2019 Y6 Common Test 1 Suggested Solutions

Section A

Question 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Answer C A B D B B D C A C C D A B D

Question 1 (C) Question 4 (D)

From Na2O to P4O10, In this question, 0.10 mol dm3 NH3(aq) in burette is
A covalent character increases since added to 25 cm3 of 0.10 mol dm3 HCl(aq). This is
electronegativity increases from Na to P. also evident from initial acidic pH and the label on
B melting point increases to MgO before the horizontal axis.
decreasing.
For pH = pKa of NH4+,
C pH decreases as the oxides go from ionic
 it is in the buffer region i.e.
(basic) oxides to ionic with covalent character
[NH4  ]
(amphoteric) oxides to covalent (acidic) pOH  pK b  lg , and
oxides. [NH3 ]
D solubility in aqueous alkali increases. The  [NH3] = [NH4+], so
acidic oxides are more soluble in aqueous
alkali. pOH  pK b  lg(1)
 pOH  pK b

Question 2 (A)
There is a large decrease in first IE from element A
to B ⇒ element A is from Group 18. Element A is Ne,
not He, since A to E are from Periods 2 or 3. B is Na;
C is Mg; D is Al; E is Si.
1 Incorrect. From the Data Booklet, Mg+ is
smaller than Na+.
2 Correct. D (Al) has the highest electrical
conductivity among elements A to E.
3 Correct. Electronegativity increases from B
to E due to increasing nuclear charge with
approximately constant shielding.
Question 3 (B)
Deductions from statement
A R is from Group 1, 2, 13, 14 or 15. Fits C, D
B Chloride of R is ionic in nature. --
C R is from Group 15. Fits A, D
D Chloride of R is covalent in nature. Fits A, C
 14  pOH  14  pK b
 pH  pK a
When NH3(aq) is mixed with HCl(aq),
NH3 + H+ (from HCl) ⟶ NH4+.
Most popular wrong answer : B
At B, 12.5 cm3 of 0.10 mol dm3 NH3(aq) is added to
25 cm3 of 0.10 mol dm3 HCl(aq). The resultant
mixture consists of NH4+ and unreacted HCl i.e.
not a buffer.
Correct answer : D
To reach D, 50 cm3 of 0.10 mol dm3 NH3(aq) is
added to 25 cm3 of 0.10 mol dm3 HCl(aq). All of the
The resultant mixture consists of 0.0025 mol of
excess NH3 and 0.0025 mol of NH4+, which satisfy
the criteria state above.

1
Question 5 (B)
(1) C6H5COOH + HCO3– ⟶ C6H5COO– + H2CO3 Question 7 (D)
In the free radical substitution of cyclohexane by Br2
2 Incorrect. Benzoic acid is the acid in the with UV light, products involving the collision of the
forward reaction of (1) while carbonic acid is cyclohexyl radicals in the termination steps may be
the acid in the backward reaction of (1). formed.
Since the forward reaction of (1) proceeds,
The number of carbons in these products should be
benzoic acid is more acidic than carbonic acid.
multiples of 6 i.e. 6, 12, 18 etc
4 Correct. Since the forward reaction of (1)
proceeds, benzoate is more stable than A Total of 11 carbons – cannot be formed from
hydrogen carbonate i.e. hydrogen carbonate cyclohexyl radicals.
is less stable than benzoate. B Total of 10 carbons – cannot be formed from
cyclohexyl radicals.
(2) C 6H 5 OH  HCO 3   C 6H 5 O  + H 2 CO 3 C Total of 13 carbons – cannot be formed from
1 Correct. Phenol is the acid in the forward cyclohexyl radicals.
reaction of (2) while carbonic acid is the acid D Total of 18 carbons – formed from the
in backward reaction of (2). following radicals.
Since the forward reaction of (2) does not
proceed, phenol is less acidic than carbonic
acid i.e. carbonic acid is more acidic than
phenol.
3 Incorrect. Since the forward reaction of (2)
does not proceed, hydrogen carbonate is
more stable than phenoxide.

