Example Responses – Paper 4

Cambridge International AS & A Level

Chemistry 9701
For examination from 2022
© Cambridge University Press & Assessment 2022 v1
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Contents
Introduction........................................................................................................................................................................4
Question 1.........................................................................................................................................................................5
Question 2.......................................................................................................................................................................10
Question 3.......................................................................................................................................................................14
Question 4.......................................................................................................................................................................17
Question 5.......................................................................................................................................................................21
Question 6.......................................................................................................................................................................23
Question 7.......................................................................................................................................................................28
Question 8.......................................................................................................................................................................30
Question 9.......................................................................................................................................................................33
 Example Responses – Paper 4

Introduction
The main aim of this booklet is to exemplify standards for those teaching Cambridge International AS & A Level
Chemistry 9701.
This booklet contains responses to all questions from June 2022 Paper 42, which have been written by a Cambridge
examiner. Responses are accompanied by a brief commentary highlighting common errors and misconceptions where
they are relevant.
The question papers and mark schemes are available to download from the School Support Hub.

9701 June 2022 Question Paper 42

9701 June 2022 Mark Scheme 42

Past exam resources and other teaching and learning resources are available from the School Support Hub.

4
Example Responses – Paper 4

2
Question 1 Answer all the questions in the spaces provided.

1 (a) The solubility of the Group 2 hydroxides increases down the group.

Explain this trend.

• Lattice energy and enthalpy change of hydration both decrease.

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

• Lattice energy decreases more 2than enthalpy change of hydration.

....................................................................................................................................................
Answer all the questions in the spaces provided.
• Enthalpy change of solution becomes less endothermic.
....................................................................................................................................................

1 ....................................................................................................................................................
(a) The solubility of the Group 2 hydroxides increases down the group.

..............................................................................................................................................
Explain this trend. [3]

....................................................................................................................................................
Examiner
(b) Thecomment
solubility of Be(OH)2 in water is 2.40 × 10–6 g dm–3 at 298 K.
It is correct ....................................................................................................................................................
to state that ∆Hlatt and ∆Hhyd become less exothermic.
(i) Write an expression for the solubility product, Ksp, of Be(OH)2 and state its units.
Common errors included:
....................................................................................................................................................
• confusing which =
Ksp quantity decreased more
• ....................................................................................................................................................
using enthalpy of solubility instead of enthalpy change of solution
• stating that the solution becomes more exothermic rather than the enthalpy of solution becomes more exothermic.
units = ..............................
.............................................................................................................................................. [2]
[3]
(ii) Calculate the numerical value of Ksp for Be(OH)2 at 298 K.
(b) The solubility of Be(OH)2 in water is 2.40 × 10–6 g dm–3 at 298 K.

(i) Write an expression for the solubility product, Ksp, of Be(OH)2 and state its units.

Ksp = [Be2+][OH−]2
Ksp = .............................. [2]
mol dm
units = ..............................
3 –9

[2]
(c) Be(OH)2 is soluble in aqueous solutions containing an excess of hydroxide ions and forms the
Examiner comment
complex ion [Be(OH) 4] . This complex
of Kspion
forhas a similar shape to that of [CuCl 4]2–.
2–
(ii) Calculate the numerical value Be(OH) 2 at 298 K.

• Use of square brackets

(i) Define theisterm
essential
complex in theion.
Ksp expression. Some candidates used curly brackets.
• A common error was to write Ksp = [Ba ][OH−]2. This was not accepted.
2+

• Each concentration in the solubility product expression has the unit mol dm−3 so the units for Ksp should be mol3
.............................................................................................................................................
dm–9.
.......................................................................................................................................
Ksp = .............................. [1]
[2]

(ii)
Draw a three-dimensional diagram to show the structure of the complex ion [Be(OH)4]2–.
Name
(c) Be(OH) the shape of the [Be(OH)4]2– complex ion.
2 is soluble in aqueous solutions containing an excess of hydroxide ions and forms the
complex ion [Be(OH)4]2–. This complex ion has a similar shape to that of [CuCl 4]2–.

(i) Define the term complex ion.

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

shape ..................................................................................................................................
....................................................................................................................................... [1]
[1]
(ii) Draw a three-dimensional diagram to show the structure of the complex ion [Be(OH)4]2–.
5
© UCLES 2022
]2– complex ion.
Name the shape of the [Be(OH)49701/42/M/J/22
 ....................................................................................................................................................
Ksp =
Example Responses – Paper 4
....................................................................................................................................................
.............................................................................................................................................. [3]
units = ..............................
[2]
....................................................................................................................................................
(b) (ii)
The Calculate
solubility of theBe(OH)
numerical2 in water
valueisof2.40 × 10
Ksp for
–6
g dm–3atat298
Be(OH) 298K.K.
2
....................................................................................................................................................
-6
2.4 an10
(i) Write expression for the solubility product, Ksp, of Be(OH)2 and state its units.
 5.58  10-8 mol dm-3
.............................................................................................................................................. [3]
43
Ksp =
(5.58 x 10 ) (2 x 5.58 x 10 )
–8 –8 2

(b) The =solubility of Be(OH)

6.95 x 10–22 2 in water is 2.40 × 10 g dm at 298 K.
–6 –3
Kspunits 6.95 x 10
= ..............................
= .............................. [2]
–22

[2]
(i) Write an expression for the solubility product, Ksp, of Be(OH)2 and state its units.
Examiner(ii) comment
(c) Be(OH)Calculate the numerical value of Ksp for Be(OH)2 at 298 K.
2 is soluble in aqueous solutions containing an excess of hydroxide ions and forms the
K
complex =
sp ion [Be(OH) ]2–. This complex ion has a similar shape to that of [CuCl ]2–.
Common errors were: 4 4

• not to convert the solubility

(i) Define the term in of Be(OH)2ion.
complex in g dm−3 to mol dm−3. units = ..............................
• not to realise that for every one mole of Be(OH)2 there are two moles of OH− ions, so the concentration of OH [2]−
needed to be.............................................................................................................................................
multiplied by two.
(ii) Calculate the numerical value of Ksp for Be(OH)2 at 298 K. Ksp = .............................. [2]
....................................................................................................................................... [1]

(c) (ii)
Be(OH) 2 isasoluble
Draw in aqueous solutions
three-dimensional diagram tocontaining
show thean excessof
structure ofthe
hydroxide
complex ions
ionand forms]2–
[Be(OH) the
.
4
complex ion [Be(OH) ]2–
. This complex2–ion has a similar shape to that of [CuCl ] .
Name the shape4of the [Be(OH)4] complex ion. 4
2–

(i) Define the term complex ion. Ksp = .............................. [2]

An ion formed by a central metal atom or ion surrounded by one or

.............................................................................................................................................
(c) Be(OH)2 is soluble in aqueous solutions containing an excess of hydroxide ions and forms the
more
complex ion ligands.
[Be(OH)4]2–. This complex ion has a similar shape to that of [CuCl 4]2–.
....................................................................................................................................... [1]
shape ..................................................................................................................................
Examiner (i) comment
(ii) Define
Draw athe term complex ion.
three-dimensional diagram to show the structure of the complex ion [Be(OH)4]2–[1] .
Name the shape of the
This definition appears in the syllabus and is one that[Be(OH) ]2–
complex ion.
4 candidates should learn precisely. Often, answers missed key
.............................................................................................................................................
words such as metal and ligands.
© UCLES 2022 9701/42/M/J/22
....................................................................................................................................... [1]

(ii) Draw a three-dimensional diagram to show the structure of the complex ion [Be(OH)4]2–.
Name the shape of the [Be(OH)4]2– complex ion.
shape ..................................................................................................................................
2–
OH [1]
Be OH
© UCLES 2022 HO 9701/42/M/J/22
OH
tetrahedral
shape ..................................................................................................................................
[1]

Examiner comment
© UCLES 2022 9701/42/M/J/22
• The question asks for a three-dimensional diagram, which must be correct.
• Common errors in the drawings were:
– all the bonds in the plane of the paper.
2–
OH

Be

HO OH
OH

6
Example Responses – Paper 4

– an in-plane bond between the two out-of-plane bonds.

