REACTION KINETICS

LEARNING OUTCOMES

1. Explain the terms: rate of reaction, activation

energy, catalyst, rate equation, order of reaction
and rate constant.

2. Explain the 4 factors (concentration,

temperature, catalyst and particle size) that
will affect the rate of reaction.

3. Construct and use rate equation: rate = k[A]m[B]n

2
INTRODUCTION

Some chemical reactions are very fast and others

are much slower.

3
FACTORS AFFECTING REACTION
RATES

What 4 factors influence the rate of a chemical

reaction?

1. concentration of reactants

2. catalyst

3. temperature

4. surface area / particle size

4
1. CONCENTRATION OF REACTANTS
• Rate of reaction increases when the

concentration of a reactant is increased.

• A piece of steel wool burns with some difficulty

in air (20% O2) but bursts into a dazzling flame
in pure oxygen. The rate of burning increases
with the concentration of O2.

5
2. CONCENTRATION OF CATALYST
• Catalyst is a substance that increases the rate

of reaction without being consumed in the

overall reaction.

• Because the catalyst is not consumed by the

reaction, it does not appear in the balanced
chemical equation.

2H2O2(aq) 2H2O(l) + O2(g)

HBr(aq)

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3. TEMPERATURE AT WHICH THE
REACTION OCCURS
• Reactions speed up when the temperature

increases.

• It takes less time to boil an egg at sea level than

on a mountaintop, where water boils at a lower
temperature.

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4. SURFACE AREA OF A SOLID
REACTANT / CATALYST
• If a reaction involves a solid with a gas or liquid,
the surface area of the solid affects the reaction
rate.

• Because the reaction occurs at the surface of

the solid, the rate increases with increasing
surface area.

• A wood fire burns faster if the logs are chopped

into smaller pieces.
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REACTION RATE

Increase in molar concentration of product of a

reaction per unit time or the decrease in molar
concentration of reactant per unit time.

Units : mol dm-3 s-1 or mol dm-3 min-1

9
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The rate of this reaction can be found by

measuring:

1. concentration of O2

2. concentration of NO2

3. concentration of N2O5
10
We can express these changes in concentration as
follows. Square brackets mean molarity.

11
CALCULATING THE AVERAGE
REACTION RATE

Calculate the average rate of decomposition of

N2O5 during the time interval from t = 600 s to
t = 1200 s. Use the following data:

Time [N2O5]
600 s 1.24 x 10-2 M
1200 s 0.93 x 10-2 M

12
SOLUTION

13
COLLISION THEORY
In order to react with each other, particles (ions,
atoms or molecules) must collide in the ________
_____________ and with _________________.

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• For many reacting molecules ____________ are
involved: the molecules must collide in the correct
relative positions so their reactive atoms or
functional groups are aligned.

• This is known as collision geometry.

Hodder Education, IP Diploma, Chemistry 2nd edition

15
 Particles have less energy, less Particles have high energy, more
frequent and unsuccessful frequent and successful collision.
collision.

The minimum kinetic energy that colliding particles

must possess for a successful collision to take place
is called the _______________________ of that
particular reaction.
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EXOTHERMIC REACTION

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ENDOTHERMIC REACTION

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EXERCISE 1

Why does reaction rate increase as the temperature

increases?

A. Particles begin to collide at higher temperatures.

B. At higher temperatures particles move faster

and collide more often.

C. There are more particles at higher temperatures,

so they collide more.
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EXERCISE 2

Reactions eventually stop. What is generally the

reason for this?

A. The catalyst has been used up.

B. One or more of the reactants has been used up.

C. The particles have run out of energy.

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EXERCISE 3
Why does reaction rate increase as the
concentration increases?

A. The particles have more energy so there are

more collisions.

B. There are more particles so there are more

collisions.

