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# 22

2.2 Kinetics

Kinetics

## After studying this section, you will be able to:

Learning Objective(s)

understand that reactions can only occur when collisions take place between

## particles having sufficient energy

define the term activation energy and understand its significance
understand that most collisions do not lead to reaction
have a qualitative understanding of the MaxwellBoltzmann distribution
of molecular energies in gases
draw and interpret distribution curves for different temperatures
understand the qualitative effect of temperature changes on the rate of
reaction
understand how small temperature increases can lead to a large increase
in rate
understand the qualitative effect of changes in concentration on rate of
reaction
know the meaning of the term catalyst
understand that catalysts work by providing an alternative reaction route
of lower activation energy

For this topic, you should have reviewed the following definitions:
1.
2.
3.

Activation Energy
Collision Energy
Collision Frequency

4.
5.
6.

Heterogeneous catalyst
Homogeneous catalyst
Maxwell-Boltzmann distribution

1. Collision Theory
The collision theory: Reactions only happen when:
I.
II.
III.

Particles collide
Particles have the correct orientation
And they possess the minimum amount of kinetic energy particles need to react
(activation energy)

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2.2 Kinetics

## Therefore, to increase the rate of a reaction, particles must:

Collide more frequently (collision frequency) either;
o By increasing particle speed OR Having more particles in the same volume
Have more successful collisions either;
o By having more energy (collision energy) OR By lowering the activation energy

## Specific factors that affect the rate of a reaction are:

Increase the temperature generally, raising the temperature by 10oC doubles the rate.
How does energy increase rate? ____________________________________________
_____________________________________________________________________
Increase the concentration (for solutions) Increases the frequency of collisions of the
reacting molecules since there are more of them in the same volume
Increase the pressure (for gaseous reactions) Explain
Increase the surface area (for solids reacting with gases or liquids) Explain
Use a catalyst A catalyst works by providing an alternative route with lower activation
energy. Thus at a given temperature, a greater proportion of the colliding molecules will
possess the lower activation energy of the catalysed route and so the reaction will be
faster.
Use a light source (for photochemical reactions only)
Simple Energy profile diagrams are given below:
_______thermic reaction

I.
II.

_______thermic reaction

## Label the two graphs above as either exothermic or endothermic

Add labels for the diagram on the right to indicate
a. activated complex (transition state)
b. activation energy (Ea)
c. labels for the two axes
d. Enthalpy change.

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2.2 Kinetics

## 2. The Maxwell-Boltzmann distribution

In any system, the particles present will have a wide range of speeds and therefore of energies
(energy of a particle is proportional to the speed - KE = mv2). If a distribution graph is drawn to
show the molecular speed of gases on the x axis and the number of molecules on the y axis, we
get a Maxwell-Boltzmann distribution curve as shown below.

Note: these curves are not symmetrical & the peak of the
curve represents the most probable energy (Emp). The
average/mean energy (E bar) is further to the right.

A few particles will have very low energy (none will have zero energy) and a few will have very
high energy but the majority will have energies within a narrow range in the middle.
Although drawn as a curve, the distribution is actually a histogram and the area under the
curve is a measure of the total number of particles present.

## Using M-B distribution to explain Effect of Temperature Change

Since temperature affects the energy of molecules, the temperature of the system has an effect
on the size and shape of the Maxwell-Boltzmann distribution.
The effect of an increase in temperature is to make the molecules move faster and have a
higher average kinetic energy. The proportion of colliding molecules with energies equal to or
higher than the activation energy increases, and this causes an increase in successful collisions.
This is seen in the M-B distribution curve below. The curve for the higher temperature is shifted
to the right but slightly lowered. However, the area under the curve (proportional to the
number of molecules) stays the same.

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## Unit 2: Chemistry In action

2.2 Kinetics

At the higher temperature the peak of the curve is lower and shifts to the right.