2–
OH

Be OH

OH OH

– a square planar shape.

2–
HO OH

Be

HO OH
• Sometimes the correct three-dimensional shape was drawn, but the shape was described as square planar.

(d) (i) Explain why transition elements can form complex ions.

They have vacant d-orbitals that are energetically accessible.

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

....................................................................................................................................... [1]

(ii) Complete Table 1.1 to show the coordination number of each metal ion, and the shapes
Examiner comment
and overall polarities of the complex ions listed.
• Candidates frequently referred to transition elements as 3 having partially filled, or incomplete, d orbitals. This
explanation was not sufficient to explain why transition Table 1.1
elements can form complex ions.
• (d)also
It was (i) notExplain
enoughwhy transition
to state elements
that transition canhave
metals formempty
complex ions. d-orbitals, since many elements have
or vacant
empty d orbitals which are not energetically accessible. However,coordination explaining that transition polar or have empty or
metals
complex ion shape
vacant d-orbitals .............................................................................................................................................
which can form dative bonds with ligands was an acceptable number alternative non-polar
response.

cis-[Pt(H 2NCH2CH2NH2)Cl 2] square planar

....................................................................................................................................... [1]

(ii)[Ag(NH 3 )2 ]
Complete +
non-polar
Table 1.1 to show the coordination number of each metal ion, and the shapes
and overall polarities of the complex ions listed.
[Fe(C2O4)3]3– 6
Table 1.1
[2]
coordination polar or
complex ion shape
(e) (i) Define stability constant, Kstab. number non-polar

cis-[Pt(H2NCH2CH2NH2)Cl 2] square planar 4 polar

.............................................................................................................................................
[Ag(NH3)2]+ linear 2 non-polar
....................................................................................................................................... [1]
octahedral non-polar
(ii)[Fe(C 2O4)can
3] form complexes with the ligands en, H2NCH26CH2NH2, and tn, H2NCH2CH2CH2NH2,
3–
Nickel
as shown.
[2]
equilibrium 1 [Ni(H2O)6]2+ + 3en [Ni(en)3]2+ + 6H2O Kstab = 6.76 × 1017
(e) (i) Define stability constant, Kstab.
Examiner comment equilibrium 2 [Ni(H2O)6]2+ + 3tn [Ni(tn)3]2+ + 6H2O Kstab = 1.86 × 1012
The most common .............................................................................................................................................
incorrect answer was to state that [Fe(C2O4)3]3− was polar.
Construct an expression for the stability constant, Kstab, for equilibrium 1.
State the units for Kstab.
.......................................................................................................................................
7 [1]
 3 2
Table 1.1
[Fe(C2O4)3]3– 6
Example Responses – Paper 4
coordination polar or
complex ion shape
number non-polar [2]
cis-[Pt(H NCH2CH2NH2)Cl 2] square planar
(e) (i) Define2 stability constant, Kstab.

The3)2equilibrium
[Ag(NH ]+ constant for the formation of the complex non-polarion in a
.............................................................................................................................................

solvent
[Fe(C 2O4)3]
3–
from its constituent ions or molecules. 6
....................................................................................................................................... [1]

(ii) Nickel can form complexes with the ligands en, H2NCH2CH2NH2, and tn, H2NCH2CH2CH2NH 2,
[2]
Examiner comment
as shown.
• This(e) (i) Define
definition appears stability constant, K2+stab.
in the syllabus.
equilibrium 1 [Ni(H O)6] + 3en [Ni(en)3]2+ + 6H2O Kstab = 6.76 × 1017
• A common response was to state that2 Kstab was the ratio of [products] to [reactants]. This was not sufficient to
.............................................................................................................................................
define the stability constant and was ignored.
equilibrium 2 [Ni(H2O)6]
2+
+ 3tn [Ni(tn)3]
2+
+ 6H2O Kstab = 1.86 × 10 12

....................................................................................................................................... [1]
Construct an expression for the stability constant, Kstab, for equilibrium 1.
(ii) State
Nickelthe canunits for Kstab. with the ligands en, H NCH CH NH , and tn, H NCH CH CH NH ,
form complexes 2 2 2 2 2 2 2 2 2
as shown.
K stab =
equilibrium 1 [Ni(H2O)6]2+ + 3en [Ni(en)3]2+ + 6H2O Kstab = 6.76 × 1017

equilibrium 2 [Ni(H2O)6]2+ + 3tn [Ni(tn)3]2+ + 6H2O units

Kstab == 1.86
..............................
× 1012
[2]
Construct an expression for the stability constant, Kstab, for equilibrium 1.
(iii) Describe
State the what theKKstab. values indicate about the position of equilibrium for equilibrium 1
units for stab
and 2. Use the Kstab values to deduce which complex, [Ni(en)3]2+ or [Ni(tn)3]2+, is more
stable. [N1(en ) ]2  
 3 
Kstab =
[N1(H O) ]2   [ en ]3
.............................................................................................................................................
 2 6  mol dm −3 9
units = ..............................
....................................................................................................................................... [1]
[2]

Examiner
(iii) comment [Total: 16]
Describe what the Kstab values indicate about the position of equilibrium for equilibrium 1
and
Common incorrect 2. Use were:
responses the Kstab values to deduce which complex, [Ni(en)3]2+ or [Ni(tn)3]2+, is more
stable.
• to use curly brackets instead of square brackets. Candidates must remember that for expressions involving
©stability constants
UCLES 2022 and equilibrium constants, the use of square brackets is essential because they show
9701/42/M/J/22 [Turnthat over
.............................................................................................................................................
concentrations of the species are required. Here is an example where curly brackets were used:

Kstab =

[Ni (en )3 ]2  
....................................................................................................................................... [1]


[Ni (H2O)6 ]2  [ en ]  3
 [Total: 16]

• put into the expression [3en] instead of [en]3.

• to include water in the expression:
© UCLES 2022 9701/42/M/J/22 [Turn over
[Ni (en ) ] 2  6
H O 
 3   2 
Kstab =
[Ni (H O) ]2   en 3
 2 3   
It is specifically mentioned in the syllabus that [H2O] should not be included. This is because water is in such large
excess that its concentration is assumed to be constant.

8
 Kstab =
Example Responses – Paper 4
units = ..............................
[2]

(iii) Describe what the Kstab values indicate about the position of equilibrium for equilibrium 1
and 2. Use the Kstab values to deduce which complex, [Ni(en)3]2+ or [Ni(tn)3]2+, is more
stable.

Both equilibria lie to the right.

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

[Ni(en) 3]
2+
is more stable because it has the larger Kstab value.
....................................................................................................................................... [1]

[Total: 16]
Examiner comment
Common errors included:
• © candidates
UCLES 2022 stating that the equilibrium shifts to the right. This was incorrect because the Kstab values
9701/42/M/J/22 showover
[Turn the
position of the equilibria at a particular temperature and this does not shift.
• stating that the position of equilibrium is forwards. This was not sufficient; candidates needed to indicate that the
positions of both equilibria are to the right.
• stating that the position of equilibrium 2 lies to the left, when its Kstab value is so large.
• omitting the second part of the answer by not deducing which complex was the more stable.

9
 Example Responses – Paper 4

Question 2
4

2 (a) Explain why transition elements have variable oxidation states.

The 3d and 4s sub-shells are similar in energy.

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

.............................................................................................................................................. [1]
4
Examiner
2 (b) comment
(a) Sketch the
Explain shape
why of a 3d
transition xy orbital.have variable oxidation states.
elements
• A common error was to suggest that the d and s orbitals were incompletely filled.
• It was insufficient
z
....................................................................................................................................................
to say that electrons can be lost from the s and d orbitals. Candidates needed to indicate that the
d and s orbitals have similar energy. 4
.............................................................................................................................................. [1]
2 (a) Explain why transition elements have variable oxidation states.

