CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK
Exam-style questions and sample answers have been written by the authors. In examinations, the way marks are awarded
may be different.
Coursebook answers
Chapter 22
Science in context
Laser is an acronym for Light Amplification by
Stimulated Emission of Radiation. Learners may
ask how a laser works. You cannot be expected to
go into great detail because this is complex physics
rather than chemistry. Lasers produce a highly
focused beam of radiation of a single wavelength
in which the vibrations of the light are in phase
with one another.
The stages in producing laser radiation are:
1 Atoms or molecules are ‘pumped up’ to an
excited state using a light source (use an
analogy with excited electrons).
2 A few of the excited species (atoms or
molecules) lose photons (elementary
particles with zero mass which move at
speed of light).
3 Each photon reacts with other excited
species and stimulates them to emit a
photon of the same wavelength.
4 The photons travel in the same direction
and are in phase (the vibrations of the
waves are in step with each other).
• Learners should know the term absorption
from their work on infrared spectra. They
may not realise that the reconversion of
iodine atoms into iodine molecules is the
shape of a decay curve but a hint could be
given that it is similar to the curve obtained
when monitoring the loss in mass of the
reaction mixture when hydrochloric acid
reacts with calcium carbonate.
• The laser technology was new and with
any new method there are worries about
the effectiveness of the method including
its reliability, accuracy and precision.
The fact that the experimenters were
working in picoseconds means that any
1 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020
small errors in timings would influence the
results. Up to then chemists had assumed
that the solvent just slowed the rate of
reaction because the solvent just got in the
way (reducing the frequency of collisions).
The idea of a defined solvent cage around
the molecules was controversial and there
was no real evidence for it even from
these experiments.
Although the idea of solvent cages had
been suggested in the 1930s few took much
notice of it because no suitable experimental
methods were available. Solvents complicate
matters when trying to understand how
molecules react with each other. Nowadays,
the idea of solvent cages has gained more
acceptance. Solvent cages stop molecules from
breaking up by forming a ‘cage’ around them
but smaller fragments can escape the solvent
cage, therefore making them recombine
more slowly.
• This activity can stimulate arguments about
the relationship between the different sciences.
In reality, all the sciences are dependent
on each other and distinctions between
them are often blurred. There are physical
chemists, biophysicists, computer analysts:
a whole range of scientists having different
backgrounds. Because many of the ideas in
modern chemistry are complex, development
in the subject often requires co-operation
between different disciplines and often
different institutions.
Although it is obvious that developments
in physical chemistry depend on new
instrumentation, learners should see that
co-operation between the different branches
of science is essential. In the development
of X-ray diffraction (Chapter 19),
mathematicians have played an essential part
in developing methods for coping with the
 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

complex calculations required. Physicists 3 a rearrange the equation in terms of k:

have developed techniques such as the laser rate
k =
and spectroscopic techniques which were [ NO ]
2
2

originally of minor interest but have been

taken up and developed by others for a wide substitute the units:
range of uses. Sometimes it is chemists or mol dm –3 s –1
k=
biologists who have seen a possible use for (mol dm –3 ) × (mol dm –3 )
an instrument and have worked together cancel mol dm−3:
with physicists to develop it, e.g. lasers for mol dm –3 s –1
k=
specific purposes. A huge variety of lasers ( mol dm –3 ) × (mol dm –3 )
are available today, using gases, solutions,
inorganic crystals to emit radiation units of k = s−1 mol−1 dm3 = dm3 mol−1 s−1
of over a whole range of wavelengths. b rearrange the equation in terms of k:
Chemists studying rates of reaction for rate
biochemical processes often need the help k=
[NO3 ]0

of mathematicians to develop complex rate –3
s –1
equations. substitute the units: k = mol dm
1

Self-assessment questions units of k = mol dm−3 s−1

c rearrange the equation in terms of k:
1 a rate = k[cyclopropane]
rate
b rate = k[HI]2 k=
[BrO3− ] [Br – ] [H+ ]2

c rate = k[C12H22O11] [H+] substitute the units:
d rate = k[HgCl2] [K2C2O4]2 mol dm –3 s –1
k=
e rate = k[CH3COCH3] [H+] (mol dm ) × (mol dm –3 )(mol dm –3 )2
–3

cancel mol dm−3:

