Anderson Serangoon Junior College Preliminary Examinations

H2 Chemistry (9729) Paper 3 Mark Scheme

Section A
Answer all questions.

1 Many naturally occurring organic compounds contain either acidic groups or basic groups or both.
The strength of the acid or the base depends on the structure of the molecule.

(a) The pKa values of ethanoic acid and two amino acids are given in Table 1.1 below.

Table 1.1

name structure pKa1 pKa2 pKa3

ethanoic acid CH3COOH 4.7 – –

H2N CH CO2H
serine (ser) CH2 2.2 9.2 –
OH

H2N CH CO2H
aspartic acid CH2 1.9 3.7 9.6
(asp)
CO2H

(i) Suggest two reasons why the pKa1 value of serine is so much less than the pKa1 of
ethanoic acid. [2]

Electron withdrawing –NH3+ (or –NH2) group is in close proximity to the negative charge
of the carboxylate anion of deprotonated serine, hence dispersing the negative charge
and stabilizing the anion, and

–OH of the R group of serine is able to form intramolecular hydrogen bond with the O
atom of –COO–. This stabilizes the carboxylate anion.

Hence, carboxylate anion of serine is more stabilised than ethanoate ion

(ii) Draw a skeletal structure for the dipeptide, asp–ser. [2]

HO O
H
N
H2N OH
O
OH

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 Electrophoresis is a technique used to separate charged particles placed in an electric field.
The system consists of two oppositely–charged electrodes connected by a conducting
medium, typically a gel. The separation of the charged particles is based on their electrical
charge and Mr.

A sample consisting of serine and aspartic acid was analysed by electrophoresis using a gel
buffered at pH 5.7. The small quantity of the mixture was placed at the centre of the gel, at
equal distance from the two electrodes.

(iii) Using the information given in Table 1.1, suggest the structures of the major species
present in the buffer solution. Label the structures clearly. [2]

asp ser

(iv) Hence, describe the relative positions of the two species in the gel after the separation
by the electrophoresis process. Explain your answer.
You may find it helpful to draw a diagram to illustrate your descriptions. [2]

Ser has no net charge / electrically neutral / exists as a zwitterion.

Hence it will not move and remain at the centre of the strip.

Asp has an overall negative charge, and so it will migrate towards the anode.

asp
Anode (+) Cathode (–)

ser

(b) A student prepared a buffer solution of pH 5.7 by adding solid sodium hydroxide to
200 cm3 of 0.200 mol dm–3 ethanoic acid.

(i) With reference to the information in Table 1.1, calculate the mass of sodium hydroxide
the student would have used. [2]

pKa (CH3COOH) = 4.7 Alternative:

Ka = 10–4.7 mol dm–3 Ka = [H+]([A–]/[HA])
[A–]/[HA] = 10
Initial n(CH3COOH) = 200 x 10–3 x 0.200
= 0.04 mol Let x be amt of HA left
11x = 0.04
Let the no.of mol of NaOH needed be a mol. x = 3.636 x 10–3

CH3COOH + NaOH  CH3COO–Na+ + H2O mass of NaOH added

a mol a mol = (0.04 – 3.636 x 10–3) x 40.0
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 = 1.45 g
[H ][A  ]
Ka = [HA]

10–4.7 (0.04 – a) = 10–5.7 x a

a = 0.03636 mol
mass of NaOH = 0.036359 x 40.0 = 1.45 g

A buffer solution generally loses its effectiveness when one component of the buffer pair is
less than about 10% of the other.

(ii) Calculate the percentage of ethanoic acid component present in the buffer solution in
(b)(i) above and hence comment on the effectiveness of the buffer. [2]

To determine the percentage of ethanoic acid component present in the buffer solution

Alternative:
from previous part
[HA]/[A–] = 0.1

%HA in buffer = (0.1)/1.1 x 100%

= 9.09%

To comment on the effectiveness of the buffer, need to find ratio of one component to
[acid]
the other component of the buffer. That is, ratio [salt] .

[acid]
From the above calculation, [salt]
= 0.1

% [HA] with respect to the salt = 0.1  100% = 10%

Comment and mention of how the above percentage is determined:

 Buffer is useful/within limits of effectiveness as the % of one component is equal to
10% of the other component.

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 (c) Nicotinic acid and its amide, nicotinamide, are present in Vitamin B3 and are used to increase
good cholesterol levels.

