REVISION MATERIAL FOR PHYSICAL SCIENCES

TOPIC: RATES OF CHEMICAL REACTIONS

GRADE 12

2015
 Collision theory
• Chemical reactions can only occur if certain
conditions are met.
• The model used to explain reaction
mechanism (the how and why) is THE
COLLISION THEORY.
 Collision theory
On the microscopic level:
• a number of steps are essential before a
reaction will occur.
•The steps that atoms go through as their
arrangement changes from reactants to
products is known as the MECHANISM of the
reaction.
 THE MECHANISM OF
CHEMICAL REACTIONS
Collision
theory
 The Collision Theory:
• For a chemical reaction to take place, atoms or molecules
must get so close together that their outer electron energy
levels overlap.
• Reacting atoms, molecules or ions must collide with each
other.
• The particles must have sufficient energy
• Molecules must be oriented correctly.
• Bonds in the original molecules must break and new bonds
must form.
• Electrons must re-arranged in order to form new bonds.
 Example
• The reaction between hydrogen iodide
molecules

HI(g) + HI(g)  H2(g) + I2(g)

 H I I H

H I I H

Collisions ineffective, therefore no reaction.

Effective and ineffective collisions
• A reaction is unlikely to happen if molecules
approach each other from a direction that
makes it difficult for new bonds to form.
• Only a tiny proportion of the collisions between
particles are effective collisions which result in
reactions.
• As the electrons repel each other, most
molecules move away from each other and
avoid collision.
• Molecules have to collide with enough kinetic
energy for their outer electrons energy levels to
mix.
 H H
I I

A collision with enough

kinetic energy –
H H bonds broken and new
I I bonds formed.
H
I I H
Amount of energy and orientation of colliding
particles leads to some collisions being
effective and others not effective.
 Particles with sufficient energy:

This Boltzmann curve shows that there is only

a small fraction of molecules that have enough
energy for the reaction
Test your knowledge
 Answer
D
Test your knowledge
 Answer
D
 ENERGY CHANGES DURING CHEMICAL
REACTIONS
• Two types of reactions which involve energy:
– Exothermic – energy is released
– Endothermic – energy is absorbed.
• All reactions need energy to start. Most
reactions do not begin until an amount of
energy (activation energy) has been added to
the reaction mixture.
THE ACTIVATED COMPLEX

• The reacting atoms must pass over an

“energy hill” to change from reactants to
products.
• The transition state that atoms must pass
through is called the ACTIVATED
COMPLEX.
 Activated complex
• An activated complex is a temporary,
unstable, high-energy composition of atoms,
which represents a transition state between
reactants and the products.
• When the activated complex is formed during
a reaction, this complex can lead either to the
formation of new bonds i.e. molecules of the
products, or to re-formation of the old bonds,
thereby returning to being reactants.
ACTIVATION ENERGY:

• the difference in energy between the

reactants and the activated complex.
•Ea is measured in kJ.mol-1.
•Ea is the minimum amount of energy
required for a reaction to take place.
•Kinetic energy of colliding atoms/molecules
must be equal to or bigger than the Ea for
reaction to take place
Test your knowledge
 Answer

C
 Answer
A
Test your knowledge
 Answer
B
 Energy diagrams:
• shows the changes in the potential energy of
the reacting substances during the reaction:

In an exothermic reaction the energy of products is

less than the energy of the reactants.
 Energy diagrams:

In an endothermic reaction the energy of

products is greater than the energy of the
reactants.
 Answer
C
 Answer

C
 HEAT OF REACTION
• Heat of the reaction (∆H) is the difference
between the energy of the products and the
energy of the reactants.
∆H = Eproducts - Ereactants

• ΔH is measured in kJ.mol-1
 HEAT OF REACTION
• For an endothermic reaction,
Eproducts > Ereactants
• ∆H is positive
• ΔH > 0

• For an exothermic reaction,

Eproducts < Ereactants
• ∆H is negative.
• For the reaction

AB + C  A + BC
the formation of an activated complex as a
transitional step can be represented as
follows:

AB + C  [ABC]  A + BC
• If the reaction is exothermic, the graph looks
like the graph shown below:
 Activated Complex Exothermic
[ABC] Reaction
POTENTIAL

Activation
ENERGY

Energy

AB + C
ΔH = neg
(reactants) A + BC
(products)
COURSE OF REACTION
• The peak of the energy hill indicates the
energy of the activated complex.
• When an activated complex is formed
during a reaction, this complex can lead
either to the formation of new bonds, i.e.
molecules of the products or to the re-
formation of the old bonds, thereby
returning to being the reactants.
• This is the reason why we see a
reversibility in the reactions.
Comparing exothermic and endothermic
reactions:
Exothermic Endothermic
reaction reaction
ΔH < 0 ΔH > 0
negative positive
Ep of the reactants Ep of the reactants
decreases as products increases as products
form form
Net energy is given Net energy is taken
out (liberated) in (gained)
The reaction flask The reaction flask
becomes hot becomes cold
Test your knowledge
 Answer

C
 The Collision Theory &Factors
Affecting the Rate of Reactions
1. State of division or surface area exposed
• Breaking a solid into smaller pieces allows for
more intimate mixing of particles and more
freedom of movement.
• The greater the exposed surface area, the
faster the reaction rate.
• This is because the number of collisions
increases and therefore more effective
collisions.
2. The concentration of the reactants
• A higher concentration means a greater
number of particles in a given volume.
• If there are more particles, there will be more
collisions and therefore more effective
collisions.
• Hence the rate of the reaction increases
 3. The temperature of the
reaction
• The temperature of a system is a measure of the
average kinetic energy of the particles in that
solution.
• If the average kinetic energy is increased by
increasing the temperature, more particles will
have enough kinetic energy between themselves
to collide successfully and react.
• The rate of both exothermic and endothermic
reactions will increase with an increase in
temperature.
 4. The presence of a catalyst
A catalyst:
• lowers the amount of energy needed for a successful
collision.
•more collisions are successful and the rate of both the
endothermic and exothermic reactions increases.
•lowers the activation energy and therefore more
particles with sufficient energy to break bonds are
available.
•forms part of the activated complex and when this
decomposes the catalyst is released, unchanged.
 The Mechanism of a Catalyst
Activated Complex
[ABC]
POTENTIAL

Activation catalyst
ENERGY

Energy EA
EA

AB + C ΔH = neg
A + BC
(reactants) (products)
COURSE OF REACTION
 Question
• What is the function of a catalyst?
 Answer

The function of a catalyst is to provide an

alternate route for the reaction to take place.
This route has a lower activation energy and the
rate of the reaction increases.
 Two kinds of catalysis:

– Homogenous – the catalyst is the same

phase as the reactants.
– Heterogeneous – the catalyst in different
phase as the reactants.

• Catalysts cannot cause a reaction to

occur, they can only affect the rate of the
reaction.
 Answer
C
 Test Your Knowledge
1.Consider the exothermic reaction below
Na2CO3(aq) + 2HCl(aq) → 2NaCl(aq) + CO2(g)
Increasing the temperature of the reaction will
increase the reaction rate because
A. the reaction is exothermic.
B. the gaseous product expands on heating.
C. the activation energy is lowered.
D. the percentage of effective collisions increases.
 Answer
C
 Test your knowledge
2. Which of the following factors lowers
the amount of energy needed for a
successful collision?
A. Increasing the concentration
B. Introducing a catalyst
C. Increasing the temperature
D. Decreasing the surface area exposed
 Answer
B
 Test Your Knowledge
3. In endothermic reactions the reactants:
A. have more energy than the products.
B. have less energy than the products.
C. have the same energy as the products.
D. are at a lower temperature than the
products.
 Answers
A
 Test your knowledge
4. In an exothermic reaction
A. H is positive.
B. the activation energy is always more.
than the heat of the reaction.
C. there is a decrease in internal energy.
D. there is no energy change.
 Answer
C
5. A catalyst is a substance which is added to a
reaction mixture to increase the reaction
rate. A further characteristic of such a
catalyst, is that it
A. affects only endothermic reactions.
B. does not undergo any permanent changes.
C. increases the reaction rate of redox
reactions only.
D. increases the reaction rate of acid-base
reactions only.
 Answer
B
 Test your knowledge
6. The rate at which a 50 mm piece of clean
magnesium ribbon reacts with 20 cm3 hydrochloric acid
(concentration 1 mol.dm-3) is determined by measuring
the volume of hydrogen released during the first
minute of the reaction
Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g)
The experiment is repeated three times altering
only ONE factor at a time as indicated in 1.1 to 1.3.
State how the rate of this reaction will be
influenced if (simply state INCREASE, DECREASE or
REMAIN THE SAME) …
•6.1 the 50 mm piece of magnesium is filed to a
powder.
•6.2 20 cm3 of HCl of a 2 mol/dm3 concentration
is used.
•6.3 The mixture is cooled.
 Answers
6.1. increase
6.2. increase
6.3. decrease
 Test your knowledge
7. An iron nail will displace copper metal from a
solution of copper sulphate.