Question 6 (B) Question 8 (C)

When 10 cm3 of 0.10 mol dm3 HNO3(aq) and 20 cm3 In this reaction, Br2 acts as the electrophile which
of 0.10 mol dm3 CH3CH2NH2(aq) were mixed, attacks the C=C and forms the corresponding
carbocation in the slow step.
CH3CH2NH2 + H+ ⟶ CH3CH2NH3+
Initial 20(0.1) 10(0.1)
amt / 1000 1000 0
mol  0.002  0.001
Final
amt / 0.001 0 0.001
mol

The resultant solution is a 1:1 mixture of a weak A Product is formed from attack of Br– in the fast
base and its conjugate acid i.e. a buffer solution.
Therefore, step.
[CH3CH2NH3  ]
pOH  pK b  lg
[CH3CH2NH 2 ]
0.001
pOH  pK b  lg
0.001
pOH  pK b

Since the buffer was prepared at 60 °C where

pKw = 13.0 and pKb of CH3CH2NH2 = 3.0,
pOH  3.0
pH  13.0  3.0  10.0

2
 B Product is formed from attack of H2O in the fast Question 10 (C)
step. A Feasible in two steps.

B Feasible in two steps.

C Not feasible in two steps or less.

C Product cannot be formed because 2 –OH

groups were added, implying that there was an
+
OH electrophile which is not possible in this
question.
D Product is formed from an intramolecular
attack by –NH2 on the carbocation.

D Feasible in two steps.

Question 11 (C)
1 Secondary
halogenoalkane may
undergo SN1 or SN2
mechanism.
2
Lone pair of e– on Br delocalises into
Question 9 (A)
Generation of electrophile pi-electron cloud of C=C. C–Br bond has
partial double bond character and does not
+ H+
break easily i.e. it does not undergo
nucleophilic substitution easily.
sp2 sp3
hydrocarbon X
3 Tertiary halogenoalkane
A - Incorrect. X is cyclohexene. undergoes SN1
D - One of the alkene carbon changes mechanism.
hybridisation from sp2 to sp3.
Electrophilic attack 4 Primary halogenoalkane
undergoes SN2
slow mechanism.

H
electrophile
B - Correct.
C - Correct. Benzene donates a pair of electrons
to the electrophile i.e. it acts as a nucleophile.

Loss of proton from intermediate

fast
+ H+
Question 12 (D)
H
3
When treated with alcoholic KOH, the bromoalkane
undergoes elimination to form an alkene. The C–Br
bond in the bromobenzene cannot be broken easily
due to its partial double bond character.
Question 14 (B)
Under the conditions of H2/Ni, heat, H2 is added to
C=C to form the corresponding alkane and to –C≡N
to form –CH2NH2. The benzene ring is not
hydrogenated.

Question 13 (A)
1

Question 15 (D)
The compounds given in the question are alcohols.
Only alcohols of the form –CH(OH)CH3 give a yellow
ppt of CHI3 with aqueous alkaline iodine.

HCl(aq) does not react with alcohols.

Typically, heating with HCl(g) is required.

4
Section B

B1(a)(i) NaCl(s)  Na+(aq) + Cl(aq)

pH = 7

AlCl3(s) + 6H2O(l)  [Al(H2O)6]3+(aq) + 3Cl–(aq)

[Al(H2O)6]3+(aq) + H2O(l) ⇌ [Al(H2O)5(OH)]2+(aq) + H3O+(aq)
pH = 3
Examiner’s Comments
 When NaCl is added to water, hydration of NaCl (NOT hydrolysis) occurs, where water
molecules surround Na+ and Cl ions, forming Na+(aq) and Cl(aq). O-H bonds in H2O
are not broken and there is no NaOH or HCl formed.
 When AlCl3 is added to excess water, AlCl3 forms the aqua complex [Al(H2O)6]3+, which
then undergoes hydrolysis to generate H3O+, due to the high charge density of the Al3+
ion. During the process of hydrolysis, the O-H bond in H2O is broken.

B1(a)(ii) Na+ has low charge density and does not undergo hydrolysis.