O O
1 2
N OH N NH2

Nicotinic acid Nicotinamide

The structure of nicotinamide consists of a single delocalised system of electrons which

includes:
 an electron in the unhybridised p–orbital of the nitrogen atom in the six–membered ring
 electrons from the carbon atoms of the six–membered ring
 two electrons in the  bond of the >C=O group
 two electrons in lone pair on the nitrogen atom of the amide group

(i) State the number of delocalised electrons in one molecule of nicotinamide. [1]
10

(ii) Using the information provided, suggest the H–N–H bond angle in the NH2 group in
nicotinamide. [1]

120⁰

High tendency for the lone pair of electrons on N atom to delocalised and reduces it
availability. Lone pair–bond pair repulsion is not as significant and thus greater chance
of it forming a trigonal planar structure about the N atom resulting in bond angle to go
close to 120o.

(iii) Predict and explain the relative basicity of the two N atoms, labeled N1 and N2, in the
nicotinamide molecule. [2]

N2 is neutral because the lone pair on nitrogen atom is delocalised into the π bond of
the adjacent C=O by resonance, hence not available for donation to a proton.

N1 is more basic as the lone pair of electrons on the nitrogen are not in the same plane
as the unhybridised 2p orbitals, thus making it more available for dative bond to a proton.

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2 (a) A lithium–iodine electrochemical cell can be used to generate electricity for a heart pacemaker.
The cell is non–rechargeable and it consists of a lithium electrode and an inert electrode
immersed in bodily fluids. When current flows, lithium is oxidised and iodine is reduced.

(i) Write two half–equations for the reactions taking place at the two electrodes. Hence,
write the overall equation. [2]

Oxidation: Li → Li+ + e–
Reduction: I2 + 2e– → 2I–
Overall equation 2Li + I2 → 2Li+ + 2I–

(ii) Use the Data Booklet to calculate the Eocell for this cell. [1]

Eocell = +0.54 – (–3.04)

= +3.58 V

(iii) A current of 2.5 × 10–5 A is drawn from this cell.

Calculate how long a pacemaker will last when 0.1 g of lithium electrode is remaining in
the cell.
Assume the current remains constant throughout this period. Give your answer to the
nearest day. [3]

Amount of Li = 0.10/6.9 = 1.45 × 10 –2 mol

Q = 96500 × 1.45 × 10–2 = 1399 C
t = 1399/(2.5 × 10–5) = 5.60 × 107 s = 648 days

(iv) Hence, suggest a reason why lithium–iodine battery can be used to power a heart
pacemaker. [1]

A small mass of lithium anode is sufficient to power the pacemaker for very long (0.10 g
can last for almost 2 years (648 days)
 This ensures that the battery is very lightweight (and can be used in the body
without too much additional load)
 can last for very long without replacement needed

(b) Unlike the lithium–iodine cell, Lithium–ion (Li–ion) batteries are designed to be recharged
hundreds of times.

One type of lithium–ion battery consists of a cobalt oxide, CoO2, electrode and a graphite
electrode with lithium atoms inserted between the layers. An electrolyte of LiPF6 dissolved in
ethylene carbonate is used between the two electrodes.

During discharge, the Li atoms in the graphite electrode form Li+ ions. Electrons are released
and move through external circuit to the cobalt oxide electrode. The Li + ions migrate through
the electrolyte and are incorporated into the cobalt oxide electrode. This is illustrated in
Fig. 2.1 in which C–C–C–C–C is a simplified representation of a layer of carbon atoms in
graphite.

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 external circuit
–
e e–

C–C–C–C–C
Li+
Li

PF6– C–C–C–C–C

electrolyte

during discharge

Li+ C–C–C–C–C
Li+
PF6– C–C–C–C–C

electrolyte

Fig 2.1

The overall redox equation can be represented as:

LiC6 + CoO2 C6 + LiCoO2

where C6 represents the graphite layers.

(i) Suggest the type of bonding between the lithium atoms and the layers of graphite.
Explain your answer. [1]

Metallic bonding between the lithium ions and the delocalised electrons on the graphite
layers.

(ii) State the change in oxidation number of cobalt in the cobalt oxide electrode during
discharging process.
Hence, or otherwise, suggest if this electrode is the anode or cathode during discharge.
[2]

From +4 to +3
It is the cathode as shown by the decrease in oxidation state of Co.
OR
It is the cathode as it gains electrons for reduction during discharge process.

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 (iii) The cell potential, Ecell is said to be related to the standard cell potential, EO
cell by the
Nernst equation:
RT [LiCoO2 ][C6 ]
Ecell = EO
cell – ln
F [LiC6 ][CoO2 ]

where concentration of the species are measured in the solid phase electrodes.