Give three ways in which the rate of this

reaction can be increased.
 Answers
7.
• Use iron powder instead of the nails,
• heat the reaction mixture,
• increase the concentration of the CuSO4
solution
Measuring the rate of a reaction:

For the products:

Average rate = change in amount of product
time taken
For the reactants:
Average rate = change in amount of reactant
time taken
Rate is usually measured in moles per
second (mol.s-1)
 Example
Zn(s) + 2HCl (aq)  ZnCl2(aq) + H2 (g)
The rate of the reaction can be expressed as:

Av rate = No. of moles of Zn used up

Reaction time in s

Av rate = number of moles of H2 liberated

Reaction time in s
• As the concentration of the reactants
decreases, the concentration of the products
increases, as shown in the following graph
For the Reaction : A + B  AB

Product AB
concentration
(mol.dm-3)

reactants A and B

time in s
H2 + I2 → 2HI
The gradient of either curve will give the
average rate of reaction for the time interval
Δt.
 Test your knowledge
Calculate the rate of reaction if it takes 18
seconds to produce 42 moles of carbon
dioxide from a wood fire.

Average rate = change in amount of product

time taken
= 42 mol
18s
= 2,3 mol.s-1
 Test your knowledge
Name two experimental measuring techniques
that can be used to measure the rate of
chemical reactions.
Two most common ways are
Answer
to measure how fast the …

1) products are formed

by means of gas
collection

2) reactants are used up

by means of change in the
mass of the reaction
vessel
 Phases in which reactions can occur

• There are two types of reactions,

1. homogeneous where reactants and
products in the same phase and
2. heterogeneous where reactants and
products in different phases.
 Rates of Reaction
Chemical reactions occur when
different atoms or molecules collide:

The rate at which the reaction happens depends on four factors

that affect the reaction rate.
In the case of homogeneous reactions :
1) The temperature of the reactants
2) Their concentration (pressure in gases)
3) Whether or not a catalyst is used
4) The nature of reactants (type of substance)
In the case of heterogeneous reactions, a fifth factor, the
surface area (state of division) of the solid reactant affects the
reaction rate.
 1. Nature of reactants
• When two substances react to form new
products, existing bonds have to be broken and
new bonds formed during the reaction.
• The nature of the bonds will depend on the
nature of the particles which make up the
substance.
• Therefore reactions that do not involve breaking
of existing bonds can be expected to take place
faster than those which involve breaking of
bonds.
2. Concentration (pressure in gases)
• The reaction rate is directly proportional to
the concentration of the reactants, i.e. as
the concentration increases, the rate of the
reaction increases.
• By doubling the concentration of one of the
reactants, the reaction rate is doubled.
3. Temperature
• An increase of approximately 10oC in the
temperature of the reactants causes the reaction
rate to double.