Since Al3+ has high charge density and hence high polarising power, it is able to distort the
electron cloud in H2O molecules, thus causing –OH bond to break/hydrolysis, releasing
H+/H3O+.
Examiner’s Comments
 Students need to read the context of the question, which says that NaCl and AlCl3 form
aqueous solutions with different pH values. Hence the answer should focus on why
Al3+(aq) is acidic and Na+(aq) is not.
 Many answers showed poor understanding that the cause of acidity is due to excess
H+ in solution, which comes from the breaking of the O-H bond in H2O. Some answers
also showed poor understanding of “polarising power” or “distortion of the electron
cloud in H2O”.

B1(a)(iii) Effervescence of CO2 gas which forms a white precipitate with aq. Ca(OH)2 / limewater
White precipitate of Al(OH)3 is formed.
Examiner’s Comments
 When writing observations for gases evolved, the test used to identify the gas should
be included.
 The white precipitate of Al(OH)3 was often left out of students’ answers.

B1(b)(i) W Na[Al(OH)4] or Al(OH)4

X Mg(OH)2

Examiner’s Comments
 Adding dropwise until no further change means that a reagent is added slowly until in
excess.
 In step 2, aq. NaOH was added dropwise until no further change was observed. Since
Al3+ and Mg2+ are present in the solution after step 1, the following transitions have
occurred with excess NaOH added in step 2:
Al3+(aq)  Al(OH)3(s)  Al(OH)4(aq)
Mg2+(aq)  Mg(OH)2(s)
Hence the species present in the filtrate is the soluble Al(OH)4(aq), and the insoluble
species present in the residue is Mg(OH)2(s).
 A common mistake was naming Al(OH)3 as the filtrate, when Al(OH)3 is an insoluble
solid.

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B1(b)(ii) Al3+ (aq) + 3OH (aq)  Al(OH)3(s)

Al(OH)3(s) + OH (aq)  Al(OH)4 (aq)

Examiner’s Comments
 Ionic equations were required, so the spectator ions like Na+ should be removed from
the equations.
 Answers were often missing in the state symbols, even though the question stated that
state symbols should be included.
 Answers also included Mg2+/Mg(OH)2 which is not present in the filtrate.
 It is important that students learn to follow a sequence of steps and understand the
chemistry behind them. Many students seem to have difficulty following through
questions which have long sequences or have a lot of information provided.

B1(b)(iii) Y is Al(OH)3

Equation: Na[Al(OH)4] + CO2  NaHCO3 + Al(OH)3

Examiner’s Comments
 A very common mistake was identifying Y as Al2(CO3)3, which does not exist in
aqueous solution, as Al3+(aq) is acidic and reacts with CO32 to form CO2.

B2(a)(i) HNO3 + (CH3CO)2O ⇌ NO2+ + CH3COOH + CH3COO–

Examiner’s Comments
 Many mistakes were made in balancing the final equation. Students should know that
all chemical equations must be balanced by atoms and by charge.
 In order to write the overall equation from the given process, students need to
 identify the reactants (namely HNO3 and (CH3CO)2O as seem from the scheme
provided), and
 identify and remove any intermediates by ensuring that the intermediates are
consumed in one of the processes.
(I) 2HNO3 + (CH3CO)2O ⇌ N2O5 + 2CH3COOH
(II) N2O5 + (CH3CO)2O ⇌ 2CH3COONO2
2 X (III) 2CH3COONO2 ⇌ 2NO2+ + 2CH3COO–
Summing the above will allow give you the overall equation.

