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2.2 Kinetics
Kinetics
Learning Objective(s)
understand that reactions can only occur when collisions take place between
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
I.
II.
_______thermic reaction
24
2.2 Kinetics
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.
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2.2 Kinetics
At the higher temperature the peak of the curve is lower and shifts to the right.
26
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.
Maxwell-Boltzmann distribution
A catalyst does not change the distribution curve but more molecules now have an energy
exceeding the new, lower activation energy.
27
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.
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.
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2.2 Kinetics
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.
Chemical feedstock
Dynamic equilibrium
Equilibrium Mixture
4.
5.
Le Chteliers Principle
Maxwell-Boltzmann distribution
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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
reaction? Explain your answer with reference to the Maxwell-Boltzmann distribution.
Effect.........................................................................................................................
Explanation.............................................................................................................
...............................................................................................................................
...............................................................................................................................
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2.2 Kinetics
(iii) What is the effect of the addition of a catalyst on the rate of a chemical
reaction? Explain your answer with reference to the Maxwell-Boltzmann distribution.
Effect........................................................................................................................
Explanation............................................................................................................
................................................................................................................................
................................................................................................................................
(9 marks)
(Total 13 marks)
2.
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)
31
(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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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)
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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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.
Explain your deduction.
Change in number of moles................................................................................................
Explanation.........................................................................................................................
.............................................................................................................................................
...........................................................................................................................................
(4)
(b)
Use the information given above to deduce whether the forward reaction is
exothermic or endothermic. Explain your answer.
The forward reaction is..............................................................................................
Explanation................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
34
(c)
(i)
2.2 Kinetics
dynamic
equilibrium.
...................................................................................................................................
(iii)
State what effect, if any, a catalyst has on the position of the equilibrium.
Explain your answer.
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)
..............................................................................................................................................
(ii)
.........................................................................................................................................
(2)
(Total 15 marks)
35
6.
2.2 Kinetics
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
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)
(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
answer.
Reaction most affected by a temperature change. ...........................................
Explanation. .....................................................................................................
..........................................................................................................................
(3)
(Total 8 marks)
7.
36
CO(g) + 2H2(g)
2.2 Kinetics
CH3OH(g)
= 91 kJ mol1
Explain why a low temperature and a high pressure favour a high yield of methanol in
this reaction.
Low temperature ........................................................................................................
.....................................................................................................................................
.....................................................................................................................................
High pressure .............................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
37
(b)
2.2 Kinetics
(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)
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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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)
(b)
Give one reason why the reaction between hydrogen and chlorine is very slow at room
temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)
(c)
(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)
(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)
40
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)
(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)
(c)
(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
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)
(b)
(c)
Give a reason why a high pressure of 50 MPa is not normally used in the Haber
process.
.....................................................................................................................................
(1)
(d)
State and explain, by using Le Chateliers principle, one advantage, other than
cost, of using a temperature lower than 800 K.
Advantage .........................................................................................................
Explanation ......................................................................................................
...........................................................................................................................
(ii)
(iii)