Temasek Junior College 2022 Jc2 March Common Test Higher 2: Worked Solutions

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TEMASEK JUNIOR COLLEGE

2022 JC2 MARCH COMMON TEST
Higher 2
CANDIDATE
WORKED SOLUTIONS
NAME
SUBJECT
CG / 21 TUTOR’S NAME
CHEMISTRY 9729
Section C Free Response 24 March 2022
1 hour
Candidates answer on the Question Paper.
Additional Material: Data Booklet


READ THESE INSTRUCTIONS FIRST
Write your name, CG and subject tutor’s name on all the work you hand in.
Do NOT open this booklet until you are told to do so.
Answer all questions in the spaces provided on the Question paper.
If additional space is required, you should use the pages at the end of this booklet. The question number must be
shown clearly.
For Examiner’s Use
Section C Q1 / 20
Q2 / 20
TOTAL / 40
This document consists of 15 printed pages and 1 blank page.
9729 / TJC MCT / 2022 [Turn over

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Section C Free Response

Answer all the questions
1 (a) In an experiment to investigate the mechanism of reaction between 2-bromobutane and

aqueous sodium hydroxide, a small quantity of 0.01 mol dm-3 sodium hydroxide is added to an
excess of 2-bromobutane in the presence of a few drops of phenolphthalein.
As the reaction proceeds, the hydroxide ions are used up and a colour change is observed in
the solution. The experiment is repeated with varying concentrations of hydroxide and 2-
bromobutane, and the time taken for the colour change is recorded in Table 1.1.
Table 1.1
Experiment Volume of 2- Volume of Volume of Volume of time taken for
bromobutane/ NaOH(aq)/ solvent/ phenolphthalein/ colour to
cm3 cm3 cm3 cm3 change/ s
1 0.50 6.00 3.40 0.10 60
2 1.00 6.00 2.90 0.10 30
3 1.00 3.00 5.90 0.10 15
(i) Write a balanced equation for the reaction between 2-bromobutane and aqueous sodium
hydroxide. [1]
•
CH3CHBrCH2CH3 + NaOH → CH3CH(OH)CH2CH3 + NaBr

Do not allow answers in terms of molecular formula C4H9Br, C4H10O
(ii) State the colour change observed in the experiments. [1]

• From pink (due to the presence of hydroxide) to colourless
(iii) Calculate the initial rate for each of the three experiments and use the results to deduce
the order of reaction with respect to 2-bromobutane and sodium hydroxide. Explain your
reasoning. [3]
Volume of NaOH
initial rate ∝ time
Experiment initial rate

1 6/60 = 0.100
2 6/30 = 0.200
3 3/15 = 0.200
• 1 mark for all initial rates
• Comparing experiments 1 and 2, when [2-bromobutane] increases by 2 times, the rate
increases by 2 times. Reaction is first order with respect to [2-bromobutane].
• Comparing experiments 2 and 3, when [OH-] decreases to half, the rate remains
unchanged. Reaction is zero order with respect to [OH-].
9729 / TJC MCT/ 2021 [Turn over

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(iv) Hence, state the rate equation and name the mechanism of the reaction between 2-
bromobutane and sodium hydroxide. [1]
✓ rate = k[2-bromobutane]
✓ SN1
1 mark for 2 marking points
Allow ECF from (iii). If order of reaction wrt [OH-] was deduced to be 1,
rate = k[2-bromobutane][OH-] SN2
Do not accept other incorrect orders of reaction with respect to hydroxide e.g. -1
(v) The experiment was separately repeated using 2-bromobut-1-ene and 2-chlorobutane
instead of 2-bromobutane.
Cl
2-bromobut-1-ene 2-chlorobutane

Arrange 2-bromobut-1-ene, 2-chlorobutane and 2-bromobutane in order of increasing
ease of hydrolysis. Explain your answer. [3]
Increasing ease of hydrolysis:
• 2-bromobut-1-ene, 2-chlorobutane, 2-bromobutane
• In a hydrolysis reaction, the C-X bond needs to be broken, and since the bond energy
of C-Br (280 kJ mol-1) is lower than that of C-Cl (340 kJ mol-1), 2-bromobutane is more
reactive than 2-chlorobutane.
• 2-bromobut-1-ene is resistant towards hydrolysis OR is the least reactive due to the
overlapping p orbitals of Br atom and the carbon atoms in C=C OR delocalisation of
electrons of the bromine atom into the  bond, resulting in partial double bond
character of C-Br bond, which is stronger.
OR 2-bromobut-1-ene is resistant towards hydrolysis as the electrons of the  bond
repel the attacking nucleophile

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(b) Two common qualitative analysis tests are used to differentiate between the different classes of
alkyl halides.
Test 1: Alcoholic silver nitrate test