## Lets try these

1.
Use one of the following three phrases to fill in the blanks - i) increase, ii)
decrease or iii) stay the same;
For reactants in a vessel, if the temperature increases from T1 to T2
a. the number of particles and therefore the area under a Maxwell-Boltzmann
curve will
___________________________
b. The overall Enthalpy of the reaction will __________________________
c. The Activation energy will __________________________
d. The proportion of molecules with energy higher than that of the activation
energy will __________________________
2.

## Is the following statement True or False?

An increase in temperature has no effect on the activation energy or enthalpy of a
reaction; it only increases the proportion of particles with a greater energy than Ea.
___________________________

## Using M-B distribution to explain Effect of Change in Concentration

The greater the concentration of the species in a liquid or gaseous mixture, the greater the
number of species per unit volume and the greater the frequency with which they will collide.
Hence an increase in concentration causes the rate of reaction to increase by increasing the
collision frequency.
The collision energy, activation energy and hence the fraction of successful collisions remains
the same.

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## Unit 2: Chemistry In action

2.2 Kinetics

For a gaseous mixture, the effect of an increase in pressure is the same as that of an increase in
concentration of a liquid reactant. The greater the pressure in a gaseous mixture, the greater
the number of species per unit volume and the greater the frequency with which they will
collide. Hence an increase in pressure causes the rate of reaction to increase by increasing the
collision frequency. The pressure of a system is generally increased by reducing its volume.
The collision energy, activation energy and hence the fraction of successful collisions are
unaffected.

3. Catalysts
We have already seen that a catalyst works by providing an alternative route with lower
activation energy which enables more particles to have the necessary energy for reaction.
This can be seen in the M-Boltzmann distribution at the bottom right. The green shaded area
represents the proportion of molecules initially with energy higher than the activation energy.
In the presence of the catalysed, an alternative route with lower activation energy is provided.
More particles (grey-shaded + green-shaded areas) now have the required energy to react.

## Energy profile diagram

Maxwell-Boltzmann distribution

A catalyst does not change the distribution curve but more molecules now have an energy
exceeding the new, lower activation energy.

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## Unit 2: Chemistry In action

2.2 Kinetics

Heterogeneous catalyst
A heterogeneous catalyst is in a different phase (physical state) from the reactants. Examples
include gaseous reactants using a solid catalyst.

## Examples of Heterogeneous catalysts

Production of sulphur trioxide and eventually sulphuric acid by
the contact process

## 2SO2 (g) + O2 (g) 2SO3 (g)

Production of ammonia (NH3) by the Haber Process

## Catalytic converter Reactions (to remove pollutants like unburnt

Platinum
and
Rhodium
hydrocarbons, CO & NO from car exhausts)
catalyst (supported on a
2CO (g) + 2NO (g) 2CO2 (g) +N2 (g)
ceramic honeycomb)

## How Heterogeneous catalysts work

In general reactant molecules diffuse towards the catalyst
surface, are adsorbed onto the catalyst and this weakens their
bonds allowing reaction to take place. Following reaction the
products are desorbed from the catalyst

Homogeneous catalyst
A homogeneous catalyst is in the same phase as the reactants.
Examples include gaseous reactions in the atmosphere which utilize gaseous catalysts or
reactions in aqueous solution where the catalyst is a liquid.

## Examples of Homogeneous catalysts

Breakdown of ozone in upper atmosphere (stratosphere)

formed by action of UV on
CFCs

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

O (g) + ClO. (g) O2 (g) + Cl. (g)
Production of esters from alcohols & carboxylic acids

## Acid catalyst (H+) usually

concentrated H2SO4

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2.2 Kinetics

## Lets try these

1.

Use one of the following three phrases to fill in the blanks - i) increase, ii)
decrease or iii) stay the same;
For a chemical reaction, if a catalyst is used to increase the speed of the reaction;
a. the number of reactant particles and therefore the area under a MaxwellBoltzmann curve will
___________________________
b. The overall Enthalpy of the reaction will __________________________
c. The Activation energy will __________________________
d. The proportion of molecules with energy higher than that of the activation
energy will __________________________

2.

