1

Section A
Answer all questions in this section. Begin each question on a fresh sheet of writing paper.

1 The ethoxide ion, CH3CH2O−, can act as a nucleophile or a base when reacted with bromoethane.

(a) Write an equation for the reaction to form the ethoxide ion from ethanol. [1]

• CH3CH2OH + Na → CH3CH2O−Na+ + 1/2 H2

Note:
1. Using NaOH to generate the ethoxide ion, note that alcohols do not react with NaOH.
2. Writing the dissociation equation of ethanol as a weak acid, without reading the question
that it should be a “REACTION” that generates the ethoxide ion.

(b) Suggest why the ethoxide ion can function as a Brønsted-Lowry base. [1]

• Lone pair of electrons on oxygen atom of the CH3CH2O− ion is available to accept a
proton/form dative bond with a proton.

Note:
1. Bronsted-Lowry base is not a nucleophile (Lewis Base); differentiate between the
different definition of acid/bases - Arhennius vs. Bronsted-Lowry vs. Lewis.
2. Must answer in context of the question.

(c) The rate of the nucleophilic reaction between the ethoxide ion and bromoethane was followed by
measuring the concentration of remaining bromoethane after fixed time intervals. Two
experiments were carried out, starting with different concentrations of ethoxide ions. The following
results were obtained.

Experiment 1, when Experiment 2, when

Time/min [CH3CH2O−] = 0.10 mol dm−3 [CH3CH2O−] = 0.15 mol dm−3
[CH3CH2Br] / mol dm−3 [CH3CH2Br] / mol dm−3
0 0.0100 0.0100
40 0.0079 0.0070
80 0.0062 0.0049
120 0.0049 0.0034
160 0.0038 0.0024
200 0.0030 0.0017
240 0.0024 0.0012
l
(i) Using the same axes, plot graphs of [CH3CH2Br] against time for the two experiments. [2]

• Axes correct way round + correct labels + scale must be chosen so that graph
is more than half grid in both x and y direction
• All points correctly plotted within ±½ small square, graph line is a best-fit line

Note:
1. Recurring scale on the x-axis (15 small squares for 40 units).
2. Graph drawn must be a smooth curve.

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Use your graphs to determine

(ii) the order of reaction with respect to [CH3CH2Br] and [2]

(iii) the order of reaction with respect to [CH3CH2O−] using initial rates method. [2]

Show your workings clearly.

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(ii) • Correct t½ determined and working shown (at least two constant t½ and
construction lines)

For [CH3CH2O−] = 0.15 mol dm-3 (Experiment 2),

1st t½ = 78 min; 2nd t½ = 78 min  Average t½ = 78 min

OR For [CH3CH2O−] = 0.10 mol dm-3 (Experiment 1),

1st t½ = 118 min; 2nd t½ = 118 min  Average t½ = 118 min

• Since t½ is a constant, 1st order with respect to [CH3CH2Br].

Note:
1. Working lines (dotted lines) to indicate how you read off your half-life must be
drawn clearly on the graph.
2. Half-life is to be clearly indicated on the graph.
3. Please use a dark pencil for your working lines on the graph.

(iii) • Correct determination of initial rates from graph (include tangent drawing)

When [CH3CH2O−] = 0.10 mol dm−3 (Experiment 1),

(𝟏𝟎−𝟐)×𝟏𝟎−𝟑
Initial rate of reaction = | | = 6.06  10−5 mol dm−3 min−1
𝟎−𝟏𝟑𝟐

When [CH3CH2O−] = 0.15 mol dm−3 (Experiment 2),

(𝟏𝟎−𝟐)×𝟏𝟎−𝟑
Initial rate of reaction = | | = 8.89  10−5 mol dm−3 min−1
𝟎−𝟗𝟎

𝟖.𝟖𝟗  𝟏𝟎−𝟓
• When [CH3CH2O−] increases by 1.5 times, rate increase by = 1.48 ≈ 1.5
𝟔.𝟎𝟔  𝟏𝟎−𝟓
−
times, reaction is first order with respect to [CH3CH2O ].