(b) ....................................................................................................................................................
Sketch the shape of a 3dxy orbital.

y zz x
.............................................................................................................................................. [1]

(b) Sketch the shape of a 3dxy orbital. [1]

z
(c) Explain why transition elements
y form coloured compounds.
x
....................................................................................................................................................
x
....................................................................................................................................................
[1]
4
y
y x
....................................................................................................................................................
2 (a) Explain why transition elements have variable oxidation states.
(c) Explain why transition elements form coloured compounds.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
[1]
....................................................................................................................................................
.............................................................................................................................................. [1]
....................................................................................................................................................
.............................................................................................................................................. [3]
Examiner comment
(c) Explain why transition elements form coloured compounds.
....................................................................................................................................................
(b) Sketch the shape of a 3dxy orbital.
Many candidates drew this incorrect shape, with the lobes of the d-orbital going along the x- and y- axes.
....................................................................................................................................................
....................................................................................................................................................
z
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [3]
....................................................................................................................................................

y x
....................................................................................................................................................

.............................................................................................................................................. [3]

[1]

(c) Explain why transition elements form coloured

10 compounds.
Example Responses – Paper 4
[1]

(c) Explain why transition elements form coloured compounds.

The degenerate d orbitals are split into two non-degenerate sets of d

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

orbitals of higher energy.

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

An electron is promoted between two non-degenerate d-orbitals by

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

absorbing a frequency of light.

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

The colour seen is complementary to the frequency of light absorbed.

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

.............................................................................................................................................. [3]

Examiner comment
• If a candidate stated that an electron ‘jumps’, they needed to make it clear that this is to a higher d-orbital.
Electrons could jump to the same energy level, which would not be correct.
• Alternative words for frequency, such as wavelength or photon, were correct.
• ‘Adsorbed’ was not accepted instead of absorbed.
• It was not sufficient to state that colour was absorbed.
• Occasionally, candidates explained that colour was emitted. This was not accepted.

(d) Aqueous solutions of copper(II) salts contain [Cu(H2O)6]2+ ions.

Equilibrium 3 and equilibrium 4 show two reactions of these ions.

equilibrium 3 [Cu(H2O)6]2+(aq) + 2OH–(aq) Cu(OH)2(s) + 6H2O(l)

equilibrium 4 [Cu(H2O)6]2+(aq) + 4NH3(aq) [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)

(i) State the colour of Cu(OH)2(s) and [Cu(NH3)4(H2O)2]2+(aq).

© UCLES 2022 9701/42/M/J/22

pale blue
colour of Cu(OH)2(s) ...........................................................................................................

dark blue
colour of [Cu(NH3)4(H2O)2]2+(aq) .........................................................................................
[1]

Examiner
(ii) comment
Use Le Chatelier’s principle to explain why a precipitate is formed when NaOH(aq) is
• The question only asked for colours to be2O)
added dropwise to [Cu(H 6] (aq).
2+
given.
• While the vast majority of candidates gave both colours correctly, others gave a range of colours from yellow to
black. .............................................................................................................................................
• Answers that gave a mix of colours, such as blue-green for Cu(OH)2(s), were not awarded the mark.
.............................................................................................................................................
• Candidates should be encouraged to memorise the colours given in the qualitative analysis notes in the syllabus
for the various reactions specified.
....................................................................................................................................... [1]

(e) There are two possible stereoisomers with the formula [Cu(NH3)4(H2O)2]2+.

Draw three-dimensional diagrams to show the two stereoisomers.

11
 colour of Cu(OH)
equilibrium 3 2(s) ...........................................................................................................
[Cu(H 2O)6] (aq) + 2OH (aq)
2+ –
Cu(OH)2(s) + 6H2O(l)
Example Responses – Paper 4
colour of [Cu(NH
equilibrium 4 3)4(H22O)
[Cu(H O)26]]2+
2+(aq) .........................................................................................
(aq) + 4NH3(aq) [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
[1]
(i) State the colour of Cu(OH)2(s) and [Cu(NH3)4(H2O)2] (aq). 2+

(ii) Use Le Chatelier’s principle to explain why a precipitate is formed when NaOH(aq) is
addedofdropwise
colour Cu(OH)2to
(s)[Cu(H 2O)6] (aq).
2+
...........................................................................................................
The concentration
colour of [Cu(NH3)4(H2O)2of OH .........................................................................................
]2+(aq)
−
ions increases and shifts equilibrium 3 to
.............................................................................................................................................
[1]
the right.
.............................................................................................................................................
(ii) Use Le Chatelier’s principle to explain why a precipitate is formed when NaOH(aq) is
.......................................................................................................................................
added dropwise to [Cu(H2O)6]2+(aq). [1]

.............................................................................................................................................
Examiner comment
(e) There are two possible stereoisomers with5 the formula [Cu(NH3)4(H2O)2]2+.
.............................................................................................................................................
The question asks candidates to use Le Chatelier’s principle, so answers based on the amount of OH− increasing, or
(d) Draw
the common three-dimensional
ion effect,
Aqueous were ignored.
solutions diagrams
of copper( to show
II) salts contain the[Cu(H
two stereoisomers.
2O)6]
2+
ions.
....................................................................................................................................... [1]
Equilibrium 3 and equilibrium 4 show two reactions of these ions.

(e) Thereequilibrium
are two possible
3 stereoisomers
[Cu(H with the –formula [Cu(NH3)42(H
(s)2O)
+2]6H
2+
. O(l)
2O)6] (aq) + 2OH (aq) Cu(OH)
2+
2

Drawequilibrium
three-dimensional
4 diagrams
[Cu(H 2+ to show the two stereoisomers.
2O)6] (aq) + 4NH3(aq) [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)

(i) Cu of Cu(OH)2(s) and [Cu(NH3)4(H2O)2]2+(aq).

State the colour Cu
2+ 2+
colour of Cu(OH)2(s) ...........................................................................................................
NH3 NH3
H2colour
O NH]2+
of [Cu(NH3)4(H2O) H2O NH3
3 (aq) .........................................................................................
2
[1]
Cu Cu
(ii) Use Le Chatelier’s principle to explain why a precipitate is formed when NaOH(aq) [2] is
added dropwise to [Cu(H2O)6]2+(aq).
H2O NH3 H3N OH2 [Total: 9]
NH3 NH3
.............................................................................................................................................

.............................................................................................................................................
[2]
....................................................................................................................................... [1]
Examiner comment [Total: 9]
• The diagrams needed to indicate correct three-dimensional structures and the convention for drawing these can be
(e) There are two possible stereoisomers with the formula [Cu(NH3)4(H2O)2]2+.
found in the syllabus.
• The formulae of the ligands must be correct: O2H and 3HN were not accepted. For example, both these diagrams
Draw three-dimensional diagrams to show the two stereoisomers.
are incorrect:

© UCLES 2022 9701/42/M/J/22 [Turn over

+2+
H2O NH3
3 HN H2O O2H NH3

© UCLES 2022 Cu 9701/42/M/J/22 Cu [Turn over

NH3 NH3 O2H NH3

NH3 H2O

[2]

[Total: 9]
12
 ....................................................................................................................................... [1]
Example Responses – Paper 4

(e) There are two possible stereoisomers with the formula [Cu(NH3)4(H2O)2]2+.
• Candidates
Drawsometimes drew two diagrams
three-dimensional diagramsthat were ofthe
to show thetwo
same isomer. In the example below, both the isomers
stereoisomers.
drawn are the same cis-isomer:

NH3 NH3
NH3 NH3 NH3 NH3

Cu Cu

H2O NH3 H3N H2O

H2O H2O

[2]

[Total: 9]

© UCLES 2022 9701/42/M/J/22 [Turn over

13
 Example Responses – Paper 4

Question 3
6

3 (a) (i) Define first electron affinity.

The enthalpy change when one mole of electrons is gained by one

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

mole of gaseous atoms to form one mole of gaseous 1− ions.