## Is the following statement True or False?

The use of a catalyst has no effect on the activation energy or enthalpy of a reaction; it
only increases the proportion of particles with a greater energy than Ea.
___________________________

## For the next topic (Equilibria), learn the following definitions:

1.
2.
3.

Chemical feedstock
Dynamic equilibrium
Equilibrium Mixture

## AQA AS Chemistry (CHEM 2)

4.
5.

Le Chteliers Principle
Maxwell-Boltzmann distribution

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## Unit 2: Chemistry In action

2.2 Kinetics

Practice Questions
1.

(a)

State what is meant by the terms rate of reaction and activation energy.

Rate of reaction...........................................................................................................
.....................................................................................................................................
Activation energy.........................................................................................................
.....................................................................................................................................
(4 marks)
(b)
The diagram below shows the Maxwell-Boltzmann energy distribution curve for
a sample of gas at a fixed temperature. Ea is the activation energy for the
decomposition of this gas.

Number of
molecules
with a given
energy

Ea

Energy

(i)
On this diagram sketch the distribution curve for the same sample of gas at a
higher temperature.
(ii)
What is the effect of an increase in temperature on the rate of a chemical
Effect.........................................................................................................................
Explanation.............................................................................................................
...............................................................................................................................
...............................................................................................................................

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## Unit 2: Chemistry In action

2.2 Kinetics

(iii) What is the effect of the addition of a catalyst on the rate of a chemical
Effect........................................................................................................................
Explanation............................................................................................................
................................................................................................................................
................................................................................................................................
(9 marks)
(Total 13 marks)
2.

## The diagram below shows the MaxwellBoltzmann distribution of molecular energies in a

sample of a gas.

Number of
molecules

Z
Energy

(a)

(i)

State which one of X, Y or Z best represents the mean energy of the molecules.
...........................................................................................................................

(ii)

Explain the process that causes some molecules in this sample to have very low
energies.
...........................................................................................................................
...........................................................................................................................
(3)

(b)

On the diagram above, sketch a curve to show the distribution of molecular energies in
the same sample of gas at a higher temperature.
(2)

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## Unit 2: Chemistry In action

(c)

(i)

2.2 Kinetics

Explain why, even in a fast reaction, a very small percentage of collisions leads
to a reaction.
...........................................................................................................................
...........................................................................................................................

(ii)

Other than by changing the temperature, state how the proportion of successful
collisions between molecules can be increased. Explain why this method causes
an increase in the proportion of successful collisions.
Method for increasing the proportion of successful collisions........................
...........................................................................................................................
Explanation......................................................................................................
...........................................................................................................................
(4)
(Total 9 marks)

3.
Explain why the rate of the reaction between magnesium and dilute hydrochloric acid is
increased much more by changing the magnesium from ribbon to powder than by doubling the
concentration of the acid.
.........................................................................................................................................
.........................................................................................................................................
.........................................................................................................................................
.........................................................................................................................................
(2)
(Total 2 marks)

4.

The curve below shows how the volume of oxygen evolved varies with time when 50
cm3 of a 2.0 mol dm3 solution of hydrogen peroxide, H2O2, decomposes at 298 K.

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## Unit 2: Chemistry In action

2.2 Kinetics

Volume
of oxygen
/ cm 3
A

Time / s

(a)

State how you could use the curve to find the rate of reaction at point A.

.........................................................................................................................................
(1)
(b)
Sketch curves, on the above axes, to illustrate how the volume of oxygen
evolved would change with time if the experiment was repeated at 298 K using the
following.
(i)

100 cm3 of a 1.0 mol dm3 solution of H2O2. Label this curve X.

(ii)

## Label this curve Y.

(4)
(Total 5 marks)

5.
The equilibrium yield of product in a gas-phase reaction varies with changes in
temperature and pressure as shown below.