Note:
1. Drawing of tangent at t=0 is required to be accurate for the calculation of the value
of gradient as “initial rate”.
2. Initial rate is not 1/(half-life).
3. Initial rate should be found at t=0 and not at any other timings (as it would then be
known as instantaneous rate)

(iv) Hence, give the rate equation for the reaction. [1]

• Rate = k [CH3CH2Br] [CH3CH2O−]

Suggest the effect on the half-life of Experiment 1 if the initial concentration of

(v) [CH3CH2Br] was doubled, [1]

(vi) [CH3CH2O−] was doubled. [1]

(v) • No effect/no change in half-life.

Explanation:
Since [CH3CH2O−] is in excess, the reaction is pseudo first order with a constant half-life.
Rate = k’ [CH3CH2Br] where k’ = k[CH3CH2O−]

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(vi) • Half-life will be halved.

Explanation:
𝑙𝑛2 𝑙𝑛2
t1/2 = ′ = , if [CH3CH2O−] is doubled, half-life will be halved.
𝑘 𝑘[𝐶𝐻3 𝐶𝐻2 𝑂− ]

(d) (i) When the ethoxide ion undergoes a similar nucleophilic reaction with 2-bromo-2-
methylpropane, it was found that the rate of reaction is independent of the concentration
of the ethoxide ion.

Draw diagrams to illustrate the mechanism for this reaction. Show relevant lone pairs and
dipoles, and use curly arrows to indicate the movement of electron pairs. [2]

Nucleophilic substitution (SN1)

•• 2 marks for mechanism

Note
- partial charges (+ and -) on the C-Br bond
- curly arrow coming from C-Br bond to Br
- the lone pair of electrons on the attacking nucleophile, with the curly arrow coming
from the lone pair
- slow/fast step labelling
- accept drawings with no wedge-dash notation
- Show trigonal planar shape of intermediate

(ii) The ethoxide ion can function as a base when reacted with 2-bromo-2-methylpropane,
forming three products which include the bromide ion.

Write a balanced equation for the reaction and name the type of reaction. [2]

•
• Elimination

(iii) Suggest a 2-stage synthesis to prepare 3-bromocyclopentene from cyclopentene, in the

absence of UV light.

You should state the reagents and conditions needed for each step, and show clearly the
structure of any intermediate compounds. [2]

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• 1 mark for step 1 reagents and conditions and intermediate

• 1 mark for step 2 reagents and conditions
•
(e) Alkyl halides can be formed from alcohol and hydrogen halides, for example:

CH3CH2OH + HCl → CH3CH2Cl + H2O ⎯ (1)

Hydrogen chloride in reaction (1) is generated from concentrated H2SO4 and an ionic solid A.

(i) Suggest the identity of A. [1]

• NaCl(s)

Note
- NaCl + H2SO4 → NaHSO4 + HCl
- Accept other ionic salts (except AgCl)

(ii) Reaction (1) occurs via a mechanism where CH 3CH2OH acts as a base. Suggest the
structure of the intermediate in this mechanism. [1]

Ethanol can also be converted to chloroethane using phosphorus pentachloride.

(iii) Explain, with the aid of an equation, the reaction when excess water is added to
phosphorus pentachloride. [2]

• PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(aq)

• Hydrolysis is possible because of the energetically accessible vacant 3d
orbitals in P available for dative bonding with water molecules.

Note
- State symbols not required but if wrong state symbol of HCl is written, penalise
equation mark

(iv) A small amount of water is added to another sample of phosphorus pentachloride. Write
an equation for the reaction. [1]

• PCl5(s) + H2O(l) → POCl3(l) + 2HCl(g)

Note
- State symbols not required but if wrong state symbol of HCl is written, penalise
equation mark

[Total: 22]

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2 This question is about oxygen-containing compounds. Oxygen is found in many compounds,

both organic and inorganic.
An organic oxygen-containing compound, cocaine, was first used as a local anaesthetic. Its
structure is shown below :

cocaine

Student X was asked to suggest a suitable synthetic route to prepare cocaine from methylbenzene
and compound A.