4. Catalyst
• A catalyst is a substance which, when added to a
reaction mixture, speeds up the reaction without
taking part in the reaction itself.
• A catalyst remains unchanged throughout the
reaction.
5. State of division (surface area)

• By increasing the exposed surface area of a

solid reactant, the reaction rate is increased.
 Test Your Knowledge
1. The increase in the rate of a chemical
reaction with a rise in temperature is
most likely due to
A. the reaction being exothermic.
B. the increase in activation energy.
C. the larger number of reacting particles
with enough energy to react.
D. the increase in the heat of the reaction.
 Answer
C
 Test your knowledge
2. Consider the reaction:
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g) ∆H< 0
The reaction took place by adding 10 ml of a
0,1 mol.dm-3 hydrochloric acid solution to about 1 g
zinc granules. Which one of the conditions below
will increase the rate of the reaction?
A. Lowering the temperature of the acid solution.
B. The use of about 1 g powdered zinc in the place of zinc
granules.
C. Doubling the volume of the original acid solution.
D. Using 150 ml of a 0,1 mol.dm-3 solution of HCl.
 Answer
B
 Test your knowledge
3. Consider the exothermic reaction between
magnesium &hydrochloric acid:
Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)
Which one of the following factors will have
NO EFFECT on the rate of the reaction?

A. doubling the volume of acid used

B. adding a suitable catalyst
C. increasing the surface area of magnesium
D. using hot hydrochloric acid
 Answer

A
EXPLAINING THE FACTORS THAT
AFFECT THE RATE OF A REACTION:

• the greater the concentration of a solution

the greater the chance of collisions and so the
greater the rate of reaction.

• the greater the pressure of a reactant in the

gas phase the greater the chance of collisions
and so the greater the rate of reaction.
• the greater the exposed surface area of the
particles of a solid (the finer the particles) the
greater the chance of collisions with the
particles on the surface and so the greater the
rate of reaction.

small chips
Loss of mass

Large chips

time
The effect of increasing the temperature of
the reaction mixture:
Low temperature

High temperature

More molecules with sufficient energy to react at the

higher temperature
Effect of a catalyst on reaction rate:

A catalyst always lowers the activation energy

and so more molecules have sufficient energy
to make effective collisions.
A catalyst speeds up a reaction without
taking part in the reaction.
 Test your knowledge
1. Explain the mechanism of a
chemical reaction by using the
following factors that can influence
the rate of a chemical reaction:
a. The catalytic effect
b. The size of the reactants’ surface area
c. The temperature of the reaction
 Answer
a. The catalytic effect - The presence of a catalyst
lowers the activation energy – it provides a
low-energy alternate pathway for the
production of products. The energy for a
successful collision is lowered by a catalyst and
therefore there is an increased number of
effective collisions. This results in an increase
in the reaction rate of both endothermic and
exothermic reactions.
 Answer
b. The size of the reactants’ surface area -
When a given mass is subdivided into smaller
particles, the surface area is increased and a
greater number of particles are exposed. This
results in a greater number of effective collisions
between the particles and therefore an
increased reaction rate.
 Answer
c. The temperature - is a measure of the average
kinetic energy of the particles. If the reaction
temperature rises there is an increase in the
number of molecules with kinetic energy in excess
of EA, sufficient for effective collisions leading to a
reaction. The activation energy (EA) is unchanged
but there will be more particles with kinetic energy
greater that EA. Both exothermic and endothermic
reactions will have an increased reaction rate.
 Test your knowledge
The Contact process is used to prepare sulphuric
acid in the high concentration needed for
industry. This process involves the oxidation of
sulphur dioxide in the presence of a
vanadium(V)oxide catalyst:

2SO2(g) + O2(g) ⇌ 2SO3(g)

Use the reaction and the graph, where

applicable, to answer the questions that follow
1.1 ls the forward reaction exothermic or
endothermic? Prove your answer by calculating
the value of ∆H for this reaction.
 Answer
1.1 exothermic
ΔH = Eproducts - Ereactants
= -197 - 1580
= - 1777 kJ.mol-1
ΔH is negative for an exothermic reaction.
 1.2 What is the activation energy for the
forward reaction in the absence of the
vanadium(V)oxide catalyst.
 Answer
1.2 1580 kJ.mol-1
1.3 The graph indicates that 1580 kJ.mol-1 is
needed to break the bonds in the SO2(g) and
O2(g) molecules.
How much energy is released when the new
bonds in the SO3(g) molecules form?
 Answer
1.3 197 kJ.mol-1
1.4 Determine the activation energy for the
REVERSE REACTION in the presence of the
vanadium(V)oxide catalyst
 Answers

