Worked solutions: Chapter 7

Kinetics

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Section 7.1 Exercises
1 a

b i Between t = 0 s and t = 400 s rate =
400
) 25 . 2 43 . 1 (
= 2.05 10
3
mol dm
3
s
1

ii Between t = 400 s and t = 800 s rate =
400
) 43 . 1 88 . 0 (
= 1.38 10
3
mol dm
3
s
1

iii Between t = 1600 s and t = 2000 s rate =
400
) 22 . 0 13 . 0 (
= 2.25 10
4
mol dm
3
s
1

c Of the three 400 s periods measured, the rate of reaction was the smallest for the period of
time from t = 1600 s to t = 2000 s. This is because the concentration of reactants has
diminished greatly, and so the chance of collisions is the lowest. (NB: t = 2000 s to 2400 s
would be even lower.)
Worked solutions: Chapter 7
Kinetics

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2 a

b NO
2
is the reactant that is decomposing, so its concentration decreases, while that of the
others (the products) increases.
c The rate of increase of [O
2
] is half that of the rate of increase of [NO] as 1 mole of O
2

forms when 2 moles of NO
2
are formed.
3 n(S
2
O
3
2
) = 2n(I
2
) produced in the reaction.
So volume of S
2
O
3
2
that reacts with I
2
is proportional to n(I
2
).
therefore the rate can be expressed in terms of cm
3
of S
2
O
3
2
that reacts.
a In the first 15 min: rate =
15
15
= 1.0 cm
3
min
1
(or 1.0 10
4
mol I
2
min
1
)
b In the second 15 min: rate =
15
15 24
= 0.60 cm
3
min
1
(or 6.0 10
5
mol I
2
min
1
)
c In the final 15 min: rate = 0 cm
3
min
1
(or 0 mol I
2
min
1
)
Worked solutions: Chapter 7
Kinetics

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4 a

b A tangent is drawn to the curve. The slope of the tangent will give the reaction rate at any
given time, as reaction rate =
t
] reactants [
.
c

d The reaction rate is proportional to the concentration of SO
2
Cl
2
.
Worked solutions: Chapter 7
Kinetics

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Section 7.2 Exercises
1 a There is a great amount of space between the gas particles, so they can be brought closer
together without any difficulty.
b Gas particles move rapidly and randomly, so will move to completely fill any container.
c Gas particles move rapidly and randomly.
d In a given volume, there are fewer gas particles than there are solid particles, so the density
is lower.
2 a As the sample of gas is heated, the average speed of the gas particles will increase.
b The pressure of the gas on the container walls will increase.
c The average space between the gas particles will stay the same.
d The frequency of collisions between the particles will increase.
3 a

b i The area under the graph stays the same.
ii The spread of gas speeds increases.
iii The velocity at which the graph peaks increases.
4 In addition to colliding with sufficient energy to break the bonds in the reactants and so
overcome the activation energy, particles must also collide with the correct orientation if a
reaction is to occur.
5 a Increasing temperature increases the kinetic energy of the particles and so makes it more
likely that they will collide with sufficient energy to overcome the activation energy. More
collisions with E E
a
will occur in a given time.
Worked solutions: Chapter 7
Kinetics