OH

OH
Compound A

Student X suggested the following steps:

Step 1 Methylbenzene is oxidised with hot, acidified KMnO4 to give benzoic acid.
Step 2 Benzoic acid is converted into benzoyl chloride by reacting the resultant
solution from step 1 with solid PCl5.
Step 3 Benzoyl chloride is reacted with compound A at room temperature.
Step 4 The resultant compound from step 3 is reacted with methanol in the
presence of concentrated sulfuric acid at room temperature.

(a) Cocaine cannot be obtained from the method suggested. Give 2 reasons to explain which
step(s) will not work. [2]
••
1. In step 2, PCl5 will hydrolyse in the presence of aqueous solution.
2. The final product will be the protonated form of cocaine since it is prepared in an acidic
medium.
3. Heat is required for step 4

Note: Acyl halides cannot react with tertiary amines to form amides. There is no H on nitrogen
for substitution to take place.

Cocaine can be consumed by inhaling its hydrochloride salt (a protonated salt of cocaine) or
smoking freebasing cocaine. Freebasing cocaine is the process of freeing the cocaine base from
the salt form.

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(b) Suggest a suitable reagent to convert cocaine hydrochloride back into cocaine. [1]
• dilute NaOH

Note: Cocaine hydrochloride is a conjugate acid of cocaine. Cannot use an acid to convert the
conjugate acid to the corresponding base. A strong base is needed.

(c) After obtaining the cocaine from the hydrochloride salt, it is then extracted with a suitable organic
solvent. Smoking cocaine involves lighting up the free basing cocaine.
Give a possible reason why cocaine produced in this manner is considered hazardous. [1]

• Some of the flammable organic solvent may still be present in the cocaine and may cause
burns when ignited.
Note: The key phrase is ‘produced in this manner’. This means that the extraction with an organic
solvent is the problem.

The human liver uses carboxylesterase enzymes hCE1 and hCE2 to metabolise cocaine. If
cocaine is taken in combination with ethanol, hCE1 can turn cocaine into the even more toxic
cocaethylene (the ethyl ester).

cocaethylene

(d) Describe how you would distinguish cocaethylene from cocaine. [2]

To samples of both compounds, ●hydrolyse by heating with aqueous NaOH. Distill and
collect the alcohol. Cocaine produces methanol whereas cocaethylene produces ethanol.
●The ethanol collected can be detected by warming with alkaline aqueous iodine. A
yellow precipitate of CHI3 will be observed. No yellow ppt observed for methanol.

Note: Hydrolysis of ester using alkaline medium is preferred rather than in acid conditions if tri-
iodomethane test is used to distinguish the esters. Tri-iodomethane test requires aq. iodine in
NaOH. If acid is used for the hydrolysis, then NaOH has to be added in excess for the tri-
iodomethane test.

Reagents need to be specified for the tri-iodomethane test.

A 25.0 cm3 sample of 0.25 mol dm–3 cocaine hydrochloride was titrated with aqueous KOH of the
same concentration. The pKb of cocaine is 5.59 at 25 C.

(e) (i) Calculate the pH of the cocaine hydrochloride sample. [2]

pKa cocaine hydrochloride = 14-5.59 = 8.41

●Ka = 3.89 x 10-9 mol dm-3

[H+] = √(3.89 x 10-9 x 0.25) = 3.12 x 10-5 mol dm-3
●pH = -lg[H+] = 4.51

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Note: Cocaine hydrochloride is a weak conjugate acid. Calculation of pH requires using K a

and not Kb.

(ii) Calculate the pH at the equivalence point. [2]

Amt of cocaine at equivalence point = 25/1000 x 0.25 mol
= 6.25 x 10-3 mol

Total volume of solution at equivalence point = 50 cm3

[cocaine] at equivalence point = 1000/50 x 6.25 x 10 -3 mol dm-3 = 0.125 mol dm-3

Kb = 2.57 x 10-6 mol dm-3

●[OH-] = √Kb x c= √2.57 x 10-6 x 0.125 mol dm-3
pOH = -lg[OH-]
= 3.25
●pH = 14-pOH = 10.75

Note: pH =pKa is not the pH at equivalence point. It is the maximum buffering capacity.