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

....................................................................................................................................... [2]

(ii) The first electron affinity of an atom is usually an exothermic process, whereas the second
electron affinity is an endothermic process.
6
Suggest why.
3 (a) (i) Define first electron affinity.
The first electron affinity releases energy because there is attraction
.............................................................................................................................................
.............................................................................................................................................
between the positive nucleus and the incoming electron. The second [1]
.......................................................................................................................................
.............................................................................................................................................
(iii) electron
Describe the affinity
generalrequires
trend in first energy
electrontoaffinities
overcome for Cl,the Br andrepulsion
I. Explainbetweenyour answer.
....................................................................................................................................... [2]
the negative ion and the electron.
.............................................................................................................................................
(ii) The first electron affinity of an atom is usually an exothermic process, whereas the second
electron affinity is an endothermic process.
.............................................................................................................................................
Examiner comment
Candidates neededSuggest why.
.......................................................................................................................................
to clearly state that the repulsion for the second electron affinity was between the electron and [2] the
negatively charged anion. It was not sufficient to describe repulsion between an incoming electron and the electrons
already present. .............................................................................................................................................
(b) Table 3.1 shows energy changes to be used in this question and in (c).
....................................................................................................................................... [1]
Table 3.1
(iii) Describe the general trend in first electron affinities for Cl, Br and I. Explain your answer.

The general trend energy

is less change
exothermic down the group value / kJ mol
because
–1
of the
.............................................................................................................................................
standard enthalpy change of atomisation of zinc +131
increasing distance between the nucleus and the outer electron shell.
.............................................................................................................................................
first ionisation energy of zinc +906
This means there is less attraction between the nucleus +1733 and the
.......................................................................................................................................
second ionisation energy of zinc [2]

incoming
standard electron,
enthalpy soofless
change energy
formation is released.
of ZnI2(s) –208
(b) Table 3.1 shows
lattice energy,energy, changes to be used
of zinc iodide, in this question and in (c).
ZnI2(s) –2605

Examiner comment
first ionisation energy of iodine Table 3.1 +1008
second
Explanations often did notionisation
state that energy of iodine
the attraction +1846 decreases.
between nucleus and the incoming electron
I–I bond energy energy change value / kJ mol–1
+151
standardchange
enthalpyof change of atomisation
of iodine, Iof zinc +131
+62
enthalpy sublimation 2(s) → I2(g)
first ionisation energy of zinc +906
second ionisation energy of zinc +1733
standard enthalpy change of formation of ZnI2(s) –208
lattice energy, , of zinc iodide, ZnI2(s) –2605
first ionisation energy of iodine +1008
second ionisation energy of iodine 14 +1846
 .............................................................................................................................................

.......................................................................................................................................
Example Responses – Paper 4 [2]

(b) Table 3.1 shows energy changes to be used in this question and in (c).

Table 3.1

energy change value / kJ mol–1

standard enthalpy change of atomisation of zinc +131
first ionisation energy of zinc +906
second ionisation energy of zinc +1733
standard enthalpy change of formation of ZnI2(s) –208
lattice energy, , of zinc iodide, ZnI2(s) –2605
first ionisation energy of iodine +1008
second ionisation energy of iodine +1846
I–I bond energy +151
7 I2(s) → I2(g)
enthalpy change of sublimation of iodine, +62

Calculate the first electron affinity for iodine. Use relevant data from Table 3.1 in your working.
It may be helpful to draw a labelled energy cycle.
Show all working.

Zn2+(g) + 2I(g) + 2e–

+1733 Zn+(g) + 2I(g) + e– Zn2+(g) + 2I–(g)

+906 Zn(g) + 2I(g) 131 + 62 + 151 + 906 + 1733 + 2x

© UCLES 2022 9701/42/M/J/22 = 2983 + 2x
+151 Zn(g) + I2(g)
–2605
+62 Zn(g) + I2(s) → –208 – (2983 + 2x) = –2605
→ –208 – 2983 – 2x = –2605
+131 Zn(s) + I2(s) → –3191 – 2x = –2605
→ 2x = –586
–208 ZnI2(s)

–293
first electron affinity for iodine = .............................. kJ mol–1 [3]

Examiner comment
• The(c) Predict
question how
asks candidates of to
CdI 2(s) all
show differs fromMany candidates
working. of ZnI2(s).made at least one error, but they still received
some marks through applying error carried forward based on3.2.
Place a tick (✓) in the appropriate box in Table the errors they had made.
• Common errors were:
Table 3.2
– a final answer of −586 kJ mol−1. This was obtained because candidates did not realise that there were two
moles of iodide ions in ZnI2, so 2 × the electron affinity was required in the calculation.
of CdI
– a final answer (s) iskJ
of 2−262 less
mol−1. This resulted of fromCdI2(s)
not is the
using of CdIchange
+62 kJ mol−, the enthalpy 2(s) is more
of sublimation of
negative
iodine. than of ZnI2(s) same as of ZnI2(s) negative than of ZnI2(s)

Explain your answer.

15
....................................................................................................................................................
 first electron affinity for iodine = ..............................
Example Responses [3] 4
kJ mol–1– Paper

(c) Predict how of CdI2(s) differs from of ZnI2(s).

Place a tick (✓) in the appropriate box in Table 3.2.

Table 3.2

of CdI2(s) is less of CdI2(s) is the of CdI2(s) is more

negative than of ZnI2(s) same as of ZnI2(s) negative than of ZnI2(s)


Explain your answer.

Cd is larger than Zn . There is less attraction between Cd ions

2+ 2+ 2+
....................................................................................................................................................

and I ions in the lattice.

−
.............................................................................................................................................. [1]

[Total: 9]

Examiner comment
Many candidates recognised that Cd2+ was larger than Zn2+ but did not mention that there was less attraction between
Cd2+ ions and I− ions in the lattice.

© UCLES 2022 9701/42/M/J/22 [Turn over

16
Example Responses – Paper 4

Question 4
8

4 (a) Calcium carbonate decomposes on heating.

CaCO3(s) → CaO(s) + CO2(g)

Table 4.1 shows the values of the Gibbs free energy change, ∆G o, for this reaction at various
temperatures.

Table 4.1

T/K ∆G o / kJ mol–1
1050 9.9
1085 4.3
1120 –1.3
1148 –5.8
1176 –10.3

Assume the standard enthalpy change, ∆H o, and the standard entropy change, ∆S o, for this
reaction remain constant over this temperature range.

(i) Use the data in Table 4.1 to plot a graph of ∆G o against T on the grid.

12.5

10.0 x
7.5

5.0 x
G o / kJ mol–1 2.5

0.0 T/K
1040 1060 1080 1100 x
1120 1140 1160 1180 1200
–2.5

–5.0 x
–7.5

–10.0 x
–12.5
[2]

(ii) Calculate the gradient of your graph. Determine the ∆S o in J K–1 mol–1 for this reaction.
Show all working.

 ∆S o = .............................. J K–1 mol–1 [2]

17
 1085
T/K 4.3
∆G o / kJ mol–1
1120
1050 –1.3
9.9
Example Responses – Paper 4
1148
1085 –5.8
4.3
1176
1120 –10.3
–1.3
Examiner comment
1148 –5.8
Assume
Common errors were:the standard enthalpy change, ∆H o, and the standard entropy change, ∆S o, for this
1176 –10.3
• not usingreaction remain
a ruler to constant
draw the overfitthis temperature range.
line of best
• to plot points incorrectly and then not draw a line of best ofit, which
o would have received an error carried forward
mark. For
(i) Use the data
Assume
example:
in Table
standard 4.1 tochange,
enthalpy plot a graph
∆H ,ofand∆Gthe against T onentropy
standard the grid.
change, ∆S o, for this
reaction remain constant over this temperature range.
12.5
(i) Use the data in Table 4.1 to plot a graph of ∆G o against T on the grid.
10.0
12.5
7.5
10.0
5.0
7.5
2.5
G o / kJ mol–1
5.0
0.0 T/K
1040 1060 1080 1100 1120 1140 1160 1180 1200
G o / kJ mol–1 2.5
–2.5
0.0 T/K
–5.0
1040 1060 1080 1100 1120 1140 1160 1180 1200
–2.5
–7.5
–5.0
–10.0
–7.5
–12.5
–10.0 [2]

(ii) –12.5
Calculate the gradient of your graph. Determine the ∆S o in J K–1 mol–1 for this reaction.
Show all working. [2]
coordinates: (1080, 4.8) (1180, 11.2)
(ii) Calculate the gradient of your graph. Determine the ∆S o in J K–1 mol–1 for this reaction.
Show all working.
4.8  ( 11.2 )
gradient =  0.160
 1080  1180 ∆S o = .............................. J K–1 mol–1 [2]
gradient = −ΔSθ ΔSθ = 0.160 × 1000
 +160
∆S o = .............................. J K–1 mol–1 [2]

© UCLES 2022 9701/42/M/J/22

Examiner comment
Common errors were:
© UCLES 2022 9701/42/M/J/22
• using values from Table 4.1 which did not lie on the line of best fit
• not understanding that the gradient gave −ΔSθ and calculating a negative value for the entropy
• not converting the entropy value to J K−1 mol−1 by multiplying by 1000.

