Topic 6

Chemical Kinetics
Topic 6.1: Collision theory and
rate of reaction
E S S E N T I A L I D E A : T H E G R E AT E R T H E P R O B A B I L I T Y
T H AT M O L E C U L E S W I L L C O L L I D E W I T H S U F F I C I E N T
E N E R G Y A N D P R O P E R O R I E N TAT I O N , T H E H I G H E R
T H E R AT E O F R E A C T I O N
Chemistry Guide Statements T6.1 SL
Topic 6.1 —Collision theory and rates of reaction
Nature of science
The principle of Occam’s razor is used as a guide to developing a theory—although we cannot directly see reactions taking place at the
molecular level, we can theorize based on the current atomic models. Collision theory is a good example of this principle. (2.7)
Understandings:
• Species react as a result of collisions of sufficient energy and proper
orientation.
• The rate of reaction is expressed as the change in concentration of a particular
reactant/product per unit time.
• Concentration changes in a reaction can be followed indirectly by monitoring
changes in mass, volume and colour.
• Activation energy (Ea) is the minimum energy that colliding molecules need in
order to have successful collisions leading to a reaction.
• By decreasing Ea, a catalyst increases the rate of a chemical reaction, without
itself being permanently chemically changed.
Applications and skills:
• Description of the kinetic theory in terms of the movement of particles whose
average kinetic energy is proportional to temperature in Kelvin.
• Analysis of graphical and numerical data from rate experiments.
• Explanation of the effects of temperature, pressure/concentration and particle
size on rate of reaction.
• Construction of Maxwell–Boltzmann energy distribution curves to account for
the probability of successful collisions and factors affecting these, including the
effect of a catalyst.
• Investigation of rates of reaction experimentally and evaluation of the results.
• Sketching and explanation of energy profiles with and without catalysts.
Guidance:
• Calculation of reaction rates from tangents of graphs of concentration, volume
or mass against time should be covered.
• Students should be familiar with the interpretation of graphs of changes in
concentration, volume or mass against time
SL
International-mindedness:
• Depletion of stratospheric ozone has been caused largely by the catalytic
action of CFCs and is a particular concern in the polar regions. These chemicals
are released from a variety of regions and sources, so international action and
cooperation have been needed to ameliorate the ozone depletion problem.
Theory of knowledge:
• The Kelvin scale of temperature gives a natural measure of the kinetic energy
of gas whereas the artificial Celsius scale is based on the properties of water.
Are physical properties such as temperature invented or discovered?
Utilization:
Syllabus and cross-curricular links:
Topic 5.3—what might be meant by thermodynamically stable vs kinetically
stable?
Topic 13.1—fireworks and ions
Option A.3—everyday uses of catalysts
Option B.2—enzymes
Biology topic 8.1—metabolism
Aims:
• Aims 1 and 8: What are some of the controversies over rate of climate change?
Why do these exist?
• Aim 6: Investigate the rate of a reaction with and without a catalyst.
• Aim 6: Experiments could include investigating rates by changing concentration
of a reactant or temperature.
• Aim 7: Use simulations to show how molecular collisions are affected by
change of macroscopic properties such as temperature, pressure and
concentration.
• Aim 8: The role that catalysts play in the field of green chemistry.
What is rate of reaction? SL
When considering the rate of a chemical reaction, we
are looking at how fast or slow the reaction is. This
leads to the definition of rate of reaction as the speed
at which reactants are used up or products are formed.

An example of a very slow chemical reaction is the

rusting (figure 6.1) and an example of a very fast
chemical reaction is explosion (figure 6.2) or fireworks.
Experiments to measure the rate of reaction SL
Consider the reaction between calcium carbonate and hydrochloric acid:

CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)

The rate of this reaction can be measured in various ways, mainly two:
1. measurement of the rate at which CO2 is produced
2. measurement of the rate at which the mass decreases

3. Measurement of the rate at which CO2 is produced

The apparatus for the experiment is shown on the
right. At the beginning there is no calcium carbonate.
Then the bung in the conical flask is removed, the
calcium carbonate added, the bung quickly replaced,
and the timer started. The reactions starts readily, and
this experiment can be used to generate a graph of
volume of carbon dioxide produced against time (i.e.
by noting the volume on the cylinder every 10 s).
Experiments to measure the rate of reaction SL