(iii) Using your answer from e(i) and e(ii), sketch a graph to show how the pH changes during
this titration. Your sketch should clearly include the
● equivalence volume
● pH value and volume at maximum buffering capacity, if any. [3]

pH

10.75

8.41

4.51

vol of KOH / cm3

12.5 25.0

● Shape
● labelling of axes with
units
● Equivalence vol
● 8.41
●12.5
● 4.51 & 10.75

Note: No marks awarded if graph is downward sloping.

(iv) Suggest an indicator for this titration and explain your choice. [1]

• Thymol blue/phenolphthalein. The working range of the indicator lies within the
sharp pH change at the equivalence point.

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Note: Equivalance point is a point on the vertical portion of the pH curve.

Thus the correct phrasing of the answer should be:

“Equivalence point is within the working range of the indicator”
OR “working range of the indicator is within the vertical portion of the pH curve”
And NOT the other way round.
(f) Examples of oxygen-containing inorganic compounds are the oxides from Period 3 elements.
Three such oxides, Al2O3, SiO2 and P4O10 are shown in the table below.
oxide melting point / C electrical conductivity when molten
L 1713 very poor
M 340 nil
N 2072 good

(i) Identify L, M and N. [1]

• L: SiO2 M: P4O10 N: Al2O3

(ii) Describe, with the aid of equations, how you can carry out reactions to determine the
identity of the oxides. [4]

Case 1
1. Add water to all three oxides. Both SiO2 and Al2O3 are insoluble. P4O10 is soluble
to give an acidic solution.
P4O10 + 6H2O → 4H3PO4
2. Add dil.HCl to the two remaining oxides. Al2O3 dissolves in acid and SiO2 is
insoluble.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)
Or Add NaOH(aq) to the two remaining oxides. Al2O3 dissolves in base and SiO2
is insoluble.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)

Case 2
1. Add NaOH(aq) to all three oxides. Both Al2O3 and P4O10 dissolves. SiO2
insoluble.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
P4O10(s) + 12NaOH(aq) → 4Na3PO4(aq) + 6H2O(l)

2. Add water to the two remaining oxides. P4O10 dissolves and Al2O3 insoluble.
P4O10 + 6H2O → 4H3PO4

Case 3
1. Add dil. HCl to all three oxides. SiO2 insoluble. Both Al2O3 and P4O10 dissolves.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)
P4O10 + 6H2O → 4H3PO4

Note: That P4O10 does not undergo acid-base reaction, rather it dissolves in the aqueous
solvent.

2. Add water to the two remaining oxides. P4O10 dissolves and Al2O3 insoluble.
P4O10 + 6H2O → 4H3PO4

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● Observations to identify the oxide (The solid dissolves)

● Logical flow and steps/ sequence to identify all 3 oxides (i.e. 2 reagent chosen)
●● For correct equations for each reagent suggested

Note:
All equations must be balanced.
There are visible observation where the solid dissolves in the reagent hence the use of
indicators (such as litmus or universal indicator) is not necessary.
Common errors are seen from the confusion of oxide reactions with chlorides reactions.
There is no effervescence of gas for reaction of the oxides with water, acids and bases.

(iii) Suggest the pH values of the solutions formed when L, M and N are added separately to
water. [1]

●The pH values for L (SiO2) M (P4O10) and N (Al2O3) are 7, 2 and 7 respectively.

ECF awarded based on the identity of L, M and N in f(i)

[Total: 20]

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3 Propofol is a powerful sedative used to maintain general anesthesia.

Propofol
The half-life for the elimination of propofol from the body is 30 min. For a particular surgery, the
(a)
patient needs to be sedated for 45 min. When the blood plasma propofol concentration drops to
5.0 x 10–7 g cm–3 in the body, the patient will become unsedated.