18
Example Responses – Paper 4
9

(b) Group 1 hydrogencarbonates, MHCO3, decompose on gentle heating to give the corresponding
metal carbonate, carbon dioxide and water vapour.

(i) Write an ionic equation for the decomposition of the hydrogencarbonate ion.

2HCO3 → CO3 – 2–
+ CO2 + H2O
....................................................................................................................................... [1]

(ii) The thermal stability of Group 1 hydrogencarbonates increases down the group.
Examiner comment
9
• Suggest
Candidates needed to an
read explanation
the question forcarefully.
the trendThey in thermal
neededstability
to give an of the Group
ionic equation1 hydrogencarbonates.
which shows the
decomposition of the hydrogen carbonate ion and the formation
(b) Group 1 hydrogencarbonates, MHCO3, decompose on gentle heating to give the of a carbonate ion, carbon dioxide and water.
corresponding
• Commonmetal .............................................................................................................................................
errorscarbonate,
were: carbon dioxide and water vapour.
– 2MHCO3 → M2CO3 + CO2 + H2O This is not an ionic equation.
.............................................................................................................................................
– HCO(i)
3 → H
− Write
+
+ an
COionic
3
2− equation
This does not forshow
the decomposition
the formation of carbon of the hydrogencarbonate
dioxide and water. ion.
.............................................................................................................................................
....................................................................................................................................... [1]
.......................................................................................................................................
(ii)
The thermal stability of Group 1 hydrogencarbonates increases down the group. [2]
9
Suggest an explanation for the trend in thermal stability of the Group 1 hydrogencarbonates.
(c) Group
(b) The buffer system in seawaterMHCO
1 hydrogencarbonates, contains a mixture of HCO3– and
3, decompose on gentle
H2CO
heating to3.give the corresponding
The ionic radius
carbonate, of M and
carbon dioxide +
increases down the group.
metal.............................................................................................................................................
water vapour.
equilibrium 5 H2CO3 + H2O HCO3– + H3O+
There
(i) Write an is lessequation
ionic polarisation of the HCOof
for the decomposition −
3 theanion by the M+ ion.
hydrogencarbonate ion.
.............................................................................................................................................
(i) Define a buffer solution.
....................................................................................................................................... [1]
.............................................................................................................................................
.............................................................................................................................................
(ii) The thermal stability of Group 1 hydrogencarbonates increases down the group.
....................................................................................................................................... [2]
.............................................................................................................................................
Suggest an explanation for the trend in thermal stability of the Group 1 hydrogencarbonates.
Examiner comment
(c) The .......................................................................................................................................
buffer system in seawater contains a mixture of HCO3– and H2CO3. [2]
• Answers which referred to decreasing charge density of the cation down the group were an acceptable alternative
.............................................................................................................................................
to increasing cation size.two equations to show how equilibrium
(ii) Construct
equilibrium 5 H2CO3 + H2O HCO3– + 5Hacts 3O
+ as a buffer solution.
• Many candidates did not explain that the hydrogencarbonate ion would be less polarised as the metal ions became
.............................................................................................................................................
larger. .............................................................................................................................................
(i) Define a buffer solution.
.............................................................................................................................................
• Some candidates used the term ‘depolarisation’ instead of polarisation. This was ignored.
.......................................................................................................................................
• Some candidates stated that the ion becomes less polarised. It is essential that candidates refer to the anion [2]being
.............................................................................................................................................
.......................................................................................................................................
less polarised. [2]
(iii) The [HCO3–] / [H2CO3] ratio in a sample of seawater is 14.1.
.............................................................................................................................................

(c) The Calculate

buffer system the pH of this sample.
in seawater contains a mixture of HCO3– and H2CO3.
....................................................................................................................................... [2]
[pKa: H2CO3, 6.35]
equilibrium
(ii) Construct 5 H2COto3 show
two equations + H2Ohow equilibrium
HCO3– + 5Hacts 3O
+
as a buffer solution.

(i) Define a buffer solution.

.............................................................................................................................................
A solution which resists changes in pH when small amounts of acid
.............................................................................................................................................
....................................................................................................................................... [2]
or alkali– are added to it.
.............................................................................................................................................
(iii) The [HCO3 ] / [H2CO3] ratio in a sample of seawater is 14.1.

.......................................................................................................................................
Calculate the pH of this sample. [2]
[pKa: H2CO3, 6.35]
Examiner
(ii) comment
Construct two equations to show how equilibrium 5 acts as apH = ..............................
buffer solution. [3]
• Many candidates described the buffer solution as ‘keeping the pH constant’ or ‘maintaining the pH’ and omitted the
word ‘small’ when referring to the amounts of acid and alkali added. [Total: 14]
.............................................................................................................................................
• Answers such as ‘it is a solution which keeps the pH constant when any acid or base is added to it’ contained both
....................................................................................................................................... [2]
© of the common
UCLES 2022 errors and was not awarded either of the two marks available.
9701/42/M/J/22 [Turn over
(iii) The [HCO3–] / [H2CO3] ratio in a sample 19
of seawater is 14.1.
 .............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
Example Responses – Paper 4
....................................................................................................................................... [2]
....................................................................................................................................... [2]

(c) (ii)
The Construct two in
buffer system equations
seawatertocontains
show how equilibrium
a mixture 5 acts
of HCO – as a buffer solution.
3 and H2CO3.

with acid: HCO3 + H → H2CO3 – +

.............................................................................................................................................
equilibrium 5 H2CO3 + H2O HCO3– + H3O+
with alkali: H2CO3 + OH → HCO3 + H2O – –
....................................................................................................................................... [2]
(i) Define a buffer solution.
(iii) The [HCO3–] / [H2CO3] ratio in a sample of seawater is 14.1.
.............................................................................................................................................
Examiner comment
This is also aCalculate the pH HCO of this sample.
–
• correct equation: 3 + H3O → H2CO3 + H2O.
.............................................................................................................................................
+

•
[pK : H
These incorrect equations
a 2 CO , 6.35]
3 were frequently seen:

– H2CO3 + OH .......................................................................................................................................
–
→ HCO3 + H2O. HCO3 should have a minus charge. It is worth emphasising to learners the [2]
importance of balancing equations for charges as well as species. If the candidate had done this they would
have(ii) Construct
detected two equations to show how equilibrium 5 acts as a buffer solution.
this error.
– HCO3 + OH → CO32− + H2. Although this reaction can occur, it is an equilibrium that lies well to the left. It was
– –

ignored and.............................................................................................................................................
candidates did not receive a mark for this.

....................................................................................................................................... [2]

(iii) The [HCO3–] / [H2CO3] ratio in a sample of seawater is 14.1.

Calculate the pH of this sample. pH = .............................. [3]

[pKa: H2CO3, 6.35]
[Total: 14]

Ka = 10–6.35 = 4.47 x 10–7

© UCLES 2022 9701/42/M/J/22 [Turn over

4.47 10 7
[H ] 3.17 10 8
14.1

−log [H ] = 7.5 [3]

+
pH = ..............................

[Total: 14]
Examiner comment
An alternative calculation involved the Henderson–Hasselbalch equation. [Turn over
© UCLES 2022 9701/42/M/J/22

[ A]
pH  pKa + log
[HA ]
pH = 6.35 + log (14.1)

pH= 7.50

20
Example Responses – Paper 4

Question 5
10

5 (a) Complete Table 5.1 to predict the substance liberated at each electrode during electrolysis of
the indicated electrolyte with inert electrodes.