C. The surface area is increased so there are more

collisions.
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EFFECT OF CONCENTRATION ON RATE OF
REACTION

Solutions

When concentration of reactants increases, collision

frequency between reacting particles increases. The
proportion of reactant molecules that exceeds the
activation energy is higher. Thus, the rate of the reaction
will be increased. 22
EFFECT OF TEMPERATURE ON RATE OF
REACTION

• For many reactions happening at around room

temperature, the rate of reaction doubles for
every 10°C rise in temperature.

• In any system, the particles present will have a

very wide range of energies.

• This can be shown on a graph called the ________

________________________________.
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MAXWELL-BOLTZMANN DISTRIBUTION

At a given temperature, the particles will not all

possess the same amount of energy as each other.
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• Change the shape of the curve
• Move the Ea further to the left
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Effect of temperature change on the rate of
reaction (Boltzmann Distribution)

As the temperature increases the curve shifts to

the right.
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 TEMPERATURE
T2 > T1

T1 Extra
molecules with
NUMBER OF MOLECUES WITH

sufficient
T2
energy to
A PARTICULAR ENERGY

Ea overcome the
energy barrier

MOLECULAR ENERGY

• Increasing the temperature gives more particles an

energy greater than Ea (activation energy).
• More reactants are able to overcome the Ea and
form products.
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 Effect of catalyst on the rate of reaction
(Boltzmann Distribution)

Ea = without catalyst
Eb = with catalyst
NUMBER OF MOLECUES WITH

Extra molecules
with sufficient
A PARTICULAR ENERGY

energy to
overcome the
Eb
energy barrier

MOLECULAR ENERGY Ea

• Catalyst provides a lower activation energy

pathway, Eb.
• More reactants are able to overcome the Eb and
form products.
EXERCISE 4

Sketch a potential energy diagram for the

decomposition of nitrous oxide.

N2O(g) → N2(g) + O(g)

The activation energy for the forward reaction is

251 kJ; ΔH° = +167 kJ mol-1.

(a) Label your diagram appropriately.

(b) What is the reverse activation energy?

29
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SOLUTION

30
EFFECT OF PARTICLE SIZE ON RATE
OF REACTION

If the solid is broken up into smaller pieces, the

surface area is increased, giving a greater area over
which collisions can occur.
Hodder Education, IP Diploma, Chemistry 2nd edition

31
EFFECT OF CATALYST ON RATE OF
REACTION
It increases reaction rate by providing alternate
reaction pathway that have lower activation energy
than the original, uncatalyzed pathway.

Hodder Education, IP Diploma, Chemistry 2nd edition

32
EFFECT OF CATALYST ON RATE OF
REACTION

Catalyst

• Increase the rates of both reversible and

irreversible reactions (lowers the Ea)

• Do not alter the position of equilibrium

• Do not increase the yield of products

• Do not alter the enthalpy change

33
CALCULATING RATE OF REACTION
GRAPHICALLY
• Rate of reaction changes as the reaction proceeds.
This is because [reactants] is decreasing.

cyclopropane propene

• The progress of this reaction can be followed by

measuring the decrease in [cyclopropane] or
increase in [propene]. 34
35
Changes in rate as the reaction proceeds
We can find the rate at different concentrations of
cyclopropane by drawing tangents at several points
on the graph.

36
[cyclopropane] Rate Rate
(mol dm-3) (mol dm-3 s-1) [cyclopropane] First order of reaction
(s-1)
1.50 1.00 x 10-3 6.67 x 10-4
1.00 6.67 x 10-4 6.67 x 10-4
0.50 3.30 x 10-4 6.60 x 10-4

Rate of reaction is proportional to

[cyclopropane]
We can express this mathematically as:

rate = k [cyclopropane]

where k is rate constant, a proportionality constant in

the relationship between rate and concentrations
37
RATE EQUATION / RATE LAW

• Rate equations can only be determined from

experimental data. They cannot be found from the
stoichiometric equation.

• For a generic reaction:

aA + bB +cC → dD + eE

the rate equation is

38
• For the reaction

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the rate equation is

Rate = k [NO2][F2]
• In this case, the exponent for both NO2 and F2 is 1
(which does not need to be written).