2 a rate = k[cyclopropane]
mol dm –3 s –1
i 1st order with respect to cyclopropane k=
( mol dm –3
) × (mol dm –3 )(mol dm –3 )2
ii 1st order overall units of k = s−1 mol−3 dm9 = dm9 mol−3 s−1
b rate = k[HI]2 d rearrange the equation in terms of k:
i 2nd order with respect to HI k=
rate

ii 2nd order overall [ cyclopropane ]

–3 –1

c rate = k[C12H22O11] [H+] substitute the units: k = mol dm –3s

(mol dm )
i 1st order with respect to C12H22O11 mol dm –3 s –1
and 1st order with respect to H+ cancel mol dm−3: k =
( mol dm –3 )
ii 2nd order overall
units of k = s−1
d rate = k[HgCl2] [K2C2O4]2
4 a 2nd order reaction, so upward curve
i 1st order with respect to HgCl2 and (see red line in Figure 22.4)
2nd order with respect to K2C2O4
b zero order reaction, so horizontal
ii 3rd order overall straight line
e rate = k[CH3COCH3] [H+] c 1st order reaction, so straight line through
i 1st order with respect to CH3COCH3 (0,0) showing direct proportionality
and H+, 0 order with respect to I2 (see blue line in Figure 22.4)
ii 2nd order overall

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

5 a shallow curve (see blue line in Figure 22.4) This allows the order of reaction with
b straight line in constant decline respect to HCl to be deduced.
(see black line in Figure 22.4) 9 a There is only one molecule in the rate
c steep curve, which then levels out equation so the reaction is 1st order.
(see red line in Figure 22.4) b rate = k[NO2]
6 a By measuring the increase in pressure so k =
rate
with time in a closed system where [ NO ]2

the reaction is taking place or by 3.15 × 10−5

k = 3.00
measuring the volume of nitrogen gas
given off with time using a gas syringe.   = 1.05 × 10−5 s−1
b Graph is a smooth downward curve (Did you spot the ‘10−5’ in the heading
levelling off gradually so seems of column 2?)
to be first order with respect to
10 a rate = k[CH3COCH3] [H+] [I2]0
benzenediazonium chloride.
= k[CH3COCH3] [H+]
c 1st half-life (from 0.58 × 10−4 mol dm−3
to 0.29 × 10−4 mol dm−3) = 470 s b Rearranging the rate equation then
substituting the data:
2nd half-life (from 0.29 × 10−4 mol
rate
dm−3 to 0.145 × 10−4 mol dm−3) = 450 s k=
[CH3COCH3 ][H+ ]
d 1st order reaction because successive
10.9 × 10 −6
half-lives are more or less the same k =
(0.5 × 10 −3 ) × (1.25 )
(within experimental error).
7 a rate = k[H2O2][I−] = 1.74 × 10−2 dm3 mol−1 s−1
rate 11 The rate-determining step is the slow
so k =
[H2O2 ][I − ] step. This involves the reaction of
for experiment 2: rate H2O2 with I− ions. These are the only
5.30 × 10 −6 two species that appear in the rate
= equation. The hydrogen ions do not
(0.0300) × (0.0100)
appear in the rate equation because
= 0.0177 dm3 mol−1 s−1 they are involved in a fast step, which
for experiment 3: rate takes place after the rate-determining
1.75 × 10 −6 step.
=
(0.0050) × (0.0200) 12 D
= 0.0175 dm3 mol−1 s−1 13 a ii Mn3+ and Mn2+ and
0.693
b k= = 1.44 × 10−3 s−1 iii C
 e4+ and Ce3+; these are the only
480
pairs that have E  values between
0.693 those of the S2O82− / SO42− and
c t 1 = ; k = 9.63 × 10 −5 s −1
2 k
I− / I2 pairs.
so t 1 = 0.693 −5 = 7200
2 9.63 × 10 b i ox. no. change = –2
reduction
(to 3 significant figures)
SO2 (g) + NO2 (g) —————→ SO3 (g) + NO(g)
8 The temperature must remain constant
+4 +4 +6 +2
throughout the experiment. The
experiment should be designed to study oxidation
the effect of changing the concentration ox. no. change = +2
of only one reactant at a time. The
best approach is to ensure a large
excess of methanol. The concentration
of methanol is then assumed to be
constant, as it is much higher than that
of the hydrochloric acid, so we can
monitor the concentration of HCl.

