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uk A2 1029 01-Jun-2016
INTRODUCTION

Catalyst = substance that speeds up reaction without being


used up.
They provide an alternative mechanism with lower activation
energy.
For an equilibrium, they speed up both reactions equally and
so do not effect equilibrium position.
Heterogeneous catalyst is in different phase to the
reactants.
Homogeneous catalyst is in the same phase as the
reactants.

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INTRODUCTION
HETEROGENEOUS CATALYSTS

Usually a solid catalyst and gaseous reactants.


Most industrial catalysts are like this (e.g. Haber, Contact).

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HETEROGENEOUS CATALYSTS

1) Reactants adsorbed onto surface (onto active sites).


weakens bonds
brings molecules closer
more favourable orientation
2) Reaction takes place.

3) Products are desorbed (leave the surface).

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HETEROGENEOUS CATALYSTS
HETEROGENEOUS CATALYSTS

Strength of adsorption:

Too strong (e.g. W)


W
Reactants cannot move round surface.
Products cannot desorb.

Too weak (e.g. Ag)


Reactants not adsorbed.

Ideal (e.g. Ni, Pt)

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HETEROGENEOUS CATALYSTS

Nature of catalyst

Large surface area.


Spread thinly over ceramic
honeycomb.
HETEROGENEOUS CATALYSTS

Poisoning

Some substances may block active sites (i.e. they adsorb and
will not come off). Can ruin catalyst.
e.g. S in Haber process
e.g. Pb in catalytic converters

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HETEROGENEOUS CATALYSTS

Example reaction V2O5 in Contact Process

V2O5 + SO2 V2O4 + SO3

V2O4 + O2 V2O5

Overall: SO2 + O2 SO3

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HOMOGENEOUS CATALYSTS

Most examples involve reactions in solution with catalyst in


solution.
Some gas phase examples.

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HOMOGENEOUS CATALYSTS

1) Catalyst reacts with a reactant to form intermediate.


2) Intermediate reacts to form product faster than original
reactant (and regenerates catalyst).

e.g. acid catalyst X + Y products

1) X + H+ HX+
2) HX+ + Y products + H+

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HOMOGENEOUS CATALYSTS

e.g. acid catalyst in esterification


e.g. CH3COOH(l) + CH3OH(l) CH3COOCH3(l) + H2O(l)

No H+ catalyst
SLOW step
:

H+

With H+ catalyst : +
FASTER - H+

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HOMOGENEOUS CATALYSTS

e.g. transition metal catalyst


works by metal varying oxidation state

Fe2+ or Fe3+
e.g. 2 I- + S2O82- I2 + 2 SO42-

Slow because both ve ions so repel.


1) 2 Fe2+ + S2O82- 2 Fe3+ + 2 SO42-
2) 2 Fe3+ + 2 I- 2 Fe2+ + I2

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HOMOGENEOUS CATALYSTS

0 +

+ 0.54 V + 1.51 V
I2 + 2 e- 2 I- S2O82- + 2 e- 2 SO42-
+ 0.77 V
Fe3+ + e- Fe2+

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HOMOGENEOUS CATALYSTS

e.g. transition metal catalyst


works by metal varying oxidation state

Mn2+
e.g. 2 MnO4- + 16 H+ + 5 C2O42- 2 Mn2+ + 8 H2O + 10 CO2

the reaction is catalysed by one of the products (Mn2+) so is


autocatalysis

4 Mn2+ + MnO4 + 8 H+ 5 Mn3+ + 4 H2O


2 Mn3+ + C2O42 2 CO2 + 2 Mn2+

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