The reaction appears to finish

at 90 s because no more gas is
produced after that time

The tangent is drawn at

the initial point to
determine the initial
rate

The average rate of reaction during the first 90 s can be calculated

and it is given by the change in volume 90 s:
cm3/s

The rate at any particular time is given by the slope (gradient) of

the graph at that time. The gradient can be worked out by drawing
a tangent to the curve at that point.
The initial rate would then be calculated as:

cm3/s
Experiments to measure the rate of reaction SL
It can be seen from the graph that the gradient decreases as time goes on, which means the rate is
fastest at the beginning and then gets slower. At 90 s, the reaction has stopped, and the gradient
of the graph is zero.
The volume of carbon dioxide produced can be used to calculate the concentration of
hydrochloric acid in the flask at any time. The more gas (product) that has been produced, the
lower the concentration of the remaining hydrochloric acid (reactant). The actual concentration
of acid at any time could be worked out using a moles calculation, assuming that the initial
volume and concentration of the acid are known. These data could, then be used to plot a graph
of concentration of hydrochloric acid against time.
Possible problems with experiments like this are:
• the fact that some gas is likely to escape before the bung is put on the flask (resulting in all
values for the volume of carbon dioxide being lower than expected)
• variations in the sizes of the calcium carbonate pieces.
Experiments to measure the rate of reaction SL
2. Measurement of the rate at which the mass decreases

The rate of this reaction can also be determined by measuring the speed at which the mass decreases. The
experimental set-up for this is shown in the picture. The mass decreases as carbon dioxide is given off.

The cotton wool allows

the gas to escape but
stops mass being lost
as a result of spills and
splashes
Experiments to measure the rate of reaction SL

Mass of carbon dioxide lost

plotted against time
(196.27 – mass at any time)

The average rate of reaction can be calculated and it is given by the change in mass at 90 s:

g/s

The rate at any particular time is given by the slope (gradient) of the graph at that time. The gradient can be
worked out by drawing a tangent to the curve at that point.
The initial rate would then be calculated as:

gradient=
Rate of reaction defined SL
Rates are most often considered in terms of concentrations.
Rate of reaction can be defined as the change in concentration of reactants or products per unit
time (s or min..).
Therefore the units measure for rate of reactions are: mol dm -3 s-1 or mol dm-3 min-1.

• For the reaction A + B → C

the rate at which the reactants are used up is equal to the rate at which the products are produced,
i.e. if the rate of reaction with respect to A is 0.12 mol dm −3 s−1, the rate of reaction with respect to
C will also be 0.12 mol dm−3 s−1.

• For the reaction A → 2D

the rate at which D is produced will be twice the rate at which A is used up, because one mole of
A will produce 2 moles of D. Therefore, if the rate of reaction with respect to A is 0.16 mol dm −3
s−1, the rate of reaction with respect to D will be 0.32 mol dm −3 s−1.

The rate of reaction at any time can be found from a graph of concentration against time by
drawing a tangent at the particular time and finding the gradient (slope) of the tangent, like we
did before with ‘volume vs time’ graph.
Rate of reaction defined
The rate of reaction can also be defined in terms of calculus notation. For the reaction:
A+B→C+
D

The rate of reaction can be given as d[C]/dt , where [C] is the concentration of C.
Because the concentration of A is decreasing, −d[A]/dt = d[C]/dt

and for this reaction: rate = −d[A]/dt = −d[B]/dt = d[C]/dt = d[D]/dt

Note: the course of a chemical reaction can also be followed using changes in colour – if the reaction
itself allows it.

Example: The iodination of propanone in the presence of an acid catalyst can be followed conveniently using
a colorimeter to monitor the changes in colour that occur as iodine is used up. Since iodine is brown and all
the other species are colourless: the reaction mixture fades from brown to colourless as iodine is used up in
the reaction and the decrease in the absorption of light can be measured using the colorimeter.
H+
CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + H+(aq) + I−(aq)
propanone iodopropanone

A colorimeter measures the amount of light absorbed by the sample at a particular wavelegnth – the darker the colour of the
sample the more light is absorbed. Then a graph of absorbance vs time can be drawn.
Collision theory: particles must collide to react SL
Reaction rates are generally discussed in terms of collision theory, which states that for a
reaction to occur particles must collide; however for collisions to result in a reaction there are
2 conditions to be satisfied:
1. A collision must involve more than a certain minimum amount of energy
2. Molecules must collide with the correct orientations

Therefore it is important to note that not all collisions result in a reaction!