The elimination of propofol from the body follows a first order kinetics.
Calculate the mass of propofol that needs to be administered by an anesthetist at the start
(i)
of surgery.
You may assume that the body blood volume is 5 dm3. [2]
Half–life for the elimination of propofol = 30 min
45
● No of half–lives needed for effective sedation in 45 min = = 1.50
30

Method 1
Use the formula to solve,

[A]t = [A]o  (½)n where n = number of half-lives

[A]o= the original/ initial concentration of A
[A]t = the concentration of A at time t

𝐦𝐚𝐬𝐬
5 x 10–7 =  (½)1.5
𝟓.𝟎𝟎 / 𝟏𝟎𝟎𝟎

Mass of propofol to be administered = 7.07 x 10–3 g

Method 2
Minimum mass of propofol before patient wakes up
= 5 x 10–7 x 5 x 103 = 2.50 x 10–3 g

● Mass of propofol to be administered = 2.50 x 10–3 x 21.5 = 7.07 x 10–3 g

Comments:
1 It is not possible to use proportion to solve as the rate follows first order kinetics depicted
as a decreasing curve for conc vs time graph (and not a straight line graph). You need to
use the relationship of [A]t = [A]o  (½)n to solve the question.

The anesthetist will usually adjust the dosage of the sedative according to the body
(ii)
temperature of the patient.

Using the Arrhenius’ equation below, deduce qualitatively how the half-life of the
elimination of propofol is affected in a patient having a high fever.
Ea
−
k = Ae RT

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where k is the rate constant, A is the Arrhenius constant, Ea is the activation energy, R is
the gas constant and T is the temperature. [1]
When T increases due to a fever, k will increase
ln2
According to t½ = , half–life will decrease
k
● for both points with increasing k.

(b) Propofol is sometimes administered as a phosphate salt tablet, fospropofol, which has less side
effects than propofol.

fospropofol
Using your knowledge of chemical bonding, suggest an advantage of administering propofol in
the phosphate salt form. [1]

● The phosphate salt is an ionic compound which makes it more soluble in aqueous
solution/ better absorbed when ingested by the human body, forming ion–dipole
interaction with the water molecules.

(c) Isopropyl coumarin is another compound commonly used in the pharmaceutical industry.

isopropyl coumarin
Draw the structures of the organic compounds formed when isopropyl coumarin reacts with the
following reagents and conditions.
Hot alkaline KMnO4, followed by aqueous H2SO4 [1]
(i)

Type of reaction :
1 Vigorous oxidation of alkene
2 Alkaline hydrolysis of ester
● 3 Aq H2SO4 – for acidification of products

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Comments
1 R group directly attached to the benzene ring ( with at least one alkyl hydrogen atom) is
oxidised to –COOH group with strong oxidising agent,hot KMnO4 (under acidic or
alkaline conditions)

(ii) BrCl in CCl4 [1]

Type of reaction : Electrophilic Addition of alkene using interhalogen.

● Accept either one answer

Comments
1 No electrophilic substitution occurs as there is no halogen carrier eg AlB 3 stated in the
question. Only electrophilic addition of alkene group using interhalogen occurs.
Candidates to note that the reaction of interhalogen is identical to that of pure halogens;
the main difference is that in interhalogens, you would need to identify the electrophilic end
as the atom that is less electronegative atom to determine the major product. In this
particular question, there is no major or minor products hence both products above are
acceptable answers.

The boiling points of isopropyl coumarin and propofol are given in the table below.

Compounds Names Mr Boiling point/ oC

isopropyl coumarin 188.0 301

propofol 178.0 256

(iii) Both isopropyl coumarin and propofol are simple molecular structures.