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## Unit 2: Chemistry In action

2.2 Kinetics

70
60
50
350C
% Yield
of product

40
450C
30
550C

20
10
0

50

100

150

200
250
Pressure/kPa

300

350

400

(a)
Use the information given above to deduce whether the forward reaction
involves an increase, a decrease, or no change in the number of moles present.
Change in number of moles................................................................................................
Explanation.........................................................................................................................
.............................................................................................................................................
...........................................................................................................................................
(4)

(b)
Use the information given above to deduce whether the forward reaction is
The forward reaction is..............................................................................................
Explanation................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

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(c)

(i)

2.2 Kinetics

## 350C use only and a pressure of 250 kPa.

...................................................................................................................................
(ii)
The
reaction
is
an
example
of
State what is meant by the term dynamic equilibrium.

dynamic

equilibrium.

...................................................................................................................................
(iii)
State what effect, if any, a catalyst has on the position of the equilibrium.
Effect on position ..............................................................................................................
Explanation .........................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
(6)
(d)
A 70% equilibrium yield of product is obtained at a temperature of 350 C and a
pressure of 400 kPa. Explain why an industrialist may choose to operate the plant at
(i)

## a temperature higher than 350 C;

..............................................................................................................................................
(ii)

## a pressure lower than 400 kPa.

.........................................................................................................................................
(2)
(Total 15 marks)

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6.

2.2 Kinetics

## Nitrogen, hydrogen and oxygen undergo the reactions shown below.

Reaction 1

1
2

N2(g) +

Reaction 2

1
2

N2(g) + 1 12 H2(g)

Reaction 3

H2(g) +

1
2

1
2

O2(g)

O2(g)

NO(g)

= +91 kJ mol1

NH3(g)

= 46 kJ mol1

H2O(g)

= 242 kJ mol1

## Use this information in answering the questions that follow.

(a)

In which, if any, of the reactions above would the percentage yield of products at
equilibrium increase if the temperature were to be raised? Explain your reasoning.
Yield increased with increased temperature. ..................................................
Explanation. ....................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)

(b)

In which, if any, of the reactions above would the percentage yield of products at
equilibrium not increase if the pressure were to be raised? Explain your reasoning.
Yield not increased with increased pressure. .................................................
Explanation. ....................................................................................................
..........................................................................................................................
(2)

(c)

(i)

## In which direction, if any, would any equilibrium reaction move if H = 0 and

the temperature were to be decreased?
..........................................................................................................................

(ii)

Predict for which of the reactions above the percentage yield of products at
equilibrium would be most affected by a change in temperature. Explain your
Reaction most affected by a temperature change. ...........................................
Explanation. .....................................................................................................
..........................................................................................................................
(3)
(Total 8 marks)

7.

## Methanol can be produced by direct combination of carbon monoxide and hydrogen

according to the equation below

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CO(g) + 2H2(g)

2.2 Kinetics

CH3OH(g)

= 91 kJ mol1

## Side reactions can also produce unwanted by-products.

(a)

Explain why a low temperature and a high pressure favour a high yield of methanol in
this reaction.
Low temperature ........................................................................................................
.....................................................................................................................................
.....................................................................................................................................
High pressure .............................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)

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(b)

2.2 Kinetics

## The industrial manufacture of methanol using this reaction is carried out at a

compromise temperature of 400 C under a pressure of 20 MPa in the presence of a
Cr2O3/ZnO catalyst.
(i)

## Justify the use of a compromise temperature.

............................................................................................................................
............................................................................................................................

(ii)

What effect, other than on the yield, does the use of high pressure have on the
reaction?
............................................................................................................................

(iii)

Suggest two reasons for using a catalyst in this method for producing methanol.
Reason 1 ...........................................................................................................
Reason 2 ...........................................................................................................
(5)
(Total 9 marks)

8.
(a)
State and explain, using the collision theory, the effect of concentration,
temperature and a catalyst on the rate of a reaction.
(10)
(b)

N2(g) + 3H2(g)

## 2NH3 (g) H = 92 kJ mol1

Explain how the equilibrium yield of ammonia in the Haber process is affected by
changing the pressure, changing the temperature and by using a catalyst.
(11)
(Total 21 marks)

...
...