3. Collision must involve more than a certain minimum amount of energy

Particles must collide with sufficient energy in order to react. The minimum amount of energy
that colliding particles must possess to result in a reaction is called the activation energy (Ea).

If two particles with less than the activation energy collide, they will just bounce off each other
and no reaction will result; however, if the particles have energy greater than or equal to the
activation energy then, assuming the orientation of the collision is also correct, the particles
will react. A collision that results in a reaction is called a successful or effective collision.

Activation energy: the energy needed to overcome repulsions, to start breaking bonds, to
deform molecules and to allow rearrangement of atoms, electrons etc.
Collision theory: particles must collide to react SL
The activation energy for an exothermic reaction is shown on the graph:
Imagine the reaction between two particles (A and B-
C):

A + B–C → A–
B+C
As the two particles approach, repulsion between the
atoms (internuclear and between electrons) causes an
increase in the potential energy.
The B–C bond begins to break and the A–B bond
begins to form. The highest point along the curve is
called the transition state (activated complex) and for
an instant all three atoms are joined together by partial
bonds (A….B….C).
As the A–B bond continues to form, the potential
2. Molecules
energy must collide
falls (remember: with the correct
bond-making orientations
releases energy).

If molecules do not collide with the correct orientation they will not react.
Therefore not every collision with energy greater that the activation energy (E a) results in
a reaction.
Factors affecting reaction rate SL
The main factors affecting the rate of a chemical reaction are:
1. Concentration of reactants
2. Pressure (for reaction involving gases)
3. Surface area of solid reactants
4. Temperature
5. Catalysis

6. The effect of concentration of reactants on the reaction rate

The higher the concentration of reactants b, the higher the collision frequency (because
particles are closer together and therefore they will collide more often) b and the greater is the
chance of having a successful collision in a certain time.

2. The effect of pressure on the reaction rate

(only for reactions involving gases)
The higher the pressure b , the higher the collision frequency
(because particles are closer together).
Factors affecting reaction rate SL
3. The effect of surface area of solid reactants on the reaction rate
Reactions generally only occur at the surface of a solid. Making a solid more finely divided b

increases the surface area and therefore the number of particles exposed at the surface. The
effective concentration of the particles of the solid has thus been increased and there is a
greater chance of a particle of the other reactant colliding with a particle on the surface and
reaction occurring

4. The effect of temperature

The average kinetic energy of the particles in a gas is
proportional to its temperature (K). This relationship does
not depend on the type of gas but on its mass.
At the same temperature lighter particles travel faster
than heavier ones.
Example: at 300 K the average kinetic energy of O 2 and He
gases is the same (regardless of the identity of the
substance) but because the mass of an O2 molecule is eight
times the mass of a He atom, the He atoms will be Therefore a large increase in temperature
travelling much faster at the same temperature. is required for a significant increase in
the average speed of the particles and
hence in the collision frequency
Factors affecting reaction rate SL
Increasing the temperature has a major effect on the rate of reaction: as the temperature rises,
the rate of reaction increases exponentially.

As the temperature increases, the molecules

have more energy:
1. Particles move faster, therefore the number
of collision among particles increases: this
is a minor effect - responsible for a small
2% of the overall exponential increase.
2. Particles collide harder/with more energy:
this is the major cause for the exponential
increase in the rate of reaction.
Factors affecting reaction rate SL
Why is rate of reaction increasing with temperature?

In a sample of gas, the molecules are constantly colliding with each other and, therefore, do not all have the
same speed and hence energy. The Maxwell– Boltzmann curve shows the distribution of molecular kinetic
energies at a particular temperature.
It can be seen that there are only a few particles with high energy and only a few with very low energy. Most
particles have energy around the average. As temperature increases, the distribution of energies changes.

