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Reaction Mechanisms
e.g.
2 NO(g) + O2(g) 2 NO2(g)

Kinetics 15.4

es

Most reactions do not happen in one step.

Occurs in two elementary steps

Reaction Mechanisms
Catalysis

2 NO(g) N2O2(g)
N2O2(g) + O2(g) 2 NO2(g)

N
ot

Reaction
Mechanism

2 NO(g) + O2(g) 2 NO2(g)

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Reaction Mechanisms are the series of steps that sum

to the overall reaction.

Determining a Rate Law

Consumed

e.g. Consider this overall reaction.

NO2(g) + CO(g) NO(g) + CO2(g)
Rate = k [NO2]2 [CO]o
Rate = k [NO2]2

of

2 NO(g) + O2(g) 2 NO2(g)

Produced

St

2 NO(g) N2O2(g)
N2O2(g) + O2(g) 2 NO2(g)

The rate law for an overall reaction can

only be found experimentally.

ud
en

Reaction Intermediate
A substance that is produced and then
consumed during the overall reaction.

ts

Reaction Mechanisms

op

N2O2 is a reaction intermediate

Determining a Rate Law

Overall Reaction: NO2(g) + CO(g) NO(g) + CO2(g)

Overall Reaction: NO2(g) + CO(g) NO(g) + CO2(g)

pl
e

Determining a Rate Law

But, rate laws for elementary steps are predictable!
2 NO2(g) NO(g) + NO3(g)
Same rate law as
Rate = k1 [NO2]2

m
Sa

Step 1.

Step 2.

the overall reaction!

NO3(g) + CO(g) NO2(g) + CO2(g)

Rate = k2 [NO3][CO]

For any elementary step

aA + bB dD + eE
Rate = k[A]a[B]b

Step 1.

2 NO2(g) NO(g) + NO3(g)

[Slow]
Rate = k1 [NO2]2

Step 2.

NO3(g) + CO(g) NO2(g) + CO2(g) [Fast]

Rate = k2 [NO3][CO]

NO3 is consumed
as soon as it is
produced.

Adding CO does not increase

the rate, making it zero order
in the overall reaction.

The rate of the overall reaction is always equal

to the rate of the slowest elementary step.

2009 High School Chem Solutions. All rights reserved.

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Determining a Rate Law

Catalysis

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The rate law tells them what the slowest step is.
Then they try to figure out what the fast steps
are.

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2) They use the rate law to figure out what the

elementary steps are.

A catalyst increases the rate of a chemical

reactions by providing a mechanism with a
lower activation energy.
Catalysts are not produced or consumed in
the reaction.
They are there before the reaction starts, and
they return when the reaction is complete.

N
ot

1) Chemists determine the rate law through

experimentation.

Catalysis and Activation Energy

Cl

O3(g) + O(g) 2 O2(g)

to react
with
another O3

no catalyst

O3(g) + Cl(g) ClO(g) + O2(g)

with a catalyst

Ea

Ea

St

O3(g) + O(g) 2 O2(g)

O3(g) + O(g) 2 O2(g)

ud
en

The destruction of ozone.

Cl(g) + O3(g) O2(g) + ClO(g)
ClO(g) + O(g) O2(g) + Cl(g) Cl is back

Cl reacts
with O3

ts

Catalysis

A catalyst provides a mechanism with a lower

activation energy, thereby increasing the reaction rate.

op

of

Each Cl(g) atom will destroy about 100 ozone

molecules before it reacts with something else and
leaves with stratosphere.

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e

Catalysis and Equilibrium

A catalyst lowers the activation energy for the
forward and the reverse reactions.

Sa

no catalyst

with a catalyst

Ea

Ea

Keq for a reaction is the same at the same

temperature, with of without the catalyst.

Catalysis
Homogeneous Catalyst
The catalyst is in the same phase as the
reactants.
e.g. The destruction of ozone. (Cl, O3, and O
are all gases)
Heterogeneous Catalyst
The catalyst is in a different phase than the
reactants.
e.g. Synthesis of ammonia. (solid and gas)

2009 High School Chem Solutions. All rights reserved.

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Heterogeneous Catalysis

Heterogeneous Catalysis

N2(g) + 3 H2(g) 2 NH3(g)

N2(g) + 3 H2(g) 2 NH3(g)

H
N
H

ns
it

ion
al
M
eta
ls

Reactants are in the

gas phase.
Catalyst is a solid.

N
N
So
lid
H
H
H
Tr
H
an
sit
ion
al
M
eta
ls

Bonds within each gas

molecule break.
Bonds form between
the metal and the
individual atoms.

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So
lid
Tr
a

Reactants slam into

the surface.

H H

es

N
ot

Heterogeneous Catalysis

ts

Heterogeneous Catalysis

H H
N

Migration

H
N

Atoms move around

on the surface of the
metal.

St

H
ion
al
M
eta
ls

N
So
lid H
Tr
an
sit

Reaction

H
N

ion
al
M
eta
ls

Nitrogen atoms
form bonds with
hydrogen atoms.

op

of

H
So
lid
Tr
an
sit

N2(g) + 3 H2(g) 2 NH3(g)

ud
en

N2(g) + 3 H2(g) 2 NH3(g)

Heterogeneous Catalysis

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e

N2(g) + 3 H2(g) 2 NH3(g)

Sa

So
lid
Tr
a

ns
it

ion
al
M
eta
ls

H
N
H

Desorption
Products enter
the gas phase.

2009 High School Chem Solutions. All rights reserved.