When silver nitrate is added to an alkyl halide in ethanolic conditions, a silver halide precipitate
may form after some time:
AgNO3 + RX + CH3CH2OH ⎯→ ROCH2CH3 + HNO3 + AgX(s)
Test 2: Sodium iodide / propanone test

When sodium iodide in propanone is added to an alkyl halide (chloride or bromide), a sodium
chloride or sodium bromide precipitate may form after some time:
NaI + RCl ⎯→ RI + NaCl(s)
NaI + RBr ⎯→ RI + NaBr(s)
These two tests were performed on a series of alkyl halides and the results are tabulated in
Table 1.2.
Table 1.2

Test 1 Test 2
Alkyl Halide Time taken for precipitate Time taken for precipitate
to appear in alcoholic to appear in sodium iodide
silver nitrate test / propanone test
1-bromobutane 5 min 1 min
2-bromobutane 3 min 13 min (with heating)
2-bromo-2-methylpropane 1 min No ppt
Due to the conditions used, alkyl halides react predominantly by SN1 mechanism in test 1.
However they react predominantly by SN2 mechanism in test 2.
(i) By considering the structure of the alkyl halides used in the tests and the information in
Table 1.2, explain why the results confirm the predominant mechanism undergone in each
test. [3]
✓ Tertiary halogenoalkane (2-bromo-2-methylpropane) reacted fastest in the test 1
(AgNO3 test) while it hardly showed any reaction in test 2 (NaI test).
✓ Primary halogenoalkane (1-bromobutane) reacted slowest in test 1 while it reacted the
fastest in test 2. [1 mark for observation]
• Tertiary halogenoalkanes form stable carbocations and tend to react via SN1
mechanism, which can be seen from its fast reaction in the test 1. [1]

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• However, there is a great amount of steric hindrance caused by the 3 R- groups in

tertiary halogenoalkanes, hence causing reaction via SN2 mechanism to be very slow.
[1]
(ii) The equation for the reaction between ethanol and 2-bromobutane is shown in Fig 1.1.
H H
CH3 CH2CH3 + CH3CH2OH CH3 CH2CH3 + HBr
Br OCH2CH3
Fig 1.1
Using Fig 1.1 and the information provided in (b)(i), describe the mechanism of the
reaction between ethanol and 2-bromobutane in test 1. Show relevant lone pairs and
dipoles, and use curly arrows to indicate the movement of electron pairs. [2]
√ SN1 mechanism
CH 2CH 3 CH2CH3
+ − slow -
CH3 C Br CH3 C+ + Br

H [1]
CH2CH3 CH 2CH 3
HOC 2H5 fast +

CH3 C+ CH3 C OC2H5 + H
H H √
1 mark: step 1 with arrows, dipoles, movement of electrons, slow/fast steps
1 mark: name of mechanism and step 2
(not necessary to show how H+ is extracted from the resulting compound)
(iii) A sample of optically pure 2-bromobutane rotated plane-polarised light by +89. Describe
and explain the optical activity of the organic product formed when 2-bromobutane is
reacted with ethanolic silver nitrate in test 1. [2]
✓ The product does not rotate plane polarised light.
✓ A racemic mixture is formed.
✓ Carbocation is planar around the electron-deficient carbon atom.
✓ Nucleophile attacks the carbocation from either side of the plane with equal probability,
forming equimolar amounts of enantiomers.
2 ticks = 1 mark

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(c) X is a compound made from two Period 3 elements. X reacts with excess water to form a
solution, FA 1.
When aqueous silver nitrate was added to a portion of FA 1, a white precipitate Y was observed.
When sodium carbonate was added to another portion of FA 1, effervescence of gas Z was
observed. FA 1 forms a white precipitate with aqueous sodium hydroxide, which is soluble in
excess aqueous sodium hydroxide.
(i) State the identities of
• compound X,
• the white precipitate Y, and
• the gas Z formed. [2]
✓ X is AlCl3
✓ White ppt Y is AgCl
✓ Gas Z is CO2
3 marking points – 2 marks, 2 marking points – 1 mark
(ii) With the aid of equations, explain the reactions that take place when X is mixed with
excess water. [2]
• AlCl3 undergoes hydration and hydrolysis. The high charge density of aluminium

ion polarises water molecules, weakening the O-H bond and causing it to break.
• AlCl3(s) + 6H2O → [Al(H2O)6]3+(aq) + 3Cl–(aq)

[Al(H2O)6]3+ + H2O ⇌ [Al(H2O)5(OH)]2+ + H3O+
For markers: accept MgCl2 and ECF [1] for the concept of hydration and hydrolysis
[Total: 20]

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2 (a) (i) Aldehydes such as propanal undergo nucleophilic addition reaction to form 2-
hydroxybutyronitrile, shown below.
State the reagent and condition for the above reaction. [1]
HCN, trace KCN or NaOH, 10 to 20 oC / cold
Under acidic conditions, aldehydes undergo nucleophilic addition reaction with alcohols. In this
reaction, an aldehyde molecule reacts with 2 equivalent of alcohol molecules reversibly to form
acetals. The reaction goes through the formation of a hemiacetal, as shown below.

