Worked solutions

Chapter 6
Exercises

1 The information given on pages 275–278 is very (ii) As H+ (HCl) is consumed in the reaction
comprehensive. Suitable methods follow from we could measure the increase in pH of
an analysis of the equation given, including a the reaction mixture.
consideration of state symbols and ions. (iii) As CO2 gas is produced in the reaction
●● Reaction gives off CO2 gas: change in we could measure the increase in
volume of CO2 gas released could be volume of gas collected using a gas
measured using a gas syringe. (It cannot syringe. (It cannot be measured using
be measured using the water displacement the water displacement method as CO2
method as CO2 gas dissolves in water.) gas dissolves in water.)
●● Reaction gives off CO2 gas: loss of mass (b) The rate of the reaction decreases with
could be measured by conducting the time because the concentration of the acid
reaction in an open flask on a digital balance. decreases (rate ∝ [HCl]).
●● Reaction involves purple MnO4− ions being 4 Note that ‘time’ here is the independent variable
reduced to colourless Mn2+ ions: colorimetry so it goes on the x-axis. ‘Concentration’ is the
could be used to measure the change in dependent variable and goes on the y-axis. A
solution absorbance. graph is plotted using all the data given and a
●● Reaction involves a change in the smooth curve is drawn through the points.
concentration of ions (23 on the reactants The rate of the reaction at a particular interval
side and 2 on the products side): a of time = gradient of the tangent to the curve at
conductivity meter could be used to that time. Tangents to the curve are drawn at
measure the change in solution conductivity. time = 60 s and at time = 120 s.
●● Reaction involves a change in pH as H+ ions Gradients are calculated from Δy/Δx
are used up: a pH meter could be used to At 60 s, a tangent line passes through the points
measure the change in solution pH. (0, 0.155) and (185, 0).
2 C Here it is best to answer the question (0 – 0.155) mol dm3
gradient =
yourself without looking at the answers (185 – 0) s
= –8.4 × 10–4 mol dm–3 s–1
(remember they are designed to trick
you). Rate is expressed as the change in rate of reaction = 8.4 × 10–4 mol dm–3 s–1
concentration with time.
At 120 s, a tangent line passes through the
Δ[A]
Rate = points (0, 0.114) and (250, 0.023).
Δt (0.023 – 0.114) mol dm3
units of concentration mol dm–3 gradient =
Units of rate = = (250 – 0) s
units of time time = –3.6 × 10–4 mol dm–3 s–1
= mol dm–3 time–1
(time–1 could represent any unit of time, e.g. s–1, Note that the gradient to the tangent can be
min–1, hr–1 etc.) derived from any values of Δy/Δx so long as
they are measured from a right-angled triangle.
3 (a) (i) As CO2 gas is produced in the reaction Negative values are obtained for the gradients
we could measure the decrease in the at t = 60 s and t = 120 s as the experiment is
mass of flask + contents. measuring the decrease in concentration of the

1
H2O2 reactant. However, rates of reaction are 11 The ashes must contain a catalyst that speeds
expressed as positive values. up the reaction between sugar and oxygen.
0.25 (Deduced from the fact that all other factors that
0.2
affect reaction rate can be ruled out.)
(0, 0.155)
[H2O2] / mol dm−3

0.15 (0, 0.114) 12 (a) 2CO(g) + 2NO(g) → 2CO2(g) + N2(g)