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

ii ox. no. change = –2 d graph plotted of rate against

reduction concentration; [1]
NO(g) +
1
O (g) —————————→ NO2 (g) points plotted correctly; [1]
2 2
+2 0 +4 –2 line of best fit drawn [1]
e it is a straight line; [1]
oxidation
ox. no. change = +2 through 0,0 [1]
14 a the releasing of product molecules [it shows direct proportionality
from the surface of a catalyst gains 2 marks]
b The ethene and hydrogen are adsorbed [Total: 13]
onto the surface of the nickel. In 2 a i the power / index [1]
this process weak bonds are formed
between the ethene and the surface of to which the concentration of a
the nickel and between the hydrogen particular reactant is raised in the
and the surface of the nickel. rate equation [1]

The bonds between the hydrogen atoms ii To find the order of reaction
are weakened and the pi-bond of the with respect to A, use
ethene is also weakened. Adsorbed experiments 1, 2 and 3; [1]
hydrogen atoms close to the adsorbed doubling [A] has no (significant)
ethene then react to form ethane. effect on the rate; [1]
The bonds between the ethane and the so reaction is zero order with
surface of the nickel weaken and the respect to A. [1]
ethane moves away from the surface of To find the order of reaction
the catalyst. with respect to B, use
c i experiments 4, 5 and 6; [1]
bonds weakening
N O doubling [B] increases rate by
N O
bonds forming factor of 4; [1]
Rh Rh Rh Rh Rh Rh Rh Rh
so reaction is 2nd order with
N and O
adsorbed respect to B. [1]

ii bonds form between To find the order of reaction

adjacent N atoms
with respect to C, use
Rh surface
O N N O O N N O experiments 7, 8 and 9; [1]
desorption doubling [C] doubles the rate; [1]
so reaction is 1st order with
Exam-style questions respect to C. [1]
b i rate = k[B] [C] 2
[1]
1 a correct axes, suitably labelled; [1]
ii 3 [1]
points plotted correctly; [1]
iii rearranging the rate equation:
curve of best fit drawn [1] rate
k=  [1]
b half-life method used; [1] [B]2 [C ]
three successive half-lives shown correct value:
to be similar [1] 0.00073
= = 8.1 × 10 −3  [1]
c tangents drawn correctly at each of ( 0.300 )2 (1.00 )
the three concentrations (if 2 marks units are dm6 mol−2 s−1 [1]
not scored, 1 mark for drawing one
tangent correctly); [2] c e.g. the first step involves the collision
of two molecules of B and one of C,
rates calculated from gradients [1] forming B2C; [1]
this is the slow / rate-determining step; [1]

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the fast step involves A colliding with 0.287

= = 0.470  [1]
the intermediate; B2C + A → 0.61
ABC + B  [1] units are min−1 [1]
[Total: 19] iii rate = k[H2O2] = 0.470 × 2 = 0.940 [1]
3 a zero order [1] units are mol dm−3 min−1 [1]
b 2nd order [1] [Total: 19]
c i time taken for the concentration 5 a correct axes, suitably labelled; [1]
of a reactant to fall to half its
original value [1] points correctly plotted; [1]
ii it remains constant [1] curve of best fit drawn [1]
d graph plotted so that [propanone] b 1st order; [1]
halves every 10 s (1 mark for each rate of reaction is directly
point plotted correctly): proportional to peroxodisulfate
20 s → 2 mmol dm−3 [1] concentration [1]
30 s → 1 mmol dm−3 [1] c rate = k[S2O ] [I ]2−
8
−
[1]