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b An increase in concentration means there are more particles present in any given volume
and so there is a greater likelihood of collisions with energy E
a
occurring. The number of
collisions in a given time increases.
c An increase in the surface area of a solid ensures that there are more reactant particles
available at the surface of the solid to take part in the reaction, thus increasing the number
of collisions with the correct orientation and E E
a
in a given time.
6 a A decrease in temperature lowers the rate of reaction by decreasing the average kinetic
energy of the particles, so it takes longer for the milk to go off at the lower temperature in
the fridge.
b Wheat carries with it a great deal of fine dust. It is this dust, with its associated huge
surface area, that makes it susceptible to ignition and explosion. A filled wheat silo has
little air space available for the dust to suspend in the air.
c When pure oxygen is used the concentration of one of the reactants (oxygen) is
significantly increased, ensuring that the rate of reaction will also increase.
d Small pieces of wood, or kindling, catch alight far more easily, as they have a substantial
surface area of wood that is exposed to air to allow the combustion reaction to take place.
7 a The concentration of N
2
O
5
decreased most quickly at the start of the reaction as this was
the period of time when the concentration of this reactant was at its greatest. As the
reaction proceeds and the N
2
O
5
is consumed, the rate at which it is converted to product
must decrease.
b At a lower temperature it would be expected that the rate of reaction would decrease; it
would take longer for the initial quantity of N
2
O
5
to decompose.
c To increase the rate, a higher temperature could be used, the concentration of N
2
O
5
could
be increased or a catalyst introduced.
8 The lack of dissolved oxygen slows the decomposition process as the organisms and bacteria
that initiate the process do not have oxygen available for respiration. In addition, the presence
of organic acids lowers the pH and makes the environment less favourable for the organisms
responsible for decomposition.
Chapter 7 Review questions
1 a It is in the solid state that particles are generally packed most closely together with the least
space available for movement. In the liquid state, particles are a little more separated and
can slide past one another. The greater the space between particles, the lower will be the
density.
b In the liquid state, particles are a little more separated than is the case for solids, but they
are still close nevertheless. In gases, particles are widely dispersed, with significant
distances separating them, ensuring that they can be readily compressed to a smaller
volume.
Worked solutions: Chapter 7
Kinetics

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c Although you would expect a cigarette lighter to be used up when it is disposed of, there
will be some fuel left in the lighter. The heat of the incinerator will be enough to increase
the kinetic energy of the gas molecules and cause an explosion.
d An increase in temperature increases the kinetic energy of particles and so makes it more
likely that they will collide with sufficient energy to overcome the activation energy and
initiate reaction.
2 The second student was correct, as temperature is a measure of the average kinetic energy of
particles at a particular temperature. Boltzmann proved that particles have a range of speeds,
and hence energies, at any given temperature. If this were not the case, a chemical reaction
would not occur at all until a certain magic temperature had been reached, at which point
every particle present would react instantaneously. We know from practical experience that this
is not the case.
3 Particles must collide with sufficient energy to break the bonds in the reactants and so
overcome the activation energy. They must also collide with the correct orientation if a reaction
is to occur.
4

5 The rate of disproportionation (the redox reaction of a substance with itself) is very slow in this
case, and is decreased even further if the temperature is kept low.
6 The activation energy of a chemical reaction is the energy required to break the bonds of the
reactants; energy must be added, so this is an endothermic process.
7 The zinc could be used in powdered form to increase its surface area; the temperature of the
hydrochloric acid could be increased; the concentration of the hydrochloric acid could be
increased.
8 a The covalent bonds in the reactant molecules must be broken.
b The activation energy would be greater than 280 kJ mol
1
as a catalyst lowers the
activation energy.
Worked solutions: Chapter 7
Kinetics

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c The catalyst lowers the activation energy by providing an alternative pathway for the
reaction to proceed.
9 a Smaller pieces of wood have a larger surface area and so a greater availability of fuel for
combustion with oxygen to take place.
b Dust has a very large surface area, so that a relatively small amount of energy is enough to
initiate a combustion reaction.
c The low temperatures that exist in the frozen tundra, and the lack of water, would cause the
rate of decomposition of the woolly mammoth to decrease significantly.
d Powdered zinc has a significantly greater surface area than large pieces and so will react
far more quickly with the hydrochloric acid.
e Manganese(IV) oxide acts as a catalyst for this reaction and so increases the rate of
reaction.
10 a i Rate of reaction will increase.
ii Volume of CO
2
produced will increase.
b i Rate of reaction will not change.
ii Volume of CO
2
produced will decrease.
c i Rate of reaction will increase.
ii Volume of CO
2
produced will stay the same.
d i Rate of reaction will decrease.
ii Volume of CO
2
produced will stay the same.
Chapter 7 Test
Part A: Multiple-choice questions
Question Answer Explanation
1 B Reactions will not occur if reactants do not have energy greater than or equal to E
a
.
2 D As temperature increases, the fraction of molecules with energy equal to or greater
than the required energy increases. This is the main reason that the rate of reaction
increases.
3 A The rate of the reaction is given by the gradient of the graph. As time proceeds, the
gradient decreases and so the rate of the reaction decreases as the HCl becomes
more dilute.
4 D Rate of reaction is dependent on the energy of collision between the reactants. At
normal atmospheric pressure, rate of reaction is slow as very few of the reactants
have sufficient energy to react.
5 C Rate is the change of concentration (mol dm
3
) per unit time (s
1
).
6 C Rate of reaction will increase due to an increase in concentration of HCl, increased
surface area, or increased temperature. An increase in pressure will increase the
rate of a reaction between gaseous reactants; however, CO
2
is a product, not a
reactant.
Worked solutions: Chapter 7
Kinetics