B2(a)(ii)

6
 Examiner’s Comments
 Students need to read the question and understand the requirements of the question
 Students were asked to draw the displayed structure of the NO2+ electrophile in the
mechanism. Only a handful of students drew it correctly.
 The question asked for any movement of electron pairs to be shown using curly
arrows i.e. . Since the displayed formula of NO2+ was drawn, a curly arrow needs
to drawn to show the breaking of the N=O pi bond. Since the new covalent bond is
formed between the C on the benzene ring and the N on the electrophile, the first
arrow must be pointed at the N atom. Since N already has 8 electrons, one of the
double bonds is broken and the electrons transferred to O.
 Many students are unfamiliar with the small but important details in the electrophilic
substitution mechanism. Please clarify with your tutors if you do not understand the
following points.
 Curly arrows – Students must be mindful and intentional about where each curly
arrow starts and ends. For example, since the electrons from the pi-electron cloud
are used to form a bond with N of NO2+, the curly arrow should start at the pi-
electron cloud of benzene and point to the N of NO2+.
 When drawing the structure of the intermediate, ensure that the delocalisation of
electrons in the ring are spread across the sp2 carbon atoms only, and that the
positive charge is in the ring, and not on the sp3 carbon.

B2(a)(iii) Since O is more electronegative than N, the N atom is electron deficient and is more
prone to attack by the electron rich benzene ring.
Examiner’s Comments
 Many students wrongly explained that N was electron deficient due to the positive
charge or an empty p orbital or dative bond formation. Any answers alluding to any of
the above reasons for the electron deficiency were not accepted.
 Students should be careful about cause and effect in such explanations. For example,
“The N atom is electron deficient and positively charged” versus “The N atom is electron
deficient because of the positive charge.” The first statement gives two separate facts
which are correct and accepted. The second statement has an incorrect reasoning and
is not accepted.

B2(b)(i) 0.7 x 0.8 x 0.35 = 0.196 mol

Examiner’s Comments
 Generally, well done.

B2(b)(ii)

The product is 1,4-disubstituted. Alkylation should be the first step as alkyl groups are
2,4-directing and can direct the incoming group to the 4-position, unlike –NO2 and –COOH
which are 3-directing.

Among the alkyl side chains which has at least one benzylic hydrogen (and therefore
oxidisable), the –CH(CH3)2 substituent gives the highest percentage of 4-substituted
products via nitration. (Alternative: Although the –C(CH3)3 substituent gave the highest
percentage of 4-substituted products via nitration, it does not contain a benzylic hydrogen.
Thus, it cannot be oxidized to form the final product. Therefore, the next best –CH(CH3)2
substituent was chosen.)

7
 Examiner’s Comments
 Many students who chose the –C(CH3)3 substituent forgot that this side-chain cannot
be oxidised to benzoic acid due to the lack of the benzylic hydrogen.
 Students who chose the correct alkylbenzene left out the full explanation or explained
poorly using incorrect terminology.
 Students should avoid using terms that they are not familiar with, such as -hydrogen,
tertiary carbon / tertiary alkyl group, etc. The name depends on the number of carbon
atoms directly attached to the C of interest (underlined below).

Primary C Secondary C Tertiary C Quaternary C

(only one C atom (two C atoms (three C atoms (four C atoms
attached) attached) attached) attached)

B2(c)(i) The rates of nitration of the halogenated benzene compounds increases from
chlorobenzene to iodobenzene.

Down group 17, halogen atoms become less electronegative. This causes a decreasing
extent of electron withdrawal / less deactivating on the benzene ring.
Examiner’s Comments
 Many students did not state the trend as required in the question, or stated the trend in
vague terms, such as, “the rate increased with increasing size of the halogen.” Since
the size of the halogen was not given in the data table, it is not clear which halogen-
substituted benzene has the greatest rate of reaction.
 The reason for the increasing rate was also poorly explained. Again, students should
be mindful of the cause and effect implications in their answers. “As the halogen
increases in size, they become less electronegative” implies that electronegativity is
due solely to atomic radius.
 Many students were confused that the overlapping of the halogen p-orbitals with the -
electron cloud of benzene ring (i.e., the resonance effect) was responsible for the
electron withdrawing effect of the halogen. Halogens withdraw electrons from the
benzene ring through the  bonds (which are formed by overlapping sp2 orbitals on C
and X).
 A large number of students were also confused that the nitration reaction involved
substituting the halogen with the –NO2 group and explained the trend in terms of the
strength of the C–X bond. As clearly shown in the previous parts of this question, the
nitration reaction substitutes a H atom on the benzene ring, forming for example, 2-
chloronitrobenzene.