0.1 (b) CO is a toxic gas: it combines with
(250, 0.023)
0.05
haemoglobin in the blood and prevents it
(185, 0) from carrying oxygen. NO is a primary air
0
0 50 100 150 200 250 pollutant: it is oxidized in the air to form
Time / s
acidic oxides, NO(g) + 12O2(g) → NO2(g),
5 D Colliding particles must have a kinetic energy leading to acid rain: NO2(g) + H2O(l) →
that is greater than the activation energy in HNO3(aq). It also reacts with other pollutants
order that the reaction might take place (they in the atmosphere forming smog.
must also have the correct geometry). (c) Coating beads with the catalyst increases
the surface area of the catalyst in contact
6 A Both the orientation and energy of the
with exhaust gases and increases the
molecules are factors in determining whether
efficiency of the catalytic converter.
a reaction will occur.
(d) Catalytic activity involves the catalyst
7 The reaction requiring the simultaneous interacting with the gases, and the reaction
collision of two particles is likely to be faster. occurring on its surface. As temperature
The simultaneous collision of three particles is increases, the increased kinetic energy of
statistically less likely (i.e. the probability of three the gases increases the frequency with
particles simultaneously colliding is much lower which they bind to the catalyst as well as
than the probability of two particles colliding). the rate at which the reaction occurs on the
surface and the rate at which the products
8 B Catalysts increase the rate of both the
desorb from the surface.
forward and the backward reactions by
lowering the activation energy of the reaction (e) Catalytic converters reduce pollution from
in both directions. The use of a catalyst cars but do not remove it completely. As in
does not necessarily increase the yield of (d), they are not effective when the engine
products. first starts from cold, when an estimated
80% of pollution occurs. Other pollutants
9 B Catalysts increase the rate of both the in car exhausts are not removed by the
forward and the backward reactions catalyst, e.g. ozone, sulfur oxides, and
by lowering the activation energy of the particulates. Also the catalytic converter
reaction. By increasing the temperature the increases the output of CO2, a serious
collision frequency increases and so leads to pollutant because of its greenhouse gas
a greater rate of reaction. properties.
10 B A higher rate of a reaction involving a Note: this is a good example of a question which
solid will occur if it is present as a powder bridges several topics, and could equally well be
as it has a larger surface area. For two found under Option E: Environmental chemistry.
concentrations of acid the rate will be faster Note that in part (e) where the command verb is
for the higher concentration as there are ‘Discuss’, you are expected to try and think of
more acid (H+) particles available to collide arguments on both sides of the question.
with the CaCO3(s).

2
13 The rate expressions are written by multiplying k, (c) Rate = k[NH3]0: reaction is zero order:
the rate constant, by the concentration of each units of rate
units of k =
reactant raised to the power of its order, which is (units of concentration)0
given in the table. mol dm–3 s–1
= = mol dm–3 s–1
1
Experiment 1: rate = k[H2][I2]
(d) Rate = k[NO]2[Br]: reaction is third order
Experiment 2: rate = k[H2O2] overall:
Experiment 3: rate = k[S2O82−][I−] units of rate
units of k =
Experiment 4: rate = k[N2O5] (units of concentration)3
mol dm–3 s–1 mol dm–3 s–1
Beware the mistake of using the values for the = =
(mol dm–3)3 mol3 dm–9
coefficients in the balanced equation – they are = mol–2 dm6 s–1
not directly related to the order.
(e) Rate = k[H2][I2]: reaction is second order
14 As both NO and O3 are in the rate equation overall:
with their concentration raised to the power 1, units of rate
the reaction is first order with respect to each units of k =
(units of concentration)2
of them. The overall order is the sum of the mol dm–3 s–1 mol dm–3 s–1
= =
individual orders, therefore second. (mol dm–3)2 mol2 dm–6
= mol–1 dm3 s–1
15 Here the sum of the orders with respect to the
reactants must be 2. This would be the case if 17 As the units of k are s–1, the reaction must be
the reaction was second order with respect to first order – where the mol dm–3 terms have
one reactant and zero order with respect to the cancelled out (see the answer to question 16
other, or if it was first order with respect to each above). As there is only one reactant, the rate
reactant. expression can only be rate = k[N2O5].
The three options are: Note: this is a good example of a reaction where
rate = k[CH3Cl] 2 the rate equation does not match the overall
reaction equation.
rate = k[CH3Cl][OH−]
rate = k[OH−]2 18 From the information given in the question, we
can deduce that rate = k[A]0[B]2 or rate = k[B]2.
16 You can work out the units for k for any reaction
Substituting the initial concentration of B and the
of known order using the approach given in the
initial rate into this equation, we get:
table on page 290. This is generally better than
trying to learn the units. rate = k[B]2
(a) Rate = k[NO2]2–: reaction is second order 4.5 × 10–4 mol dm–3 min–1 = k(2.0 × 10–3 mol dm–3)2
overall: 4.5 × 10–4 mol dm–3 s–1
which gives k =
units of rate 4.0 × 10–6 mol2 dm–6
units of k =
(units of concentration)2 = 1.1 × 102 mol–1 dm3 min–1
mol dm–3 s–1 mol dm–3 s–1 Note: make sure answers for k always include
= =
(mol dm–3)2 mol2 dm–6 units.
= mol dm s
–1 3 –1