40 s → 0.5 mmol dm−3 [1] d i homogeneous (catalysis); [1]

50 s → 0.25 mmol dm−3 [1] the catalysts and reactants are

in the same phase / are all in the
e the slowest step; [1] aqueous phase [1]
its rate limits the overall rate of reaction [1] ii In equation 1, both ions are
f O OH+  [3] negative / have the same charge; [1]
so tend to repel each other. [1]
H3C C CH3 + H+ H3C C CH3
In equations 2 and 3, the ions
[1 mark for each reactant; 1 mark for are oppositely charged / one is
the product] positive and the other negative; [1]
[Total: 13] so are more likely to attract
4 a a substance that speeds up a chemical each other. [1]
reaction / changes the reaction rate; [1] [Total: 12]
but is chemically unchanged at the 6 a correct axes, suitably labelled; [1]
end of the reaction [1] points correctly plotted; [1]
b i correct axes, suitably labelled; [1] line of best fit drawn [1]
points correctly plotted; [1] b The gradient and therefore the
curve of best fit drawn [1] rate is constant, even though the
ii half-life = 1.5 min; [1] concentration of iodine is changing. [1]
c No – there must be a slow step [1]
correct working shown on graph [1]
which doesn’t involve iodine. [1]
iii tangent drawn to curve at
t = 2 min; [1] d The balanced equation tells us about
−1.18
number of molecules of reactants
gradient of tangent =  [1] consumed and products produced [1]
4.1
= −0.287 [1] and their formulae; [1]
rate = 0.287 mol dm−3 min−1 [1] the rate equation tells us how many of
each reactant molecules [1]
c i half-life is constant; [1]
are present in the slowest /
reaction is first order; [1]
rate-determining step. [1]
rate = k[H2O2] [1] [Total: 10]
rate
ii k =  [1]
[ H 2 O2 ]

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7 a i ( Catalysis in which) the catalyst is b i BrO3−: order is 1st order; [1]

in a different phase [1] compare experiments 2 and 3;
from the reactants / rest of the doubling the concentration
reaction mixture. [1] doubles the rate; [1]
ii Reactant molecules adsorbed onto Br : order is 1st order;
−
[1]
the surface (of the catalyst); [1]
compare experiments 2 and 4;
bonds within the reactant doubling the concentration
molecules weakened / broken; [1] doubles the rate; [1]
new bonds formed with adjacent H : order is 2nd order;
+
[1]
atoms to form products; [1]
compares experiments 1 and 2;
products desorbed from catalyst doubling the concentration
surface. [1] increases the rate 4-fold / (2)2. [1]
b 2NO2 → NO + NO3 slow [1] ii rate = k[BrO3−][Br−] [H+]2 [1]
NO3 + CO → NO2 + CO2 iii dm9 mol−3 s−1 [1]
fast [1] c Increase in temperature increases
[allow other reactions with suitable value of rate constant [1]
intermediate] The maximum of Boltzmann
c i NO: order is 2nd order; [1] distribution curve shifts to the right
when temperature increases [1]
when concentration of NO
increased 3-fold, rate of reaction Greater proportion of particles have
increases 9-fold / by (3)2; [1] energy greater than the activation
energy [1]
O2: order is 1st order; [1]
The rate constant is proportional to
when concentration of oxygen
the fraction of molecules with energy
increased by 4/3, rate of reaction
equal to or greater than the activation
is also increased by 4/3 (or similar
energy. [1]
argument). [1]
[Total: 16]
ii rate = k[O2] [NO2]2 [1]
iii dm6 mol−2 s−1 [1]
[Total: 14]
8 a Any two suitable methods (1 mark for
method and 1 mark for explanation);
for example:
Electrical conductivity;  [1]
because ions are present in the
reactants but not in the products. [1]
Titration of small samples with
standard alkali; [1]
because the concentration of hydrogen
ions falls during the reaction. [1]
[not titration with standard alkali
without qualification, as this suggests
that the whole reaction mixture is
being titrated]

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