B2(c)(ii) As the valence orbitals of F are smaller than Cl / the p-orbitals of F are less diffuse than
Cl, they overlap more effectively with the -electron cloud of benzene ring. This
increases the electron density of the benzene ring to a greater extent in fluorobenzene
compared to chlorobenzene.

Alternative: As the size of the valence orbital of F is smaller than Cl / the p-orbitals of F
are less diffuse than Cl, the extent of electron donation into the benzene ring by
resonance increases and fluorobenzene is more reactive than chlorobenzene.
Examiner’s Comments
 Students must show clearly the comparison between fluorobenzene and
chlorobenzene to earn full credit.
 It is incorrect to state that F is an electron-donating or activating group. It is, however,
a less withdrawing group than Cl. Please recognise the distinction between “more
donating” and “less withdrawing”.
B3(a) D contains a tertiary alcohol group
8
 Examiner’s Comments
 Students are reminded that it is insufficient to merely state the presence of hydroxyl
group, alcohol group or –OH group.
 Many students incorrectly used the term “hydroxy” group. Note that these two terms
are not interchangeable. Hydroxy compounds contain hydroxyl group.
 Students are encouraged to spell “tertiary” instead of using the 3° notation.

B3(b)(i)

D E

F G
Examiner’s Comments
 Many students erroneously drew a secondary alcohol in structures D and E. Note that
reaction 1 causes both oxidative cleavage of alkenes and oxidation of alcohols.
 Students should draw the structures of the compounds in ink.

B3(b)(ii) C8H12O + 14[O] ⟶ C4H6O5 + C2H2O4 + 2CO2 + 2H2O

Examiner’s Comments
 Many students did not balance the number of hydrogen atoms and hence failed to
include H2O as one of the products.
 Many students miscounted the number of oxygen atoms.

B3(b)(iii) Elimination / Dehydration / Condensation (depending on structure drawn for G)

Examiner’s Comments
 This question is generally well done.
 The type of reaction in this part should correspond to the structure drawn for G.

B3(c)(i) 0 in C1, +1 in C2
Examiner’s Comments
 Many students did not assign the oxidation numbers correctly. These students should
refer to page 3 of the lecture notes on Introduction to Organic Chemistry, which
contains relevant worked examples.

B3(c)(ii) KMnO4(aq), NaOH(aq), cold

Examiner’s Comments
 Students should specify the base used and preferably include the state symbols of the
reagents here.

9
 B3(c)(iii)

and

H and J

OR [1]

K
Examiner’s Comments
 Students should draw the structures of the compounds in ink.
 Many students did not read the given information carefully and were not aware that K
is a 1,2-diol.

Section C

C1(a) Alkenes contain a high electron density carbon–carbon double bond/ electron cloud
which attracts electrophiles.

Alkenes are unsaturated and are able to undergo addition reactions as the C=C bond
contains the weaker  bond, which can be broken easily in addition reactions.

Examiner’s Comments
 Most students were able to identify that an alkene contains a region of high electron
density, which makes it susceptible to electrophilic attack.
 However, many students were unable to explain why an alkene undergoes addition
reactions. They did not highlight that the pi bond is weak and can be broken easily.

C1(b) Catalyst
Examiner’s Comments
 Most students were able to identify the catalytic nature of the acid.

C1(c)

Examiner’s Comments
 Most students were able to draw the curly arrows and label the partial charges
correctly.
 There was a minority who incorrectly drew the arrow from the positively charged carbon
to the C=C in step 2. Students are reminded that the arrows represent the movement
of electrons, not the positive charges.
10
C1(d)(i) Test: Heat E and F separately with KMnO4(aq) acidified with H2SO4(aq).

Observations:
E will decolourise purple KMnO4 and effervescence of CO2 gas that will form a white
precipitate in calcium hydroxide/limewater while
F will decolourise purple KMnO4 but there is no effervescence of CO2.