19 C Here it is best to work out the order with

(b) Rate = k[CH3CH2Br]: reacton is first order
respect to each reactant first, before looking
overall:
at the answers given.
units of rate
units of k = The order for NO2 can be deduced by
units of concentration
mol dm–3 s–1 mol dm–3 s–1 comparing the first two rows where [F2] stays
= = = s–1
mol dm–3 mol2 dm–3 the same while [NO2] doubles from 0.1 to

3
0.2; the rate increases ×4 (from 0.1 to 0.4). 23 The rate-determining step is NO2 + NO2 → NO3
So it is second order with respect to NO2. + NO.
The order for F2 can be deduced by The rate expression for this step is rate = k[NO2]2.
comparing the first and third rows where Because the rate-determining step is the first
[NO2] stays the same while F2 doubles from step this will also be the overall rate expression
0.2 to 0.4; the rate doubles from 0.1 to 0.2. for the reaction. This mechanism is second order
So it is first order with respect to F2. with respect to NO2 so it is consistent with the
20 This is similar to question 19, but slightly harder experimental observation that the reaction is
as there is no data to compare two reactions second order with respect to NO2.
where [O2] stays the same. So the order for NO The mechanism is also consistent with the overall
will have to be worked out indirectly as follows. reaction as the two steps of the mechanism
From experiments 1 and 2, [NO] stays the same combine to give the overall reaction stoichiometry:
while doubling [O2] leads to a doubling of the NO2 + NO2 → NO3 + NO
rate. So the reaction is first order with respect to NO3 + NO → 2NO + O2
O2.
2NO2 → 2NO + O2
Knowing this, we can see in experiments 2 and
24 C Statement I is only true if the reaction
3 [O2] doubles, which accounts for a doubling of
can only happen via a one-step reaction
the rate. But overall the rate has increased here
involving two molecules of SO2 and one O2
×8 from 4.0 × 10–3 to 3.2 × 10–2. So the rate
colliding simultaneously. This has a very low
has increased ×4 due to the doubling of [NO].
probability compared to collisions between
Therefore it must be second order with respect
two molecules. It is more likely that the
to NO.
reaction could occur through two or more
The rate expression follows from this: rate = steps so it is not correct to say it must be
k[NO]2[O2] between two SO2 and one O2 molecule.
21 From the given rate expression we can deduce Statement II is not correct as not every
that the reaction is second order with respect to collision produces products: only those with
A and zero order with respect to B. So changes sufficient kinetic energy to overcome the
in [B] will not affect the rate of the reaction. activation energy will produce products.
Comparing experiments 1 and 2, [A] doubles Statement III is correct as the slowest step of
so the rate will increase ×4. The rate in a mechanism is always the rate-determining
experiment 2 will be four times the rate in step.
experiment 1 (3.8 × 10–3 mol dm–3 s –1) × 4 =
25 (a) The overall equation is deduced by
1.5 × 10–2 mol dm–3 s–1.
adding together the steps in the reaction
Comparing experiments 2 and 3, [A] stays mechanism.
the same so the rate does not change as
AB2 + AB2 → A2B4 slow
the change in [B] will not affect the rate. Rate
A2B4→ A2 + 2B2 fast
in experiment 3 = rate in experiment 2 =
1.5 × 10–2 mol dm–3 s–1. 2AB2 → A2 + 2B2
Here the A2B4 molecules cancel, so the net
22 Because we are told this is a one-step
equation is AB2 + AB2 → A2 + 2B2 (or 2AB2
mechanism, the rate expression can be deduced
→ A2 + 2B2).
directly from the stoichiometry of that step.
(b) The slowest step is the rate-determining
rate = k[NO2][CO]
step. The rate expression for the rate-
determining step is:
4
rate = k[AB2]2 2 Curve Y shows a greater volume of O2 being
Because the rate-determining step is the first produced after it reaches completion than in the
step this is also the overall rate expression initial reaction therefore the change being made
for the reaction. must involve a greater amount of reactants than
in the initial reaction. The only possible change
(c) The units for k are derived from the fact that
that will do this is B, where additional hydrogen
it is a second-order reaction.
peroxide solution is added.
rate = k[AB2]2
Correct answer is B.
units of rate
units of k =
(units of concentration)2 3 Consider conditions 1 and 2: [Br2] has been
mol dm–3 s–1 mol dm–3 s–1 doubled and [NO] is constant. As rate has
= =
(mol dm–3)2 mol2 dm–6 increased by a factor of four the reaction is
= mol–1 dm3 s–1 second order with respect to Br2 and rate α [Br2]2.
26 C Statement I is true (see page 301). Consider conditions 2 and 3: [Br2] is constant
Statement II is not true: activation energy is and [NO] has been quadrupled. As the rate
not temperature dependent. Statement III is has not changed the reaction is zero order with
true (see page 301). respect to NO. Rate = k[Br2]2[NO]0 = k[Br2]2
Correct answer is C.
27 D A: activation energy = Ea, B: kinetic energy is
not mentioned in the Arrhenius equation, C: 4 Rate-determining steps are the slowest steps
gas constant = R. in a reaction mechanism and correspond to the
steps with the highest activation energy.
28 B Statement I is correct, the rate of collisions
increases with temperature. Statement Correct answer is C.
II is false, the activation energy is not 5 A rate expression can be derived for the slowest
temperature dependent. Statement III is step: rate = k[N2O2][H2].
correct, k (the rate constant) increases with
Because N2O2 is an intermediate it is necessary
temperature.
to substitute for [N2O2] based on its formation
29 Using the equation ln
( ) (
k1
k2
E 1
= a −
1
R T2 T1 ) in the first step: [N2O2] = k’[NO]2 . The rate
expression is therefore rate = k[H2][NO]2.
(23.0 mol dm s )
1.3 mol dm s 3 –1
In 3 –1 Correct answer is A.