Using structure and bonding, explain why the boiling point of isopropyl coumarin is higher
than that of propofol. [2]

Size of electron cloud for : isopropyl coumarin > propofol. [✔]

Extent of polarisation/distortion of electron cloud for isopropyl coumarin > propofol
[✔] Only award for correct IMF comparison
Strength of instantaneous dipole-induced dipole attractions for : isopropyl coumarin >
propofol [✔]

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Energy required to overcome the intermolecular attraction for: isopropyl coumarin >
propofol [✔] Only award for correct IMF comparison

●● 4 ticks
● 2-3 ticks

Note: Propofol has a large non–polar R group which hinders the formation of extensive
intermolecular hydrogen bonding

Common mistakes:
- Did not relate to distortion of electron cloud
- Incorrectly linked the distortion of electron cloud to strength of permanent dipole-
permanent dipole interaction.
(d) Studies have shown that consumption of alcohol will increase the clinical dosage of propofol
required for sedation.
Liquid W has a molecular mass of 58.0. The composition by mass is C, 62.1%; O, 27.6%; H,
10.3%.

(i) Show that the molecular formula of W is C3H6O. [2]

C O H
Mass / g 62.1 27.6 10.3
Amount 62.1/12.0 =5.175 27.6/16.0=1.725 10.3/1 = 10.3
(i.e. % mass/Ar)
Division by the 3.002 1.00 5.971
smallest amount
Simplest mol ratio 3 1 6

● Empirical formula of W: C3H6O with working

Let the molecular formula of W be (C3H6O) n

n [ (12.0 x3) + 6 (1.0) + 1 (16.0) ] = 58.0
n=1
● Molecular formula of W: C3H6O with working

Common mistake:
Equated the empirical formula to molecular formula without any working.

One of the isomers of W is a primary alcohol that increases the clinical dosage of propofol
(ii)
required for sedation.
Suggest the displayed formula of this alcohol. [1]

Common mistake:
- Did not give the displayed formula.
- Gave structures which are not primary alcohols eg CH3COCH3 OR CH3CH=CH(OH)
- Gave structures which is not an isomer of W (CH3CH2CH2OH i.e.C3H8O)

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Another isomer of W does not form orange precipitate when reacted with 2,4-
(iii)
dinitrophenylhydrazine. This isomer also does not form effervescence when reacted with
potassium metal.
Deduce, with reasoning, a possible structural formula of this isomer. [2]

● Deductions [1 mark for both]

W does not undergo condensation with 2,4-DNPH  W is not an aldehyde or
ketone / or W is not a carbonyl compound.
W does not undergo acid-metal displacement with K  W is not an alcohol
● Any one of the 3 possible structures of isomers of W

(iv) Using the Valence Shell Electron Pair Repulsion Theory, explain the shape of the molecule
around the oxygen atom in your isomer in (d)(iii). [2]

There are 2 bond pairs and 2 lone pairs around O atom.

• To minimise repulsion and maximize stability, 4 electron pairs and directed in a
tetrahedral manner (or to the corners of a tetrahedron) [1]
• Since lone pair – lone pair repulsion > lone pair – bond pair repulsion > bond pair
– bond pair repulsion, the shape is bent [1] for 1st and 3rd point
Award ecf based on answer in (d)(iiii)
Note: Check if there are lone pairs around the central atom.

(e) The atomic properties of propofol was determined through analytical techniques.
The graph below gives the second ionisation energies of seven consecutive unknown elements
G to M, with atomic numbers less than 20.

3.7

3.6
log10 (2nd I.E.)

3.5

3.4

3.3

3.2

3.1
G H I J K L M
Element

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(i) Explain why K has the highest second ionisation energy value. [1]

● Element K has the highest 2nd I.E. which corresponds to the removal of the 2nd
electron from the inner (electron) shell which is closer to the nucleus.
This valence electron removed from K+ experiences a very strong electrostatic
attraction from the nucleus. Hence, it requires more energy for removal.

(ii) Identify which element is oxygen. [1]

● Element H is oxygen.
Concept:
From the graph of 2nd I.E. of consecutive elements, Element K has the highest 2nd IE ➔
Removal of 2nd electron is from inner quantum shell
`Deduction: Element H is in Group 16.

(iii) Explain why the second ionisation energy for element I is lower than that of element H. [1]
2nd I.E. of element H: H+ (g) H2+ (g) + e
2 2 3 2 2 2
1s 2s 2p 1s 2s 2p
2nd I.E. of element I: I+ (g) I2+ (g) + e
2 2 4
1s 2s 2p 2
1s 2s 2p2 3

● There is inter-electron (inter-electronic) repulsion between the doubly filled 2p

orbital of I+ ion / between paired electrons in 2p orbital of I+ ion.