• We say the reaction is ___________ in each. The

reaction is _____________________.
39
ORDER OF REACTION
The power to which the concentration of that
reactant is raised in the rate equation.

Example:
1. rate = k [NO]2: the order is 2 with respect to
[NO].
2. rate = k [H2][NO]2: the order is 1 with respect to
[H2]; the order is 2 with respect to [NO]; overall
order is 3 (the sum of powers is 1+2=3)
40
 ZERO-ORDER (EXAMPLE)

2NH3(g) → N2(g) + 3H2(g)

The rate equation derived from experiments is

rate = k [NH3]0

 The plot of reaction rate against concentration is a

horizontal straight line.

 The reaction rate does not change with concentration.

 k is numerically equal to the reaction rate: rate = k.

 This is because any number to the power of zero = 1.

41
 FIRST-ORDER (EXAMPLE)

2N2O(g) → 2N2(g) + O2(g)

The rate equation derived from experiments is

rate = k [N2O]1

 The plot of reaction rate against concentration is an

inclined straight line going through the origin.

 The reaction rate is directly proportional to the

[N2O].

 Doubling the [N2O] doubles the rate of reaction.

42
 SECOND-ORDER (EXAMPLE)

NO2(g) + CO(g) → NO(g) + CO2(g)

The rate equation derived from experiments is

rate = k [NO2]2

 The plot of reaction rate against concentration is an

upwardly curved line.

 The reaction rate is directly proportional to the

square of the [NO2].

 Doubling the [NO2] increases four-fold the rate of

reaction.
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CONCEPT CHECK
Consider the reaction Q + R → S + T and the rate law
for the reaction:

Rate = k [Q]0[R]2

(a) You run the reaction three times, each time

starting with [R] = 2.0 M. For each run, you change
the starting concentration of [Q]: run 1, [Q] = 0.0 M;
run 2, [Q] = 1.0 M; run 3, [Q] = 2.0 M. Rank the rate
of the three reactions using each of these
concentrations.
44
CONCEPT CHECK

(b) The way the rate law is written in this problem is

not typical for expressions containing reactants that
are zero order in the rate law. Write the rate law in
the more typical fashion.

45
SOLUTION

46
EXERCISE 5
The reaction A + B = products is found to be second
order in [A] and first order in [B]. The rate equation
would be:

A. r = k [A][B]

B. r = k [A]2[B]

C. r = k [A][B]2

D. r = k [B]
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EXERCISE 6
Bromide ion is oxidized by bromate ion in acidic
solution.

5Br-(aq) + BrO3-(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)

The experimentally determined rate law is

Rate = k [Br-][BrO3-][H+]2

What is the order of reaction with respect to each

reactant species? What is the overall order of the
reaction?
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SOLUTION

49
DETERMINING THE RATE EQUATION

• The initial-rate method is a simple way to obtain

reaction orders.

• It consists of doing a series of experiments in

which the initial, or starting, concentrations of
reactants are varied.

• Then the initial rates are compared, from which the

reaction orders can be deduced.

50
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Exp Initial [N2O5] Initial rate of disappearance

of N2O5
1 1.0 x 10-2 mol/L 4.8 x 10-6 mol/L s
2 2.0 x 10-2 mol/L 9.6 x 10-6 mol/L s

Rate = k [N2O5]m

Determine the value of m and rate constant, k.

51
• Suppose you divide the initial rate of reaction of N2O5
from Experiment 2 by the initial rate from Experiment
1.
9.6 x 10 -6 mol/L.s
-6
= 2.0
4.8 x 10 mol/L.s

• When the [N2O5] is doubled, the rate is double. This

corresponds to the case m = 1.

• So the rate equation / rate law is rate = k[N2O5].