8.31 J K mol 800 K 700 K )

(
E 1 1 6 Any change that increases the frequency of
= a
–1
–
–1
collisions between reactants will increase the
–2.87 = –2.15 × 10–5 J–1 mol × Ea rate of a reaction.
Ea = 1.34 × 105 J mol–1 = 134 kJ mol–1 Increasing pressure of gaseous reactants
increases the number of molecules per unit
volume so will increase the frequency of
collisions.
Practice questions
Increasing temperature results in molecules
1 For a first-order reaction rate = k[A] so the rate of moving faster and will increase the frequency of
reaction will decrease as the reaction proceeds collisions (as well as the proportion of successful
and the reactants are consumed. collisions).
Removing the product will not affect the
Correct answer is A.
frequency of collisions between the reactants.
Correct answer is A.

5
7 Increasing temperature does not affect the 11 (a) NO is acting as a catalyst for this
activation energy, order of reaction or enthalpy mechanism as it is consumed in one step
change of the reaction. Increasing temperature and then regenerated in a later step. This
does increase the frequency of collisions as well means that even though it participated in
as the proportion of collisions with sufficient the reaction there is no overall change in the
energy to overcome the activation energy. amount of NO present after the reaction has
Increasing temperature will therefore result in a reached completion.
faster reaction with a larger rate constant. (b) (i) An intermediate is a species that
Correct answer is B. is produced in one step and then
consumed in a subsequent step.
8 Because there are no acids or bases present the N2O2(g) is an intermediate in this
reaction cannot be monitored using pH changes. mechanism as it is produced in the first
No gases are released so no change in mass step and consumed in the second step.
will occur during the reaction and the volume
(ii) If step 1 was the slow step, rate = k[NO]2.
of the solutions will also not change during the
reaction. If step 2 was the slow step, rate =
k[N2O2][H2].
As discussed in Chapter 3 transition metal
complexes are coloured and the colour of the Substituting for the concentration of the
complexes of any metal ion will change for intermediate N2O2, rate = k[NO]2[H2].
different ligands. Co(H2O)62+ will therefore have The theoretical rate expression obtained
a different colour to CoCl42– and the rate of when the second step is the slow step
reaction can be monitored by the change in agrees with the rate expression obtained
colour that occurs as the reaction proceeds. experime ntally, rate = k[NO]2[H2].
Correct answer is C. (c) If k2 >> k1 the first step is slow compared
to the second step and the first step is the
9 The information provided indicates that
therefore the rate-determining step.
powdered MnO2 is a heterogenous catalyst for