Table 5.1

substance liberated substance liberated

electrolyte
at the anode at the cathode
10
PbBr2(l) bromine lead
5 (a) Complete Table 5.1 to predict the substance liberated at each electrode during electrolysis of
concentrated
the chlorine
NaCl (aq)with inert electrodes.
indicated electrolyte hydrogen

Cu(NO3)2(aq) oxygen
Table 5.1 copper

substance liberated substance liberated [3]

electrolyte
Examiner comment at the anode at the cathode
• Candidates
(b) AnPbBrcould use formulae
electrolytic instead
cell is set up toofdetermine
names, provided
a valuethefor
formulae were correct,
the Avogadro e.g. Br
constant, was electrolyte
L.2The correct but Br
2(l)
was not.
is dilute sulfuric acid and both electrodes are copper.
• Many candidates gave ions. These are not substances liberated and were ignored.
concentrated NaCl (aq)
• There were
When many incorrectofsubstances
a current 0.600 A is given,
passedthese included
through the Na from
acid forconcentrated NaCl(aq)
30.0 minutes, and NO
the anode 3 from
decreases
−

Cu(NO3)in2(aq).
mass by 0.350 g.
Cu(NO 3)2(aq)
• Water was ignored as a substance liberated from Cu(NO3)2(aq). Oxygen was the response required.
• (i) Stategave
Some candidates the relationship between the
the correct substances Faraday them
but assigned constant,
to theF, and theelectrode.
incorrect Avogadro constant, L.
[3]
....................................................................................................................................... [1]

(b) (ii)
An electrolytic cell is set upinformation
Use the experimental to determine a value
in (b) for the
and data Avogadro
from constant,
the table on pageL.23The electrolyte
to calculate a
is dilute sulfuric
value for theacid and both
Avogadro electrodes
constant, L. are copper.

When a current
Show of 0.600 A is passed through the acid for 30.0 minutes, the anode decreases
all working.
in mass by 0.350 g.

(i) State the relationship between the Faraday constant, F, and the Avogadro constant, L.

F = Le
....................................................................................................................................... [1]

(ii) Use the experimental information in (b) and data from the table on page 23 to calculate a
value for the Avogadro constant, L.

Show all working.

Avogadro constant, L = .............................. [4]

[Total: 8]
21
 in mass by 0.350 g.

(i) State the relationship between the Faraday constant, F, and the Avogadro constant, L.
Example Responses – Paper 4

....................................................................................................................................... [1]

(ii) Use the experimental information in (b) and data from the table on page 23 to calculate a
value for the Avogadro constant, L.

Show all working.

0.35
Amount of Cu2+ formed = = 5.5111811 × 10-3 mol
63.5
Q = I x t = 0.60 × 30 × 60 = 1080 C
1080
Number of electrons = = 6.75 × 1021
19
1.6  10
Cu2+ + 2e− → Cu
6.75 × 10 21
Number of Cu 2+
ions = = 3.375 × 1021
2
3.375  10 21
Number of Cu2+ ions per mole (L) = 3
= 6.123914164 × 1023
5.51  10

6.12 × 10
Avogadro constant, L = .............................. [4]
23

[Total: 8]
Examiner comment
• There were alternative calculations which were valid and could be awarded marks.
• The most common error was to use 96 500 C and divide this by 1.6 x 10-19 to give a value for L of 6.022 × 1023. This
approach
© UCLES 2022 did not use the experimental information given.
9701/42/M/J/22
• Many candidates rounded too early in the calculation and obtained an incorrect value for L.

22
Example Responses – Paper 4

Question 6
11

6 (a) The reagent and conditions required for the nitration of benzene, benzoic acid and phenol are
shown in Table 6.1.

Table 6.1

compound reagents and conditions for nitration

benzene concentrated HNO3, 50 °C, concentrated H2SO4 catalyst
benzoic acid concentrated HNO3, 100 °C, concentrated H2SO4 catalyst
phenol dilute HNO3(aq), 20 °C

Concentrated HNO3 reacts with concentrated H2SO4 to generate the electrophile NO2+.

(i) Complete Fig. 6.1 to show the mechanism of the reaction between benzene and NO2+.
Include all relevant curly arrows and charges.
NO2 NO2
H

+ +H+

NO2+

Fig. 6.1
[3]

(ii) Write an equation to show how H2SO4 is regenerated.

Examiner comment
....................................................................................................................................... [1]
• The first curly arrow must come from within the hexagon of the benzene ring and go to the N of NO2+. These are
examples of diagrams which could not be awarded marks:
(b) Draw the major products from the mononitration of benzoic acid and of phenol.

major product from benzoic acid major product from phenol

NO2 NO2 NO2+
• The diagram for the intermediate must:
– show the delocalised system as a ‘horseshoe’ shape which includes carbon 3 (C3), C4 and C5, and preferably
extends up to C2 and C6. The horseshoe should not go beyond either C2 or C6.
– show the + charge below an imaginary line which connects C2 and C6. Ideally, the + charge should lie within
the horseshoe. If + was draw above the imaginary line then it implied that C1 had a + charge, which cannot be
the case as it is surrounded by four single bonds.
– not show any other charges.
• These diagrams of the intermediate did not receive marks. The curly arrows were ignored when considering the
intermediate.
H+ HO2+
NO2 H
+ +
H NO2 [2]
+

23
 phenol dilute HNO3(aq), 20 °C

Concentrated HNO3 reacts with concentrated H2SO4 to generate the electrophile NO2+.
Example Responses – Paper 4
11
(i) Complete Fig. 6.1 to show the mechanism of the reaction between benzene and NO2+.
Include all
ed for the nitration of benzene, relevant
benzoic curly
acid andarrows
phenoland
arecharges.
•
The second curly arrow must come from the C—H bond and go into the hexagon of the benzene ring. Also, the H+
ion lost must be shown.
Table
• 6.1
This diagram was not awarded marks for the curly arrow because it did not come from the bond and did not enter
the benzene ring:
eagents and conditions H
for nitration
+ NO2+
ed HNO3, 50 °C, concentrated H2SO4 catalyst
NO2
d HNO3, 100 °C, concentrated H2SO4 catalyst
Fig. 6.1
dilute HNO3(aq), 20 °C [3]

oncentrated H2SO(ii) Write an equation to show how

4 to generate the electrophile NO2 .
+ H2SO4 is regenerated.
HSO4 + H → H2SO − +
.......................................................................................................................................
+ 4 [1]
e mechanism of the reaction between benzene and NO 2 .
ws and charges.

(b) Draw the major products from the mononitration of benzoic acid and of phenol.

major product from benzoic acid major product from phenol

COOH OH

Fig. 6.1
NO2
[3]

w H2SO4 is regenerated.

........................................................................................ [1]

mononitration of benzoic acid and of phenol. NO2

major product from phenol [2]

NO2

© UCLES 2022 9701/42/M/J/22 [Turn over

HO

[2]
Examiner comment
• Only one major product from phenol was required and either of the structures shown were awarded marks.
• Displayed formulae could also be drawn, but candidates needed to take care to ensure that the bonds connected
to the correct atoms.
• Some candidates drew the substituents in the incorrect positions on the benzene ring, e.g. 3-nitrophenol.

9701/42/M/J/22 [Turn over

24
Example Responses – Paper 4

12

(c) Compare the relative ease of nitration of benzene, benzoic acid and phenol.
Explain your reasoning; include reference to the structures of the three compounds in your
answer.

phenol
............................................... benzene benzoic
> ............................................... acid
> ..............................................
easiest least easy

One of the lone pairs on the oxygen atom of the OH group of phenol
....................................................................................................................................................

overlaps with the π-delocalised ring system. This increases electron

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

density in the ring and makes phenol more likely to be attacked by

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

NO2+ compared to benzene. The COOH group in benzoic acid is electron

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

withdrawing. This decreases electron density in the ring so it less likely

....................................................................................................................................................
[4]
to be attacked by an electrophile when compared to benzene.

