hydrogenation reactions of unsaturated organic compounds are
catalysed by finely divided nickel.
H2C==CH2 + H2 + [Ni] H3C____CH3 + [Ni]
Ethene (gas) Gas Solid Ethane
 Vegetable oils are tri-esters of glycerol with higher unsaturated
acid (oleic acid).
 When hydrogen is passed through the vegetable oils in presence
of nickel, the carbon-carbon double bonds of the acid portions are
hydrogenated to yield solid fats (vanaspati ghee).
 (iv)Combination of nitrogen and hydrogen to form ammonia in
the presence of finely divided iron, (Haber's process for
ammonia).
N2 + 3H2 + [Fe] 2NH3 + [Fe]
Gas Gas Solid
 (b) Heterogeneous catalysis with liquid reactants
 (i) Thedecomposition of aqueous solutions of hydrogen peroxide
(H2O2) is catalysed by manganese dioxide (MnO2) or platinum in
colloidal form.
2H2O2 + [Pt] 2H2O + O2 + [Pt]
Liquid Solid
 (ii)Benzene and ethanoyl chloride (CH3COCI) react in the presence
of anhydrous aluminium chloride to form phenyl methyl ketone
(C6H5COCH3)·
C6H6 + CH3COCl +[AlCl3] C6H5COCH3 +
HCl + [AlCL3]
Liquid Liquid Solid
 (c) Heterogeneous catalysis with solid reactants
 The decomposition of potassium chlorate (KCIO 3) is catalysed
by manganese dioxide (MnO2).
2KClO3 + [MnO2] 2KCl + 3O2 + [MnO2]
Solid Solid
 The above reaction is heterogeneous, though both reactants are
in the same phase (solid). because the solid forms a new phase.
[II] Classification of Catalysis

 Catalytic reactions are of the following four types:

 (a) Positive catalysis
 (b) Negative catalysis
 (c) Auto-catalysis
 (d) Induced catalysis
(a) Positive Catalysis:
 When the catalyst used accelerates the speed of a chemical reaction, it
is known as a positive catalyst and the phenomenon is known as positive
catalysis.
 For example, the rate of decomposition of hydrogen peroxide increases in
the presence of colloidal platinum as catalyst.
Pt
2H2O2 2H2O + O2
Catalyst
 Other reactions are:
MnO2
2KClO3 2KCl + 3O2
Fe
N2 + 3H2 2NH3
Pt or NO
2SO2 + O2 2SO3
(b) Negative Catalysis:
 When the foreign substance retards the speed of a chemical reaction, it
is known as a negative catalyst and the phenomenon is known as
negative catalysis.
 The following are examples of this type.
 (i) Decomposition of hydrogen peroxide
H3PO4
2H2O2 2H2O + O2
 (ii) Oxidation of chloroform
C2H5OH
4CHCl3 + 3O2 4COCl2 + 2Cl2 + 2H2O
 (iii) Tetraethyl lead as antiknock
 When tetraethyl lead, Pb(C2H5)4 is added to petrol, it retards the too rapid or
explosive combustion of the fuel which is responsible for the working of the
engine.
Explanation of Negative Catalysis
 The mechanism of negative catalysis could be different for
different reactions, e.g.,
 (1)By poisoning a catalyst. A negative catalyst may work by
poisoning a catalyst which already happens to be present in the
reaction mixture.
 For example, the traces of alkali dissolved from the glass of the
container, catalyse the decomposition of hydrogen peroxide
(H2O2).
 However, the addition of an acid would destroy the alkali catalyst
and thus prevents decomposition.
 (2) By breaking a chain reaction. In some cases, negative
catalysts are believed to operate by breaking the chain of
reactions. For example, the combination of H2 and Cl2 which is a
chain reaction, is negatively catalysed by nitrogen trichloride
(NCl3)
Cl2 Cl. +Cl.
Free radicals
H2 + Cl. HCl + H.
H. + Cl2 HCl + Cl.
 NCl3 breaks the chain of reactions by absorbing the propagating
species (Cl.) and the reaction stops.
NCl3 + Cl. ½ N2 + 2C2
(c) Auto-Catalysis:
 When one of the products formed in the
reaction itself acts as a catalyst, the substance
is known as an auto-catalyst and the
phenomenon is known as auto-catalysis.
 In auto-catalysis the initial rate of the reaction
rises as the catalytic product is formed, in-stead
of decreasing steadily (See fig.).
 The curve plotted between reaction rate and time
shows a maximum when the reaction is
complete.
 (i)For example, hydrolysis of ethyl acetate by water is an auto-catalytic
reaction, since acetic acid liberated in this reaction acts as a catalyst.
CH3COOC2H5 + H2O CH3COOH + C2H5OH
Auto-catalyst
 (ii) The
oxidation of oxalic acid by acidic KMnO4 is catalysed by the
presence of Mn2+ ions formed in the solution.
 In the beginning, the colour of KMnO4 disappears slowly, but as Mn2+
is formed in the solution, the colour discharges rapidly.
 So, Mn2+ ions acts as auto-catalyst.
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O
Violet Colourless
 (iii) The
free arsenic produced by the decomposition of arsine
(AsH3) auto-catalyses the reaction.
2AsH3 2As + 3H2
Catalyst
(d) Induced Catalysis:
 When one reaction influences the speed of other, which is not
possible under ordinary conditions, the phenomenon is known
as induced catalysis.