Examiner’s Comments
 Students are reminded to specify the acid used in the strong oxidation.
 Some students wrote concentrated KMnO4 and concentrated H2SO4, which were
incorrect.
 Many students failed to mention the decolourisation of KMnO4 as part of the
observations when performing the chemical test. Students are reminded that
all observations associated with the chemical test need to be recorded.

C1(d)(ii)

or

Examiner’s Comments
 Generally well done

C1(e)(i) Cis-trans isomerism

G: Cis isomer H: Trans isomer

Examiner’s Comments
 Many students correctly identified cis-trans isomerism. A small number of students
incorrectly stated enantiomerism.
 A minority group of students were still not able to distinguish the cis isomer from the
trans isomer based on skeletal formulae.

C1(e)(ii) There is a double bond present which restricts rotation about the bond.

Each carbon in the double bond has two different groups attached to them.
Examiner’s Comments
 Generally well done.

C1(f)(i) In the cationic intermediate of styrene, the positively charged carbon is adjacent to the
benzene ring, empty p orbital of the positively charged carbon overlaps with the pi electron
cloud of the benzene ring, allows the pi electrons of the benzene ring to delocalise over to
the positively charged carbon and disperse the positive charge.
Examiner’s Comments
 Many students were able to identify that the cation is stable due to the electron donating
effect of the phenyl group via resonance. However, many students were unable to
succinctly explain how the stability came about.
 Students who only mentioned that the cationic intermediate of styrene is stable due to
electron donating effect of the alkyl group were not given credit. This is because the
main stabilisation factor is due to the resonance stabilisation provided by the phenyl
group.

11
C1(f)(ii) No. There are electron-withdrawing fluorine groups which destabilises the carbocation,
therefore the activation energy required for its formation is high.
Examiner’s Comments
 Generally, well done.
 Some students identified fluorine as electron donating group, which is incorrect.

C2(a) Phenoxide ions are resonance-stabilised as the negative charge / lone pair of electrons on
O atom is delocalised into the ring due to the overlapping of the p–orbital of the oxygen
atom with the –electron cloud of the benzene ring. Such resonance stabilisation is absent
in the cyclohexanoxide ion.

The cyclohexanoxide ion contains electron donating alkyl groups which intensify the
negative charge on O atom. Such destabilisation does not happen in the phenoxide ion.
Phenoxide is a more stable ion and thus phenol is a stronger acid. Therefore phenol has
a lower pKa.

Examiner’s Comments
 Most students were able to recognise that the greater the stability of the conjugate
base, the stronger the acid, and they must clearly show this relationship in their answer.
 Students should phrase their answers clearly and indicate clearly whether they are
referring to the acid or the conjugate base instead of just ‘it’.
 Students should also make sure that they are communicating the correct idea.
Common mistakes such as “the p orbital of O atom is delocalised” or “the negative
charge is stabilised” show a lack of understanding of the concept.

C2(b)(i) Ka x Kb = Kw, thus Kb of phenoxide = 10–14/10–9.95 = 8.91 x 10–5 mol dm–3

Examiner’s Comments
 Student need to recognise that credit is only given when the answers are presented for
the correct part of the question. No credit was awarded to students who calculated Kb
only in (b)(ii).

C2(b)(ii) Kb = 8.91 x 10-5 = [OH–][C6H5OH] / 0.100

⇒ [OH–] = 2.98 x 10–3 mol dm–3

pOH = –lg (2.98 x 10–3) = 2.525

pH = 14 – 2.525 = 11.47 = 11.5 (3sf)
Examiner’s Comments
 Generally well done with the exception of some students calculating [H+] instead.
 Students should remember to leave the final answer to 3sf unless otherwise stated.

C2(c)(i)

Examiner’s Comments
 Very well done.

12
C2(c)(ii) The 3 electron-withdrawing –NO2 groups pull electron density away from the O- group in
the 2,4,6-trinitrophenoxide ion, and significantly disperses the negative charge. Thus the
2,4,6-trinitrophenoxide ion is much more stable than phenoxide, and J is a much stronger
acid than phenol.