1.4 1537 kJ.mol-1

 Test your knowledge
When excess dilute HCℓ is used to dissolve 1,00 g
of CaCO3(s) in a beaker in an experiment on
reaction rate, the following reaction takes place:

CaCO3(s) + 2HCℓ(aq) → CaCℓ2(aq) + H2O(ℓ)

+ CO2(g)

The results obtained are summarised in the table:

Mass of beaker, HCℓ &
CaCO3(s), (g) 31,00 30,60 30,30 30,10 30 30

Time, (s)
0 10 20 30 40 50
2.1 Explain why the mass of the beaker with
its contents decreased in the first 30 s
2.2 State the meaning of “dilute HCℓ”?
2.3 The “excess HCℓ” cannot influence the
results. Give a reason for this
2.4 At what time was the CaCO3(s) used up?
Give a reason for your answer.
 Answers
2.1 The CO2 gas (product) escapes from the
beaker and the mass of the contents of the
beaker decreases
2.2 Water has been added to the HCl
2.3 CaCO3 is the limiting reagent
2.4 At 40s. The mass of the beaker r emains
constant
2.5 Calculate the volume of CO2(g) that was
collected at STP in this experiment
2.6 When the dilute HCℓ is replaced by
concentrated HCℓ, the rate of the reaction
between HCℓ and CaCO3 increases. Use the
collision theory to explain this observation.
 Answers
2.5 n(CaCO3) that reacted = n/m = 1,00/100 = 0,01 mol
n(CaCO3) : n(CO2) = 1:1 OR n(CO2) = 0,01 mol
V(CO2) at STP = nVm = (0,01)(22,4) = 0,224 dm3

2.6 There are more HCℓ molecules that react with

CaCO3. More HCℓ molecules possess enough kinetic
energy and correct orientation. There are more
effective collisions per unit time
 Test your knowledge
Susan investigates the following reaction in order to
understand how surface area affects the rate of a
reaction:
CaCO3(s) + HCℓ(aq) → CaCℓ2(aq) + H2O(ℓ) +
CO2(g)

3.1 Explain in terms of the collision theory how a

change in surface area of the reactants would affect
the rate of this reaction.
 Answers
3.1 By grinding the calcium carbonate, the
surface area that the acid particle can collide
with, increases. This results in more collisions,
therefore more successful collisions and a
faster rate of reaction.
 Test your knowledge
3.2 Design an experimental method that
Susan can follow for her investigation. Use
the following two headings:

a) LABELLED DIAGRAM of the experimental set-

up
b) The Independent variable(s)
c) The Dependent variable(s)
 Answers
3.2
a) LABELLED DIAGRAM of experimental set-up:
Container (beaker/flask/etc.) with solids
and acids
The beaker and reactants labelled
A measuring device (scale/syringe/collection
over water)
Stopwatch
 Answers
3.2
b) Variables that Susan are dealing with:
Independent variable(s): surface area (size of
particles)
c) Dependent variable(s): time to complete the
reaction/volume of gas collected over time/mass of the
reactants and products over time, BUT NOT ‘time’
 Test your knowledge
3.3 Susan needs to measure one of the
variables over time in order for her to
determine the effect of concentration
on the rate of the reaction. Draw a
rough, qualitative sketch graph of what
you expect the outcome of her
investigation to be. Clearly label the axes
of the graph.
 Answers
3.3
Volume of gas collected

Mass loss
 Test your knowledge
3.4 Which other factor(s), that could affect
the rate of this reaction, does Susan have to
control?
3.4 Temperature of the Acid

Concentration of the Acid

The nature of the reactants (using
calcium carbonate and hydrochloric
acid in every test)