If the first step is the rate-determining step
the decomposition of H2O2. Catalysts speed up
then the theoretical rate expression is rate =
reactions by providing an alternative reaction
k[NO2]2, which agrees with the experimental
pathway with a lower activation energy and
rate expression.
are not used up in the reaction so statements
II and III are correct. Statement I is incorrect as (d) From the Arrhenius equation, k = Ae–Ea/RT
E
increasing the surface area of a solid catalyst lnk = lnA – a
RT
speeds up the rate of reaction. Therefore plotting lnk against 1/T will give a
Correct answer is C. –E
straight line where the slope = a .
R
10 Consider the rate expressions obtained for the Using points (1.29 × 10 , –2.5) and (1.75 ×
–3

slow step of each mechanism: 10–3, –12.5):

A rate = k[N2O4][CO]2; substituting for [N2O4], –12.5 – (–2.5)
slope =
rate = k[NO2]2[CO]2 (1.75 – 1.29) × 10–2 K–1
B rate = k[NO2][CO] –10.0
= = –2.17 × 104 K
4.6 × 10–4 K–1
C rate = k[NO2]
Ea = –slope × R = 2.17 × 104 K × 8.31 J K–1
D rate = k[NO2]2
mol–1 = 1.8 × 105 J mol–1 = 180 kJ mol–1
Correct answer is D.
12 (a) The square brackets represent the
concentration of NO(g). (The moles of NO
6
gas relative to the volume occupied by the within experimental error so the reaction
NO gas.) is first order with respect to CH3COCH3.
(b) A rate has units of mol dm–3 s–1. Substituting H+: In Experiments 1 and 4 [H+] has
the units into the rate expression: halved, [CH3COCH3] and [I2] are constant.
mol dm–3 s–1 = units of k × mol dm–3 × (mol The initial rate has halved so the reaction
dm–3)2 is first order with respect to H+.

mol dm–3 s–1 = units of k × mol3 dm–9 I2: In Experiments 1 and 2 [I2] has
mol dm–3 s–1 increased by 1.5 times, [CH3COCH3]
units of k = = mol–2 dm6 s–1
mol3 dm–9 and [H+] are constant. The initial rate is
constant within experimental error so
13 Note: The y-axis of the graph is incorrectly
the reaction is zero order with respect
labelled as log k. This should be labelled as lnk.
to KI.
(a) If lnk decreases with 1/T this means that k
The rate expression for the reaction is
increases with increasing T.
rate = k[CH3COCH3][H+].
(b) From the Arrhenius equation, k = Ae–Ea/RT:
(ii) Alex’s and Hannah’s hypotheses were
E
lnk = lnA – a both incorrect as they both proposed
RT
Therefore plotting lnk against 1/T will give a that the rate of reaction would be
–E dependent on [I2].
straight line where the slope = a .
R (c) For Experiment 1:
Using points (1.00 × 10–3, –2.0) and (1.108 × cV
[CH3COCH3] = i i
10–3, –5.2): Vf
–5.2 – (–2.0) 1.00 mol dm–3 × 10.0 cm3
slope = =
(1.108 – 1.00) × 10–2 K–1 100.0 cm3
–3.2 = 0.100 mol dm–3
= = –3.0 × 104 K
1.08 × 10–4 K–1 c V 1.00 mol dm–3 × 10.0 cm3
[H+] = i i =
Ea = –slope × R = 3.0 × 104 K × 8.31 J K–1 Vf 100.0 cm3
mol–1 = 2.5 × 105 J mol–1 = 250 kJ mol–1 = 0.100 mol dm –3