Examiner’s Comments
 Students should clearly compare the stability of the conjugate base of J and the
conjugate base of phenol, in terms of extent of dispersal of negative charge.
 Do take note that it is ambiguous to use of the term “phenoxide ion” to represent the
conjugate base of J as the conjugate base of phenol is also a phenoxide ion.
 Students should identify the electron-withdrawing groups used in their explanations.

C2(d)

Examiner’s Comments
 Bromination of the benzene ring can also be achieved using Br2 with a suitable Lewis
acid such as FeBr3 or AlBr3. However these Lewis acids cannot be used in aqueous
medium as they hydrolyse in water, rendering them ineffective as Lewis acids. Hence,
the aqueous state symbol should not be used.
 The activating / deactivating ability of the –OCH3 can be deduced from the Data
Booklet. Please make sure you know how.
 Like –OH, the –OCH3 group is quite activating as the lone pair of electrons on O of
–OCH3 can delocalise into the benzene ring, increasing the electron density in the
benzene ring and making it more susceptible towards electrophilic substitution. Hence,
it is possible to use Br2(aq), without the use of Lewis acid catalyst, for the bromination
of C6H5OCH3.

C3(a)(i)

Examiner’s Comments
 A common mistake was incorrectly writing the functional group as –NH3 instead.
 Some students mistakenly thought that there is electrophilic addition at the C=C.

C3(a)(ii) Slower. The C–Cl bond is stronger than the C–Br bond.
Examiner’s Comments
 For any question, students should always take reference from the indicated marks to
decide how much to write. If there were more marks allocated, a detailed explanation
as to why the C–Cl bond is stronger would then have been necessary.
 The bond should be clearly stated as a C–Cl bond, not R–Cl bond.
 Some students mixed up their explanations with reference to the H–Cl bond instead.

13
C3(a)(iii) sp2
Examiner’s Comments
 All science notations, symbols, formulae and conventions etc. should be strictly
adhered to and correctly written / presented.
 No credit can be expected for improper / incorrect notations such as sp2, sp2, SP2 etc.

C3(a)(iv) This is because the lone pair of electrons in the p orbital of the bromine atom interacts with
the pi-electron cloud of the adjacent C=C bond and is delocalised. This results in partial
double bond character in the C–Br bond. This bond is strengthened and hence not easily
broken.

The electron-rich C=C also repels the nucleophile, preventing attack at the carbon labelled
“” for Q.

(Note that in both P and Q, the carbon bearing the Br is bonded to bulky groups. Hence
the comparison of steric hindrance to the attacking nucleophile for P and Q will unlikely be
of importance.)
Examiner’s Comments
 It was evident that some students were unsure of what they were describing e.g.
incorrectly making statements such as “p electrons overlap with the pi-electron cloud”,
“p-orbital delocalises into the pi-electron cloud”, “electrons of Br delocalise into the pi-
electron cloud” etc.

Note: orbitals can overlap, and electrons can delocalise. Please do not mix the two
descriptions because they become meaningless. Also, it is the lone pair of electrons
that is in the p-orbital of Br here that can delocalise, not all or any electrons of Br.

 Also, the term “partial double bond character” should be clearly referenced to the C–Br
bond. Statements such as “p orbital of Br overlaps with the pi electron cloud of C=C,
and so partial double bond character is formed” is ambiguous.

And as it is not a “full” / “real” double bond, do not say that a double bond is formed. It
is merely that now that there is an overlap between the p-orbitals of bromine and its
adjacent carbon, there is somewhat of a pi-electron cloud existing between bromine
and that carbon, and hence a partial double bond character can be said of the carbon-
bromine bond.

C3(a)(v) The double bond on compound P that is attacked by the nucleophile is less electron rich/
more electron deficient due to the presence of an electronegative bromine atom.

In addition, the nucleophile attacks a comparatively less hindered sp2 terminal carbon atom
to yield compound O. Therefore, formation of compound O is more favourable.
Examiner’s Comments
 Please read the question properly: “a nucleophilic attack can occur at the C=C bond”.