Examiner comment
• Another way of explaining why phenol is the easiest to nitrate is to refer to the p-orbital on oxygen overlapping with
the π-delocalised ring and thus decreasing electron density.
• The lone pair which overlaps with the delocalised ring in phenol must be linked to the oxygen atom.
• It was not sufficient to use the term ‘charge density’ instead of ‘electron density’.
• Some candidates omitted the + charge on NO2. This was not accepted.
• The OH group was sometimes described as electron withdrawing, which is incorrect.

© UCLES 2022 9701/42/M/J/22

25
 Example Responses – Paper 4

13

(d) The azo compound Congo Red is used as an acid–base indicator and can be made by the
route shown in Fig. 6.2.

In step 3 of this synthesis, compound Y reacts with compound Z. Compound Z is made from
compound X. Assume that the –SO3– Na+ groups do not react.

X C12H12N2

step 1
O2N NO2 H2N NH2

step 2

Y C10H8NO3SNa Z
NH2

+ +
+ N N N N

SO3–Na+

NaOH(aq) step 3

Congo Red
NH2

N SO3– Na+
N N
SO3 Na– +
N

NH2

Fig. 6.2

(i) Suggest structures for compounds X, Y and Z and draw them in the boxes in Fig. 6.2. [3]

(ii) Give the reagents and conditions for step 1 and step 2.
Examiner comment
• This structurestep
for Z1is..................................................................................................................................
incorrect because the + charges are on the wrong nitrogen atoms.
+ +
step 2 ..................................................................................................................................
N N N N [3]

[Total: 16]

© UCLES 2022 9701/42/M/J/22 [Turn over

26
 N SO3– Na+
Example Responses – Paper 4 N N
SO3 Na– +
N

• Some candidates showed the chloride ions at both ends of Z. This was awarded as it shows the neutral compound.
NH2 be shown with minus charges.
However, the structure shown below was incorrect because the chloride ions should
+ +
ClN N N NCl Fig. 6.2

(i) Suggest structures for compounds X, Y and Z and draw them in the boxes in Fig. 6.2. [3]

(ii) Give the reagents and conditions for step 1 and step 2.

Sn and concentrated HCl are heated under reflux, followed by

step 1 ..................................................................................................................................
the addition of NaOH(aq).
HNO2 (or NaNO2 and dilute acid) below 10oC.
step 2 ..................................................................................................................................
[3]

[Total: 16]
Examiner comment
Common errors were to:
© UCLES 2022 9701/42/M/J/22 [Turn over
• describe tin as a catalyst. It is a reactant and this contradicts the mark for reactants in step 1.
• reflux the reactant mixture together with NaOH(aq) in step 1. NaOH(aq) is added to the cooled mixture after the
reaction with HNO2 has finished.
• miss out a reaction condition such as concentrated for HCl.

27
 Example Responses – Paper 4

Question 7
14

7 (a) State the uses of TMS and D2O in NMR spectroscopy.

the standard for chemical shift measurements.

TMS ...........................................................................................................................................

it is a solvent that does not contain any H atoms so does not

D2O ............................................................................................................................................
14
produce peaks which interfere with the NMR spectrum. [1]
7 (a) State the uses of TMS and D2O in NMR spectroscopy.

Examiner
(b) Thecomment
three isomeric ketones with molecular formula C5H10O are:
TMS ...........................................................................................................................................
• D2O could also be used to identify O−H and N−H protons by removing their peaks.
● pentan-2-one
• A commonD O ............................................................................................................................................
● 2error was to describe TMS as a solvent.
pentan-3-one
[1]
● 3-methylbutanone.

(i) Complete Table 7.1 to show the number of peaks observed in the proton (1H) NMR
(b) The three isomeric ketones with molecular formula C5H10O are:
spectrum and in the carbon-13 NMR spectrum for each compound listed.
● pentan-2-one
Table 7.1
● pentan-3-one
● 3-methylbutanone.
number of peaks observed in number of peaks observed in
ketone
(i) Complete Tablethe 7.1proton (1H) the
to show NMRnumber
spectrum theobserved
of peaks carbon-13inNMR
the spectrum
proton (1H) NMR
spectrum and in the carbon-13 NMR spectrum for each compound listed.
pentan-2-one
Table 7.1
pentan-3-one
number of peaks observed in number of peaks observed in
ketone
3-methylbutanone the proton (1H) NMR spectrum the carbon-13 NMR spectrum

pentan-2-one 4 5 [2]

(ii)pentan-3-one 2 formula C5H10O that have:

State all the ketones with molecular 3

3-methylbutanone 3 spectrum
a doublet in their proton (1H) NMR 4

.............................................................................................................................................
[2]
a singlet in their proton (1H) NMR spectrum.
(ii) State all the ketones with molecular formula C5H10O that have:
.............................................................................................................................................
a doublet in their proton (1H) NMR spectrum
[2]
3-methylbutanone
.............................................................................................................................................

a singlet in their proton (1H) NMR spectrum.

3-methylbutanone and pentan-2-one

.............................................................................................................................................
[2]

28
Example Responses – Paper 4
15

(c) Cortisone, C21H28O5, is a naturally occurring chemical that contains chiral carbon atoms.

cortisone
OH
O
CH3
O 15 OH
CH3
(c) Cortisone, C21H28O5, is a naturally occurring chemical that contains chiral carbon atoms.

cortisone
OH
O
O
Fig. 7.1 CH3
OHO
(i) Deduce the number of chiral carbon
CH atoms in one molecule of cortisone.
3

six
....................................................................................................................................... [1]

(ii) with an excess of NaBH4.

Cortisone is reacted O

State the molecular formula of the organic compound formed.

Fig. 7.1
C21H34O5
....................................................................................................................................... [1]
(i) Deduce the number of chiral carbon atoms in one molecule of cortisone.
(iii) Cortisone is an optically active molecule.
.......................................................................................................................................
Examiner comment [1]
Explain what is meant by optically active.
Common errors
(ii) were to:
Cortisone is reacted with an excess of NaBH4.
• work out an incorrect number of hydrogen atoms
.............................................................................................................................................
• put a sodium atom in themolecular
State the formula. formula of the organic compound formed.
.............................................................................................................................................
....................................................................................................................................... [1]
....................................................................................................................................... [1]
(iii) Cortisone is an optically active molecule.
[Total: 8]
Explain what is meant by optically active.

A molecule that is able to rotate the plane of polarised light.

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

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

....................................................................................................................................... [1]

[Total: 8]
Examiner comment
This question was not well understood by many candidates. Common errors were to:
• miss out at least one of the key words ‘rotate’ and ‘polarised’.
• state that the molecule had optical isomers.
• explain that the molecule contained a chiral carbon.

© UCLES 2022 9701/42/M/J/22 [Turn over

29
 Example Responses – Paper 4

Question 8
16

8 (a) Compare the relative acidities of ethanol, ethanoic acid, chloroethanoic acid and phenol.
Explain your reasoning.

chloroethanoic
acid
.................................. ethanoic acid
> .................................. phenol
> .................................. ethanol
> ..................................
most acidic least acidic

Chloroethanoic acid > ethanoic acid because it contains an electronegative

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

Cl . This withdraws electrons from the O—H bond, weakening it so that

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

H is more easily lost. It also stabilises the conjugate base.

+
....................................................................................................................................................

Ethanoic acid > phenol due to the negative inductive effect of C=O which
....................................................................................................................................................

weakens the O—H bond.

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

Phenol > ethanol because one of the lone pairs on the oxygen atom of the
....................................................................................................................................................
[4]
OH group of phenol is delocalised into the benzene ring. This means

that
(b) An H isof more
excess
+
easily
ethanedioic lost.
acid, HOOCCOOH(aq), is reacted with warm acidified KMnO4(aq).

Ethanol
State is the
the type least acidic
of reaction because
undergone its alkylacid.
by ethanedioic group has a positive inductive
Describe what you would observe.
effect
Write anwhich
equation strengthens the O—H bond so that H+ is most difficult to
for this reaction.

lose.equation can use [O] or [H] as necessary.

Your

type of reaction ..........................................................................................................................