R1 and R2 are alkyl groups.
(ii) The mechanism for the formation of the hemiacetal is as follows.

• The carbonyl oxygen is first protonated by the acid catalyst.
• The alcohol then acts as a nucleophile to attack the electron deficient carbonyl carbon
to form an intermediate.
• The intermediate deprotonates to produce the hemiacetal and regenerate the
catalyst.
Suggest a mechanism to show how propanal and ethanol react in the presence of acid
catalyst to form a hemiacetal. Show clearly relevant curly arrows, charges and lone pairs.
[3]

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1  for each correct step with use of curly arrows, charges and lone pairs
Accept step 3 without H2O to remove H+, but must still show curly arrow.

(iii) Under suitable conditions, the rate equation for the formation of hemiacetal in (a)(ii) is
given by:
Rate = k[CH3CH2CHO][CH3CH2OH]
With reference to the mechanism of the reaction in (a)(i) and (a)(ii), explain why the rate
of reaction of (a)(ii) is slower than in (a)(i). [1]
Reaction of propanal with ethanol would be slower than with HCN, as the  ethanol
is a weaker nucleophile than CN- since the former is neutral and attacks the
electron deficient carbon less readily.
(b) Compound E reacts with hot aqueous KOH. Analysis shows that among the mixture of
products, a non-ionic product F, C10H12O, is formed.
(i) Draw the structure of product F. [1]

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(ii) Explain briefly how product F is formed. [2]
The  phenol OH undergoes acid-base reaction with KOH to form a phenoxide ion
and undergoes  intramolecular nucleophilic substitution with the chloroalkane to
form a cyclic ether.
(iii) Other than iron(III) chloride, suggest another chemical test to distinguish E from F.
Construct an equation for the reaction involved. [3]
 Test: add aqueous Br2

 for both observation
E: decolourisation of orange solution to colourless and formation of white ppt.
F: orange solution remains / no decolourisation


Alternative test 1
 Heat both compounds with NaOH(aq), acidify with HNO3(aq) and add AgNO3(aq).
E: white ppt of AgCl
F: no white ppt of AgCl
 for both correct equations
Ag+ + Cl- → AgCl(s)
Alternative test 2

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 Heat both compounds with ethanolic silver nitrate

E: white ppt of AgCl
F: no white ppt of AgCl
 for both correct equations
Alternative test 3
(c) Hydrocarbon G, C9H8, reacts with equimolar of steam in the presence of phosphoric acid to
give C9H10O, which has 2 pairs of enantiomers. Treatment of C9H10O with hot acidified
potassium dichromate produces I, C9H8O.
Compound I reacts with bromine in UV light to produce only 2 mono-brominated products, J

and K. J reacts with bromine in UV light faster than K.
G produces H with hot acidified potassium manganate(VII), which gives yellow solid with
alkaline aqueous iodine. Further increasing the temperature produces benzene-1,2-
dicarboxylic acid.
Deduce the structures of G, H, I and J, explaining the chemistry of the reactions involved. [9]
Observation Deduction
G reacts with equimolar of ✓ Electrophilic addition → ✓ G has 1 alkene

steam to give C9H10O, which group with molecular formula C9H8 (since there is
has 2 pairs of enantiomers only 1 O atom, 1 G reacts with 1 H2O)
✓ G has high C:H ratio → G has a benzene ring.
✓ C9H10O has 2 chiral centres with non-
superimposable mirror images.
Treatment of C9H10O with ✓ Oxidation (no change in the number of oxygen

acidified K2Cr2O7 gives I. atoms) → ✓ I has a ketone group and C9H10O
has a secondary alcohol group.

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I reacts with bromine in UV ✓ Free radical substitution → ✓ I has only 2

light to produce only 2 mono- different hydrogen atoms for substitution.
brominated products, J and K.
✓ J has either tertiary or secondary hydrogen
J reacts with bromine in UV and K either has secondary or primary H for
light faster than K. substitution.
G produces H with hot KMnO4, ✓ Oxidation with KMnO4 (complete C=C

which gives yellow solid with cleavage) and alkaline aqueous iodine → ✓ H
alkaline aqueous iodine. has -COCH3 group
Further increasing the Oxidation → ✓ G and H have substituents on

temperature produces the 1 and 2 positions of the benzene ring (further
benzene-1,2-dicarboxylic acid. oxidation of phenylethanone to -COOH group)
G H I J

Every 2 ✓ = 1 m (max 5 marks, with 2 bonus ticks)
Every correct structure = 1 m
[Total: 20]


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