Many students went into a detailed suggestion of the mechanism which unfortunately
in this case ended up with a carbocation being formed (after the loss of Br –), and the
double bond shifting from between carbon-1 and carbon-2 to between carbon-2 and
carbon-3, with a positive charge placed at carbon-1.

 They then proceeded to let the nucleophile attack carbon-1. But the question clearly
states that the attack is at the C=C bond, not at a carbon bearing the positive charge.

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 Hence, any description or explanation made with reference to this carbocation is
irrelevant here.

Nevertheless, students who were able to propose this mechanism with the shifting of
the double bond should be commended, since in another context, the correct pushing
of arrows and the analysis of mechanism could have been the way to solve the
questions posed.

 Many students were unclear about what “steric hindrance” means and the appropriate
context to use it. The confusion was especially apparent when students talked about
steric hindrance being present in the products N and O.

In the formation of product N, the presence of bulky groups at the site of an attack i.e.
the carbon bearing the Br in reactant P, would hinder the attack of an incoming
nucleophile. Hence the bulky groups are a steric hindrance to the attacking species
here. Any discussion of steric hindrance in N is thus irrelevant here.

 In addition, for this question, there should be some form of comparison between the
steric hindrance present for both carbon-1 (to form O) and carbon-3 (to form N) e.g.
the sp2 terminal carbon atom has less hindrance. Just stating that there is steric
hindrance present at carbon-3 in P is not sufficient.

 Students should have made use of all information given in the question to answer this
part. Given that there is no reaction between hex-1-ene and HS–, students should then
consider how the presence of Br atom in P enables the reaction with HS– to occur.

C3(b) Evidence Deductions

T has a Mr of 46.0 and gives yellow Oxidation occurred. Yellow precipitate is CHI3.
precipitate when warmed with
aqueous alkaline iodine.

T has the following structure:

Since T is an alcohol, U is a carboxylic acid.

1 mole of U requires 2 moles of NaOH U contains 2 –COOH groups.
for complete neutralisation.

When one enantiomer of U is heated SN1 reaction has occurred.

with aqueous NaOH, followed by U is a halogenoalkane.
acidification, a racemic mixture of U and V contain chiral carbon.
compound V, C5H8O5, is obtained.

Compound V does not react with V does not undergo oxidation. V contains a
aqueous potassium dichromate(VI). tertiary alcohol group.

15
 T: U: V:

S:

Examiner’s Comments
 Many students stated that the positive iodoform test indicates “alcohol present”. This is
incorrect. Not all alcohols will give a positive test – only alcohols with the relevant
structure.
 A positive iodoform test also does not mean “a 2o alcohol is present”. Ethanol is a 1o
alcohol and gives a positive iodoform test.
 Also, please draw the complete structure as shown in the answer, including the “free”
bond. Do not try to replace that structure with wordy descriptions of –CH3, –OH being
bonded to carbon etc.
 The term “methyl ketones” can be used to refer to R-CO-CH3, however, do not use the
term “methyl alcohol”. This is because methanol, CH3OH, is known also as methyl
alcohol (as a non-IUPAC name) and so it would be best to avoid this term altogether.
Just use the structure as shown in the answer when you need to describe the range of
alcohols that give a positive iodoform test.
 The ‘3’ in –CH3 must be written clearly.

 Both phenols and carboxylic acids will react with NaOH, but only carboxylic acid groups
form esters under conc. H2SO4 conditions. Hence, deductions of “acidic groups”, or
“dibasic” is insufficient here.

 Please use proper notations: SN1, not SN1.

 “SN1” already means “unimolecular nucleophilic substitution” – there’s no need to say
“SN1 nucleophilic substitution”.

 Deducing that V contains a tertiary alcohol (learn proper terms to classify alcohols) is
crucial for solving the unknown structure V. Rather than listing the functional groups
absent in V e.g. no 1o, 2o alcohol, alkene in V, the tertiary alcohol functional group
present in V should be identified.

 Credit can be given for names of reactions written. E.g. T undergoes oxidation reaction,
accounting for the yellow ppt observed. Note: do not name this reaction as iodoform
reaction, tri-iodomethane reaction or redox reaction.

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