T increases

Note that:
• it is not symmetrical
• no molecules have zero kinetic energy
• at higher energy the line does not cross the energy axis
• the area under the curve represents the total number of
particles and will not change as the temperature changes.
The main reason that the rate of reaction
increases with temperature is an increase in
the number of particles with energy greater
than or equal to the activation energy (Ea)
Knowledge check SL
Question:
1. Which of the following best explains why an increase in temperature causes the rate of a
reaction to increase?
A the particles collide more
B the particles collide more frequently
C more particles have energy greater than the activation energy
D the activation energy is lower at higher temperature

2. An experiment was carried out to measure the rate of decomposition of hydrogen peroxide
according to the equation: 2H2O2(aq) → 2H2O(l) + O2(g)
56.0 cm3 of gas was produced in 30.0 s.
The average rate of reaction during this time was:
A 1.87 cm3 s−1 C 0.536 s cm−3
B 28.0 cm3 min−1 D 112 min cm−3

3. Which of the following will not increase the rate of the reaction between magnesium and hydrochloric
acid?
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

A increasing the surface area of the magnesium

B increasing the volume of hydrochloric acid used
C increasing the concentration of the hydrochloric acid
D increasing the temperature
Catalysis SL
A catalyst is a substance that increases the rate of a chemical reaction without itself being used up in the
reaction.
The catalyst is often written above the reaction arrow and does not appear in the chemical equation because
it does not change during the reaction.

MnO2
Example: 2H2O2(aq) 2H2O(l) + O2(g)
Manganese(IV) oxide is used as a catalyst in the decomposition of hydrogen peroxide solution.
Without the catalyst, the reaction occurs very slowly, but it is very rapid once the catalyst has been added.

A catalyst acts by allowing the reaction to proceed by an alternative pathway of lower activation energy.

A larger number of
particles have energy
greater than the
activation energy;
therefore a greater
proportion of collisions
results in reaction and
the reaction rate
increases.
Knowledge check SL
Question:

1. In the decomposition of hydrogen peroxide, manganese(IV) oxide is a catalyst. Which of the following
best describes the function of a catalyst and its mode of action?

A it speeds up the reaction by increasing the activation energy

B it slows down the reaction by decreasing the collision frequency of particles
C it speeds up the reaction by allowing the reaction to occur by an alternative pathway
of lower activation energy
D it speeds up the reaction by increasing the average energy of the particles

2. In the reaction between 1.00 g marble chips (calcium carbonate) and 25.0 cm 3 hydrochloric acid, which
of the following sets of conditions should give the fastest rate of reaction?

A 0.50 mol dm−3 HCl(aq) and small marble chips at 20 °C

B 0.10 mol dm −3 HCl(aq) and small marble chips at 30 °C
C 0.30 mol dm −3 HCl(aq) and small marble chips at 70 °C
D 0.50 mol dm −3 HCl(aq) and large marble chips at 30 °C
In these exercises, remember
both C and T are important in
increasing the rate of reaction,
surface area is less important
Knowledge check SL
Exercise:

A series of experiments was carried out to measure the volume of gas produced when magnesium reacts
with dilute hydrochloric acid.
The equation for the reaction is: Mg(s) + 2HCl(aq)→ MgCl2(aq) + H2(g)
In the first experiment, 0.10 g of Mg ribbon was reacted with 30 cm 3 of 0.50 mol dm−3 HCl. The data for this
experiment are recorded in the table. The reaction was carried out at 20 °C.

a. Draw a graph of these data and state and explain, in terms of the collision
theory, how the rate of reaction changes with time.
b. Use your graph to calculate the initial rate of the reaction with units.
c. Calculate the average rate for the first 120s.
d. The experiment was repeated under the same conditions, except that 0.10 g of
powdered Mg were used. On the same set of axes, you used in part a, sketch
the graph that would be obtained. Label this graph X.
e. The original experiment was repeated, except that 0.05 g of Mg ribbon was
used. On the same axes sketch the graph that would be obtained. Label this
graph Y.
f. The original experiment was repeated at 10 °C. On the same axes sketch the
graph that would be obtained. Label this graph Z.
g. Sketch the Maxwell–Boltzmann distribution for the original experiment and
the experiment at 10 °C and use this to explain the effect of a change in
temperature on the rate of this reaction.
Knowledge check SL
a. Graph: The gradient is steepest at the beginning – the
reaction is fastest; the concentration of reactants is
highest at the beginning, so the collision frequency is
highest. The gradient decreases as the reaction goes on
– the reaction rate decreases; reactants are being used
up – there is a lower concentration of reactants, so
lower collision frequency. The graph becomes
horizontal – the reaction has finished; the acid is in
excess, so the reaction finishes when all the
magnesium has been used up. d.e.f.

b. The initial rate is approximately 1.3 cm 3/s

c. The average rate is 0.62 cm3/s
g.

g. At the higher temperature, there are more

particles with energy greater than the activation energy.
Therefore there is a greater chance that a collision will
result in a reaction and more successful collisions per
unit time.