Examiner comment
• observations
This question ..............................................................................................................................
asks candidates to explain the relative acidities of the compounds so explanations in terms of the
ability of the anions to accept protons could not be awarded marks.
• There was equation
often no.....................................................................................................................................
reference made to weakening the O—H bond, allowing a proton to be lost more easily.
• It was not sufficient to describe the O atom in ethanoic acid as electronegative because all the compounds contain [2]
an O atom.

30
 ....................................................................................................................................................
Example Responses – Paper 4 [4]

(b) An excess of ethanedioic acid, HOOCCOOH(aq), is reacted with warm acidified KMnO4(aq).

State the type of reaction undergone by ethanedioic acid.

Describe what you would observe.
Write an equation for this reaction.

Your equation can use [O] or [H] as necessary.

oxidation
type of reaction ..........................................................................................................................

bubbles and the purple solution decolourises

observations ..............................................................................................................................

HOOCCOOH + [O] → 2CO2 + H2O

equation .....................................................................................................................................
[2]

Examiner comment
• The equation 5HOOCCOOH + 2MnO4– + 6H+ → 10CO2 + 8H2O + 2Mn2+ is also correct.
• Redox is insufficient for the type of reaction because the question specifically asks for the reaction undergone by
ethanedioic acid.
• Gas given off is not an observation; it is a conclusion based on the observation that effervescence is occurring.
• Some candidates put [O] above the reaction arrow instead of on the left of the equation. This was not accepted as
showing a balanced equation.

17

(c) A section of a polyester is shown.

polyester
O O O O

O CH2 C O CH C O CH2 C O CH C

CH3 CH3

Fig. 8.1
© UCLES 2022 9701/42/M/J/22
Draw the structures of the two monomers that form this polyester.

O O

HO HO
OH OH

[2]

(d) Serine
Examiner can polymerise to form two different types of condensation polymer; a polyester and a
comment
polypeptide.
• Structural or displayed formulae were accepted. Displayed formulae needed to show the correct connectivity
between atoms. serine
• Instead of a carboxylic acid group, an acyl chloride groupOH
was also accepted i.e.HOCH2COCl and HOCH(CH3)
COCl.
H 2C O
31
H2N C C
 17 Example Responses – Paper 4

(c) A section of a polyester is shown. [2]

(d) Serine can polymerise to form two different types of condensation polymer; a polyester and a
polyester
polypeptide.
O O O O
serine
O CH2 C O CH C O CH2 C O CH C
OH
CH H2C O 3 CH 3

H2N C C
Fig. 8.1
H OH
Draw the structures of the two monomers that form this polyester.
Fig. 8.2

Draw the structure of the polypeptide showing two repeat units. The peptide linkage should be
shown displayed.
OH
OH
H2C O
H2C O
N C C
N C C [2]
[2]
(e) Explain H
H why condensation polymers normally biodegrade more readily than addition polymers.
(d) Serine can polymerise to form H twoHdifferent types of condensation polymer; a polyester and a
....................................................................................................................................................
polypeptide.
Examiner comment
..............................................................................................................................................
serine [1]
• Many candidates did not read the question carefully enough and drew three or more repeat units.
OH [Total: 11]
• The continuation bonds were frequently missing. H C
2 O
• Candidates who drew skeletal formulae needed to show the continuation bonds clearly as dashed lines. A solid line
©at either2022
end of a skeletal formula indicates a H
methyl group. [Turn over
2N C C
UCLES 9701/42/M/J/22
• Many candidates drew trivalent carbon atoms. Learners should be reminded to check their structures to ensure
that each carbon atom has four bonds around it. This H diagramOH is incorrect:

OH OH Fig. 8.2

H2Cthe structure of theHpolypeptide

Draw 2C
showing two repeat units. The peptide linkage should be
shown displayed.

N C C N C C

H O H O

[2]

(e) Explain why condensation polymers normally biodegrade more readily than addition polymers.
Condensation polymers can hydrolyse in acidic or alkaline conditions.
....................................................................................................................................................

Addition polymers are chemically inert.

.............................................................................................................................................. [1]

[Total: 11]

© UCLES 2022 9701/42/M/J/22 [Turn over

32
Example Responses – Paper 4

Question 9
18

9 The structure of cyclohexylamine is shown in Fig. 9.1.

cyclohexylamine
NH2

Fig. 9.1

(a) Compare the relative basicities of ammonia, cyclohexylamine and phenylamine.

Explain your reasoning.

cyclohexylamine > ...............................................

............................................... ammonia > ..............................................
phenylamine
most basic least basic

Cyclohexylamine has an alkyl group which has a positive inductive effect.

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

This pushes electrons towards the N, increasing its electron density and
....................................................................................................................................................

so it accepts a proton most easily.

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

Phenylamine has a lone pair on N which delocalises into the π-ring. This
....................................................................................................................................................

decreases electron density on N so it accepts a proton least easily.

....................................................................................................................................................
[3]

Examiner comment
• Candidates must have explained clearly that the order of basicity was linked to the ability of N to accept a proton,
or donate its lone pair to a proton. Many answers were too vague, e.g.:
– ‘basicity is linked to the ability of the NH2 group to accept a proton’. This does not tell us that it is the N atom that
accepts the proton or donates its lone pair.
– ‘the lone pair on N is more available in cyclohexylamine’. This does not mention gaining a proton more easily.
• Candidates could state that the p orbital from N overlaps with the delocalised π-ring instead of the lone pair.
• For phenylamine the lone pair that is delocalised needed to be identified as belonging to N.

33
 Example Responses – Paper 4
19

(b) Cyclohexylamine reacts with ethanoyl chloride to form the corresponding amide, L.

L
O
19
C
NH2 HN CH3
(b) Cyclohexylamine reacts with ethanoyl chloride to form the corresponding amide, L.

CH3COCl L
O
C
NH2 Fig. 9.2 HN CH3

(i) Name the mechanism for the CH

reaction
3COCl
shown in Fig. 9.2.

Addition-elimination
....................................................................................................................................... [1]

(ii) Fig. 9.2between cyclohexylamine and CH3COCl.

Complete the mechanism of the reaction
Examiner comment
‘Condensation’ R–NH
(i) was
Name is used
2the
ignored as it to
mechanismrepresent
does notfor thecyclohexylamine.
reaction
accurately shown
describe the in Fig. 9.2.
mechanism.

Include all relevant lone pairs of electrons, curly arrows, charges and partial charges. [1]
.......................................................................................................................................

(ii) O the mechanism of the reaction between cyclohexylamine and CH COCl.

Complete 3

H 3C C products
R–NH2 is used to represent cyclohexylamine.
Cl
Include all relevant lone pairs of electrons, curly arrows, charges and partial charges.
δ-
R NHO2 O–
δ+ Cl
H 3C C products
H C [4]
Cl
N +
(iii) CH3 of CH3COCl forms compound M.
The reaction between cyclohexylamine and an excess
H
Compound M has the molecular formula C10H17NO2.
R NH2
R
Suggest and draw the structure of M.
[4]
Examiner comment
•
(iii) The reaction between cyclohexylamine and an excess of CH COCl forms compound M.
The lone pair should be clearly shown on the N of RNH2. This diagram is incorrect:
3
Compound M has the molecular formula C10H17NO2.
R––NH2
• The partial charges
Suggestwere
andoften
drawomitted of M.
from C=O.
the structure
• This candidate’s diagram of the intermediate showed several common errors:
– there was no minus sign on the O atom.
O
– the curly arrow should have been shown coming from the lone pair of O.
δ +
δ – the curly arrow on N—R was incorrect.
-

H3C C Cl [1]
+ [Total: 9]
NH2

R
[1]
© UCLES 2022 9701/42/M/J/22 [Turn over
34 [Total: 9]
 R NH2
Example Responses – Paper 4

[4]

(iii) The reaction between cyclohexylamine and an excess of CH3COCl forms compound M.
Compound M has the molecular formula C10H17NO2.

Suggest and draw the structure of M.

O O

C C
H3C N CH3

[1]

Examiner comment [Total: 9]

• Skeletal or displayed structures could be drawn.
• This was a common incorrect structure:
O
© UCLES 2022 9701/42/M/J/22 [Turn over

HN C CH3

C CH3

35
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