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Question Answer Explanation
7 B Increasing the activation energy means that more energy is required for the
reaction to proceed, and thus the rate will be less.
8 C For reactions to proceed, particles must collide with energy equal to or greater than
the activation energy.
9 D Increasing the amount of reactant will not change the rate. Increasing the
concentration and surface area (pulverizing) will increase the rate and decreasing
the temperature will decrease the rate of reaction.
10 A Rate of a reaction is the change in concentration per unit time.
For A, rate = 4 6 = 2; for B, rate = 2 3 = 1; for C, rate = 1 0 = 1

Note that key information is indicated in bold type.
Part B: Short-answer questions
1 Increasing the temperature creates more energetic collisions (i.e. more molecules have energy
greater than activation energy) so collisions are more frequent.
(2 marks)
2 a Rate of reaction is equal to an increase in product concentration or a decrease in
reactant concentration per unit time.
(1 mark)
b i The activation energy is too high or there are not enough molecules with
E E
a
or the geometry of collision is incorrect.
(2 marks)
ii An increase in temperature means that the average kinetic energy of the molecules
increases, so that more molecules have E E
a
, and there are more frequent collisions.
(2 marks)

iii Add a catalyst.
Increase the pressure or decrease the volume of the container.
Increase the concentration of one of the reactants.
(2 marks)
3 a Magnesium carbonate powder could be used.
A higher concentration of hydrochloric acid could be used.
The temperature of the hydrochloric acid could be increased before the magnesium
carbonate is added.
(3 marks)
Worked solutions: Chapter 7
Kinetics

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b & c

(3 marks)
Part C: Data-based question
a i Carbon dioxide is produced.
(1 mark)
ii CuCO
3
(s) + 2HCl(aq) CuCl
2
(aq) + CO
2
(g) + H
2
O(l)
(2 marks)
b 80 cm
3
of gas would be produced.
It would take 4 minutes for the reaction to be complete.
(1 mark)
c i The collision frequency is greatest at the start and decreases with time, because there is the
greatest concentration or number of reactant particles at the start. This means that the slope
of the graph is sharp initially and gradually decreases.
(2 marks)
ii Curve B does not rise up as far as A because the mass of CuCO
3
is lower for B than A, or
the concentration or amount of HCl is lower for B than A.
(2 marks)
d The curve drawn should have a steeper initial gradient than curve A but should reach the
same final volume.
(2 marks)
Worked solutions: Chapter 7
Kinetics

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Part D: Extended-response question
a i The rate of reaction increases because collisions between reactants are more frequent.
(2 marks)
ii The rate of reaction decreases because extra liquid decreases the thiosulfate concentration,
so thiosulfateH
+
collisions are less frequent.
(3 marks)
iii The rate is increased because at the higher temperature, kinetic energy increases, there are
more frequent collisions and the collisions have greater energy, so more have E E
a
in
a given time.
(4 marks)
b An increase in concentration increases only the frequency of collisions, whereas increasing the
temperature increases both the frequency and the energy of collisions (i.e. more particles with
E E
a
).
(2 marks)
c i

(2 marks)
ii Draw tangents to the graph at different times. The rate (at time t) = gradient of the tangent
(at that time).
(2 marks)