• The value of the rate constant k can also be determined

by substituting values of the rate and [N2O5] from any
of the experiments into the rate equation. Hence,
9.6 x 10 -6 mol/L.s − 4 −1
k= -2
= 4.8 x 10 s
2.0 x 10 mol/L 52
Obtain the rate law and the rate constant using the
following data for the initial rates of disappearance
of NO.
2NO(g) + O2(g) → 2NO2(g)

Exp Initial Initial Initial rate of

concentration concentration reaction of NO,
of NO, M of O2, M M s-1

1 0.0125 0.0253 0.0281

2 0.0250 0.0253 0.112

3 0.0125 0.0506 0.0561

53
• To find the order in NO, we will first identify two
experiments in which the concentration of O2 remains
constant. Then, we will divide the rate equations for
those two experiments. Finally, we will solve the equation
to find the order in NO.

• To find the order in O2, we will repeat this procedure,

this time choosing experiments in which the
concentration of NO remains constant.

• Once the order in NO and the order in O2 are known,

data from any experiment can be substituted into the
rate equation. The rate equation can then be solved for
the rate constant k. 54
• [O2] remains constant in Experiments 1 and 2.

• The generic rate equation is rate = k[NO]m[O2]n.

We will put the result from Experiment 2 in the
numerator because its rate is larger than that of
Experiment 1.
M
s = (0.0250 M ) (0.0253 M )
0.112 m n

M (0.0125 M )m (0.0253 M )n
0.0281
s
4 = 2m

m=2
The reaction is second order in NO.
55
• [NO] remains constant in Experiments 1 and 3.

• The generic rate equation is rate = k[NO]m[O2]n.

We will put the result from Experiment 3 in the
numerator because its rate is larger than that of
Experiment 1.
M
s = (0.0125 M ) (0.0506 M )
0.0.0561 m n

0.0281
M (0.0125 M ) (0.0253 M )
m n

s
2 = 2n

n =1
The reaction is first order in O2 .
56
• The rate equation is rate = k[NO]2[O2].

Solving for k, we obtain

rate
k=
NO O2 
2

Using data from experiment 1:

M
0.0281
s 7.11  103
k= =
(0.0125 M ) (0.0253 M ) M • s
2 2

• Using data from Experiment 2: k = 7.08 × 103/M2 s

• Using data from Experiment 3: k = 7.10 × 103/M2 s

• These values are the same to 2 significant figures.

57
EXERCISE 7
Iodide ion is oxidized in acidic solution to triiodide
ion, I3-, by hydrogen peroxide.

H2O2(aq) + 3I-(aq) + 2H+(aq) → I3-(aq) + 2H2O(l)

A series of four experiments was run at different

concentrations, and the initial rates of I3- formation
were determined. From these data, deduce the
reaction orders with respect to H2O2, I- and H+.
Then find the rate constant.
58
Exp Initial concentrations (mol/L) Initial rate
(mol / L s)

H2O2 I- H+
1 0.010 0.010 0.00050 1.15 x 10-6

2 0.020 0.010 0.00050 2.30 x 10-6

3 0.010 0.020 0.00050 2.30 x 10-6

4 0.010 0.010 0.00100 1.15 x 10-6

59
SOLUTION

60
WHICH ORDER OF REACTION?

We can identify the order of a reaction in 3 ways:

1. Plot a graph of reaction rate against

[reactant]

2. Plot a graph of [reactant] against time

3. Deduce successive half-lives from graphs of

concentration against time

61
GRAPHS OF REACTION RATE AGAINST
CONCENTRATION

62
GRAPHS OF CONCENTRATION OF
REACTANT AGAINST TIME
Zero-order:

• Graph is a descending straight

line.

• Rate of reaction is the

slope (gradient) of the graph.

• Reaction proceeds at the same

rate whatever the [reactant].
63
First-order:
 Graph is a curve.

Second-order:
 Graph is a much
deeper curve, with
a longer ‘tail’ as it
levels off.
64
HALF-LIFE AND REACTION RATES

Half-life, t1/2, is the time taken for the [reactant] to

fall to half of its original value.

65
SELF-ASSESSMENT

To check your understanding on this topic, you

are required to proceed to Moodle and
complete Quiz 2, followed by Tutorial 2.

The answers for Tutorial 2 will be discussed in

class.
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