Initial rate = k[CH3COCH3][H+]

Given the errors associated with determining
initial rate
the exact values of points on the line, k=
[CH3COCH3][H+]
values between 240 and 260 kJ mol–1 are
4.96 × 10–6 mol–1 dm–3 s–1
acceptable. =
90 01.00 mol dm–3 × 0.100 mol dm–3
(c) When 10% of N2O has reacted, [N2O] = = 4.96 × 10–4 mol dm3 s–1
100
× 0.200 mol dm–3 = 0.180 mol dm–3 (i)
rate = k[N2O] = 0.244 dm mol s ×
2 3 –1 –1
Number of particles with

Number of particles with

(0.180 mol dm–3)2 = 7.91 × 10–3 mol dm–3 s–1 energy > Ea uncatalysed
kinetic energy E

Number of particles with

energy > Ea catalysed
14 (a) Water was added so that the same total Particles with
volume was used for all of the trials. (Then these low
energies
the concentration of the reactant in the
cannot react
different trials is directly proportional to the
Ea catalysed Ea uncatalysed kinetic energy E
volume used.)
(b) (i) CH3COCH3: In Experiments 1 and 3 (ii) A catalyst provides an alternative
[CH3COCH3] has halved, [H+] and [I2] reaction pathway with a lower activation
are constant. The initial rate has halved energy.

7
15 Note that this question should refer to the (d) For the two steps provided in the reaction
mechanism provided as having two steps: mechanism the rate-determining step will be
Step 1: W + XY → WY + X the one with the highest activation energy.
From the diagram provided in the answer
Step 2: WY + Z → W + YZ
for part (b) we can see that the first step in
The labels 1–5 on the graph refer to stages 1–5 the mechanism (W + XY → WY + X) has the
of the reaction (not steps). highest activation energy so it will be the
(a) W + XY → WY + X slowest step.
WY + Z → W + YZ rate = k[W][XY]
XY + Z → X + YZ (e) The reaction is catalysed. W is a catalyst
Overall equation is XY + Z → X + YZ. as it is consumed in the first step and
regenerated in the second step. (This means
(b) In the diagram 1–5 represent different stages
that even though it participated in the
of the reaction (not steps).
reaction, there is no overall change in the
transition amount of W present after the reaction has
potential energy

state
2 transition
state reached completion.)
4
(f) The enthalpy change, ΔH, refers to the
3 enthalpy change that occurs between
intermediate the reactants and products. Because this
Ea 5 reaction proceeds through an intermediate,
Products and has two steps in the reaction
1 ∆H
Reactants
mechanism, there are two activation
energies. Ea (step 1) is the energy difference
extent of reaction
between the reactants and the transition
Stage 1 represents the reactants. state for the first step, W + XY → WY + X. Ea
Stage 2 represents the transition state for (step 2) is the energy difference between the
step 1 of the reaction mechanism. intermediate and the transition state for the
Stage 3 represents an intermediate. second step, WY + Z → W + YZ.

Stage 4 represents a transition state for step 2

2 of the reaction mechanism. 4
Stage 5 represents the products.
potential energy

(c) 1–5 represent different stages of the reaction

3
(not steps).
Ea (step 1)

Ea (step 2)

Species present at stage 1 are reactants XY, 5

Z and the catalyst W. ∆H

1
Species present at stage 2 is transition state
formed by W and XY: W ---- X ----Y extent of reaction

Species present at stage 3 is intermediate
WY, reactant Z and product X.
Species present at stage 4 is transition state
formed by WY and Z: W ---- Y ----Z
Challenge yourself
Species present at stage 5 are products X,
1 Collecting a gas over warm water will cause its
YZ and the catalyst W.
temperature, and therefore its volume, to increase.

8
2 If the partially made/broken bonds are treated as transition state may help to interpret its stability
containing only one electron, we can calculate and how it will react in the next step of the
formal charges which have fractional values. reaction mechanism.
The distribution of these formal charges in the