 For example, sodium sulphite solution is readily oxidised in air
but sodium arsenite solution is not oxidised by passing a current
of air through it.
 However, if air is passed through a mixture of sodium sulphite
and sodium arsenite solution, the oxidation of both take place.
 Here the oxidation of sodium sulphite acts as a catalyst for the
oxidation of sodium arsenite solution.
[III] Characteristics of Catalytic Reactions
 Although there are different types of catalytic reactions, the
following features or characteristics are common to most of them.
These features are often referred to as the criteria of catalysis.
 (1) A catalyst
remains unchanged in mass and chemical
composition at the end of the reaction.
 Qualitativeand quantitative analysis show that a catalyst undergoes
no change in mass or chemical composition.
 However, it may undergo a physical change.
 Thus, granular manganese dioxide (MnO2) used as a catalyst in the
thermal decomposition of potassium chlorate is left as a fine powder
at the end of the reaction.
 (2) A smallquantity of catalyst is generally needed to produce
almost unlimited reaction.
 Sometimes, a trace of a metal catalyst is required to affect very large
amounts of reactants.
 For example, one ten-millionth of its mass of finely divided platinum
is, however, needed to catalyse the decomposition of hydrogen
peroxide.
 On the other hand, there are catalysts which need to be present in
relatively large amount to be effective.
 Thus, in Friedel-Craft’s reaction,
Anhy. AlCl3
C6H6 + C2H5Cl C6H5C2H5 +
HCl
 Anhydrous aluminium chloride functions as a catalyst effectively when
present to the extent of 30 percent of the mass of benzene.
 (3) A catalyst cannot, in general, initiate a reaction.
 Inmost cases, a catalyst speeds up a reaction already in progress
and does not initiate (or start) the reaction.
 But there are certain reactions where the reactants do not combine
for very long period (perhaps years).
 For example, a mixture of hydrogen and oxygen, which remains
unchanged almost indefinitely at room temperature, can be brought
to reaction by the catalyst platinum black in a few seconds.
Room temp
H2 + O2 No reaction
Pt black
2H2 + O2 2H2O
 It is thus now considered that the catalyst can initiate a reaction.
 According to this view, the reacting molecules (in the absence of
catalyst) do not posses minimum kinetic energy for successful
collisions.
 The molecules rebound from collisions without reacting at all.
 (4) A catalyst is more effective when finely divided.
 In heterogeneous catalysis, the solid catalyst is more effective when
in a state of fine sub-division than when used in bulk.
 So, a lump of platinum will have much less catalytic activity than
colloidal or platinised asbestos.
 Finelydivided nickel is a better catalyst than lumps of solid nickel,
because former occupies greater surface area than the latter.
 (5) A catalyst is specific in its action.
 While a particular catalyst works for one reaction, it will not
necessarily work for another reaction.
 Different catalysts, moreover, can bring about completely
different reactions for the same substance. For example. formic
acid gives carbon dioxide and hydrogen when passed over hot
copper.
HCOOH CO2 + H2
 However,with hot aluminium oxide, formic acid gives carbon
monoxide and water.
HCOOH CO + H2O
 (6)Change of temperature changes the rate of a catalytic
reaction as it would do for the same reaction without a catalyst.
 We have already studied the effect of temperature change on
reversible reactions under Le-Chatelier's principle.
 Some catalysts are, however, physically altered by a rise in
temperature and hence their catalytic activity may be decreased.
 This is particularly true with colloidal solutions like that of
platinum, since a rise in temperature may cause their coagulation.
 Insuch a case, the rate of reaction increases up to a certain point
and then gradually decreases.
 The rate of reaction is maximum at a particular temperature
which is known as the optimum temperature.
 (7) A catalystdoes not alter the final position of
equilibrium, al-though it decreases the time
required to establish it.
 Itmeans that in a reversible reaction the catalyst
accelerates the forward and the reverse reactions
equally.
 Thus, the ratio of the rates of two opposing
reactions, i.e., the equilibrium constant, remains
unchanged.
 The effect of a catalyst on the time required for
equilibrium to be established for the reaction is
shown in figure.
 Inthe beginning, the concentrations of A and B are maximum
and so the rate of forward reaction is maximum.
 As the time passes, the rate of the re-action decreases till the
equilibrium is established.
 For the reverse reaction, the initial concentrations of C and D
are zero and the rate of reaction is lowest.
 As the time passes, the rate of reaction increases till the
equilibrium is established.
 Similar curves of the rates of reactions with the catalyst show
that the rates of the forward reaction and the reverse reaction
are changed equally but the equilibrium is established in a
much shorter time.
 For example, in the Haber's process for ammonia,
Fe
N2 + 3H2 2NH3
the reaction is very slow.
 In the presence of the catalyst, the equilibrium is reached much
earlier but the percentage yield remains unchanged.
 The iron catalyst decreases the time to attain equilibrium but
cannot change the percentage yield.
 Energy considerations also show that the final state of
equilibrium cannot be changed by the catalyst.
 Suppose the catalyst accelerates the forward reaction more
than the reverse reaction.
 Thiswill shift the equilibrium point, which cannot happen
without the supply of energy to the system.
 But a catalyst unchanged in mass and composition at the end
of the reaction, cannot supply the required energy.
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