[Total: 18]

Section B
Answer the following question in this section. Use a fresh sheet of writing paper.

4 Use of Data Booklet is relevant for this question.

This question is about the properties and reactions of metals and its alloys.

(a) Beryllium is a group 2 metal that forms a strong alloy with copper, for metalworking.
Explain how the reactivity of group 2 metals as reducing agents varies down the group, and
relate this variation to Eo values. [2]
• Down the group, atomic radius increases and valence electrons are removed more
easily
• the metals are more readily oxidised (OR reactivity increases OR strength of
reducing agents increases), Eo values become more negative.

Common errors: Not relating the reactivity of the metals as reducing agents to the atomic
radius. Some wrong use of terms e.g. use of “ionic” instead of “atomic” radius for the atoms.

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(b) Brass is an alloy of zinc and copper which was used since the 13 th century for monuments
and architectural models.
Designs on the brass metal surface are created by a process called etching. The design is
drawn on the surface using a special ink and the unprotected surface is removed by etching.

Design on brass plate shown after etching

Source: Jewelry Making Journal
One particular etching process involves placing a brass plate in a solution of iron(III) chloride,
until the copper and zinc are both removed from the unprotected surface.

(i) Using relevant EO values from the Data Booklet, explain why the exposed brass
surface can be dissolved in aqueous iron(III) chloride. [2]

Cu2+ + 2e ⇌ Cu EO = +0.34 V
Zn2+ + 2e ⇌ Zn EO = -0.76 V
Fe3+ + e ⇌ Fe2+ EO = +0.77 V
• 1 mark for calculation of two EOcell. Qualitative comparison also accepted.
Reaction between Cu and Fe3+: 2Fe3+ + Cu → 2Fe2+ + Cu2+
EOcell = +0.77 – 0.34 = +0.43 V > 0
Reaction between Zn and Fe3+: 2Fe3+ + Zn → 2Fe2+ + Zn2+
EOcell = +0.77 – (-0.76) = +1.53 V > 0
• Since both reactions are spontaneous, copper and zinc metals will be
oxidized to give Zn2+ and Cu2+ ions by Fe3+ ions and the unprotected surface
can be dissolved.
Common errors:
Some errors in choice of oxidizing agents (to be reduced) to oxidise Zn and Cu.
EoCl2/Cl- = +1.36 V (cannot choose due to absence of Cl2 for reduction)
EoFe3+/Fe = -0.04 V (cannot choose as it is less positive than EoFe3+/Fe2+ for reduction)

EoCu+/Cu = +0.52 V (cannot choose as it is less negative than EoCu2+/Cu for oxidation)

(ii) An engineer claimed that aqueous sulfuric acid can be used instead of iron(III) chloride
for etching brass.
Comment on the engineer’s claim, supporting your answer using suitable data from
the Data Booklet. [2]

2H+ + 2e ⇌ H2 EO = 0 V OR SO42− + 4H+ + 2e ⇌ SO2 + 2H2O EO = +0.17 V

Cu2+ + 2e ⇌ Cu EO = +0.34 V
Zn2+ + 2e ⇌ Zn EO = -0.76 V

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Reaction between copper and acid:

• EOcell = 0 – 0.34 = -0.34 V < 0 OR EOcell = +0.17 – 0.34 = -0.17 V
• Reaction is non-spontaneous, Cu cannot be oxidized to Cu2+, acid is unable
to dissolve copper. The claim is incorrect.