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2.2 Kinetics

...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...

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## Unit 2: Chemistry In action

9.

2.2 Kinetics

The gas-phase reaction between hydrogen and chlorine is very slow at room temperature.
H2(g) + Cl2(g) 2HCl(g)
(a)

## Define the term activation energy.

.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

Give one reason why the reaction between hydrogen and chlorine is very slow at room
temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)

(c)

## Explain why an increase in pressure, at constant temperature, increases the rate of

reaction between hydrogen and chlorine.
.....................................................................................................................................
.....................................................................................................................................
(2)

(d)

Explain why a small increase in temperature can lead to a large increase in the rate of
reaction between hydrogen and chlorine.
.....................................................................................................................................
.....................................................................................................................................
(2)

(e)

## Give the meaning of the term catalyst.

.....................................................................................................................................
.....................................................................................................................................
(1)

(f)

Suggest one reason why a solid catalyst for a gas-phase reaction is often in the form of
a powder.
.....................................................................................................................................
(1)
(Total 9 marks)

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## Unit 2: Chemistry In action

10.

2.2 Kinetics

The curve below represents the distribution of molecular energies at a temperature T1 for a
mixture of gases which react with each other. A is the activation energy for the reaction.

T1

A
(a)

energy

(i)

(ii)

## Explain the meaning of the term activation energy.

...........................................................................................................................
...........................................................................................................................

(iii)

Draw a second curve on the same axes, and label it T2, for the same mixture at a
lower temperature.

(iv)

By reference to the curves, state and explain in molecular terms the effect of
reducing the temperature on the rate of reaction.
Effect .................................................................................................................
Explanation .......................................................................................................
...........................................................................................................................
...........................................................................................................................
(8)

(b)

## The reaction is repeated in the presence of a catalyst.

Mark on the energy axis a possible activation energy B for the catalysed reaction.
(1)

(c)

## Give an example of a catalyst and a reaction which it catalyses.

Catalyst .......................................................................................................................
Reaction using this catalyst ........................................................................................
.....................................................................................................................................
(2)

## Unit 2: Chemistry In action

(d)

2.2 Kinetics

Several small pieces of calcium carbonate (an excess) were allowed to react with
100 cm3 of 0.1 M hydrochloric acid. The volume of carbon dioxide formed during the
experiment is shown on the graph below.

140
120

Volume of CO 2 /cm 3

41

100
80
60
40
20
0

Time

Using the same axes, sketch curves labeled A, B and C for the following experiments
which were all carried out at the same temperature as the original experiment:
A

carbonate;

carbonate;

## 50 cm3 0.1 M hydrochloric acid with an excess of powdered calcium carbonate.

(6)
(Total 17 marks)

11.

In the Haber process for the manufacture of ammonia, nitrogen and hydrogen react as shown
in the equation.
N2(g) + 3H2(g)

2NH3(g)

H = 92 kJ mol1

The table shows the percentage yield of ammonia, under different conditions of pressure and
temperature, when the reaction has reached dynamic equilibrium.

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2.2 Kinetics

Temperature / K

600

800

1000

50

10

60

16

75

25

(a)

## Explain the meaning of the term dynamic equilibrium.

.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

## Use Le Chateliers principle to explain why, at a given temperature, the percentage

yield of ammonia increases with an increase in overall pressure.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(c)

Give a reason why a high pressure of 50 MPa is not normally used in the Haber
process.
.....................................................................................................................................
(1)

(d)

## Many industrial ammonia plants operate at a compromise temperature of about 800 K.

(i)

State and explain, by using Le Chateliers principle, one advantage, other than
cost, of using a temperature lower than 800 K.
Explanation ......................................................................................................
...........................................................................................................................

(ii)

## State the major advantage of using a temperature higher than 800 K.

...........................................................................................................................

(iii)

## Hence explain why 800 K is referred to as a compromise temperature.

...........................................................................................................................
(5)
(Total 11 marks)