Common errors:
EoS2O82-/SO42- = +2.01 V (cannot choose due to absence of S2O82-)
(c) (i) Potassium hexacyanoferrate(III), K3[Fe(CN)6], is used an oxidant in many chemical
reactions. The colour of solid K3[Fe(CN)6] is red.
Explain the colour of the solid. [3]

 In hexacyanoferrate(III), due to the presence of ligands, the five degenerate

3d orbitals are split into two energy levels due to the repulsion of the Fe 3+
ion and the -CN ligands.
 When a d electron from lower energy group is promoted to the higher energy
group (d-d electron transition),
 radiation corresponding to ∆E, green light, from the visible region, is
absorbed. Light of wavelength not absorbed (red light) will be seen as the
colour of hexacyanoferrate(III).
Common errors:
- “Five 3d orbitals” not “5 d orbitals”
- “d electron promoted to higher energy level” not “d orbital promoted to higher
energy level”
- “Light of wavelength not absorbed (red light)” not “Light of wavelength emitted (red
light)”
(ii) The colour of potassium hexacyanoferrate(III) changes to yellow when dissolved in
water.
Suggest an explanation for the change in colour. [1]

In aqueous state,  ligand exchange has occurred resulting in a different energy

gap, ∆E, between the non-degenerate orbitals.

(iii) Cyanide-containing compounds in acidic conditions are generally toxic due to their
ability to produce poisonous hydrogen cyanide. However, potassium
hexacyanoferrate(III) is much less toxic.
Suggest a reason for the lower toxicity of potassium hexacyanoferrate(III). [1]

Cyanide ion forms  strong coordinate/dative bond with the central iron(III) ion.
Hence it is less likely to produce HCN gas.

(d) A piece of copper metal is placed in a 200 cm3 solution of K3[Fe(CN)6]. Hexacyanoferrate(III),
Fe(CN)63-, is reduced to hexacyanoferrate(II), Fe(CN)64-, during the reaction.
2Fe(CN)63- + Cu ⇌ 2Fe(CN)64- + Cu2+

(i) Calculate the standard cell potential for the above reaction. [1]

 EOcell = +0.36 – 0.34 = +0.02 V

Note: You have to use EO (Fe(CN)63-/Fe(CN)64-) = +0.36V, and not EO (Fe3+/ Fe2+) =
+0.77V for calculation of EOcell.

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When equilibrium has reached, the standard free energy change is related to the equilibrium
constant, Kc, of the reaction by the following equation:
ΔGO = -RT ln Kc
Where R is the ideal gas constant and T is the temperature in Kelvins.

(ii) Calculate a value for the equilibrium constant for the reaction in (d)(i) and comment
on the significance of the value obtained. [3]

 ΔGO = -nFEOcell = -2(96500)(0.02) = -3860 J mol-1

ΔGO = -RT ln Kc → -3860 = -(8.31)(298) ln Kc
 Kc = 4.75
 Kc > 1 implies that at equilibrium, [products] is larger than [reactants] OR
position of equilibrium lies to the right.
Note: allow ecf from (d)(i)
Kc is not an indication of the spontaneity of the reaction.

(iii) Write an expression for the equilibrium in (d) and hence, determine the mass of copper
dissolved when 90% of Fe(CN)63- ions have reacted. [3]

Ratio of Fe(CN)64- : Fe(CN)63- is 9:1

𝟒− 𝟐
[𝑭𝒆(𝑪𝑵)𝟔 ] [𝑪𝒖𝟐+ ]
 𝑲𝒄 = 𝟑− 𝟐
[𝑭𝒆(𝑪𝑵)𝟔 ]
𝟗𝟐 [𝑪𝒖𝟐+ ]
𝟒. 𝟕𝟓 =
𝟏𝟐
 [Cu2+] = 0.0586 mol dm-3
Cu2+ ≡ Cu
 Mass of copper dissolved = 0.0586(200/1000)63.5 = 0.745 g
Note: allow ecf from (d)(ii)

(e) Rhodium is a transition metal, commonly used as catalysts such as the Wilkinson catalyst
for the hydrogenation of alkenes.
State the role of rhodium and property typical of transition metals, which allows rhodium to
behave as a catalyst. [2]

Rhodium acts as a  heterogenous catalyst as it has  partially filled d-subshell that

allows adsorption of reactant molecules onto the surface as vacant d orbitals can act
as electron pair acceptors from reactant molecules.

[Total: 20]

9729/TJC H2 Chemistry MYA/2019 [Turn over