With reference to the Nernst equation, discuss how the cell potential changes as
discharging takes place. [2]

During discharging, the concentration of the products C 6 and LiCoO2 increase while
concentration of the reactants LiC6 and CoO2 falls.

Since Ecell is a constant, Ecell becomes less positive.

(iv) During charging, the reverse of the discharging process takes place and eventually, all
the lithium atoms will be stored between the graphite layers.

Suggest a property of graphite, other than its electrical conductivity, that allows the
storage of lithium atoms upon charging. [1]

It has weak intermolecular forces of attraction between layers that makes it easier to
overcome and expand the gap between layers to accommodate all the lithium atoms.

(c) Zinc and silver are often present as impurities in crude copper obtained from minerals.

Explain, in terms of electrode reactions, how zinc and silver are removed in the industrial
process of the purification of copper, using relevant data from the Data Booklet. Illustrate your
answer with a labelled diagram.
[4]

EZn2+/Zn =0.76 V ECu2+/Cu = +0.34 V EAg+/Ag = +0.80 V

At the anode, Zn is oxidised to Zn2+ (can be described in equation form) as EZn2+/Zn is more
negative than ECu2+/Cu and dissolves into the electrolyte with Cu.

Ag will not be oxidised as EAg+/Ag is more positive than ECu2+/Cu, hence Ag drops off as anode
sludge.

At the cathode, only Cu2+ is reduced as ECu2+/Cu is more positive than EZn2+/Zn. Hence Cu is
collected, whereas Zn2+ is not reduced/remains in solution.

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 (d) A set–up similar to what you have described in (c) can be used in copper electroplating.

Explain the effect, if any, each of the following changes have on the mass of copper plated if
the duration of the electroplating process is kept constant.
 Doubling the concentration of copper ions in the electrolyte.
 Doubling the current of the electroplating process. [2]

 Doubling the concentration of copper ions in the electrolyte will not increase the mass as
it does not change the quantity of charge supplied for deposition of copper atoms.

 Doubling the current of the electroplating process. Yes.

Since Q = It, increasing the current will lead to twice the amount/quantity of charge/amount
of electrons and twice the mass of copper plated.

(e) A fixed current was passed through two electrolytic cells connected in series for a known
duration. The first cell contains aqueous copper(II) sulfate while the second cell contains
aqueous silver nitrate. Inert electrodes were used in both cells.

mass of silver deposited

Calculate the ratio of under these conditions. [2]
mass of copper deposited

Reaction at the first cathode: Cu2+(aq) + 2e  Cu (s)

Reaction at the second cathode: Ag+(aq) + e  Ag (s)

Since the same amount of charge was passed thru the 2 cells (connected in series),
nAg 2
=
nCu 1

mass of Ag deposited = 2 x 107.9 g

mass of Cu deposited = 1 x 63.5 g

mass of Ag deposited 2 x 107.9

=
mass of Cu deposited 1 x 63.5
= 3.40

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3 Organic compounds are molecules that contain carbon atoms covalently bonded to hydrogen
atoms.

(a) The boiling points of some organic compounds are shown in Table 3.1.

Table 3.1

compound formula Mr boiling point / C

ethylbenzene CH2CH3 106.0 136

benzylamine CH2NH2 107.0 185

phenylmethanol CH2OH 108.0 205

benzylchloride CH2Cl 126.5 179

Suggest explanations for these differences. [3]

All four compounds have simple molecular structures.

Benzylchloride has higher boiling point than ethylbenzene as more energy is required to
overcome the stronger permanent dipole–permanent dipole attractions between the
benzylchloride molecules as compared to the weaker instantaneous dipole–induced dipole
between ethylbenzene molecules.
OR
Benzylchloride has higher boiling point than ethylbenzene as it has greater number of
electrons / larger electron cloud size so more energy is needed to overcome the stronger
instantaneous dipole–induced dipole in benzylchloride compared to the weaker instantaneous
dipole–induced dipole between ethylbenzene molecules.

Less energy required to overcome the weaker permanent dipole–permanent dipole attractions
/ weaker instantaneous dipole–induced dipole between the benzylchloride molecules
compared to the stronger hydrogen bonding between the respective molecules of
phenylmethanol and benzylamine,

The O–H bond in phenylmethanol is more polar than the N–H bond in benzylamine. Hence
more energy is needed to overcome the stronger hydrogen bonding between molecules of
phenylmethanol than between molecules of benzylamine. Hence, phenylmethanol has a
higher melting point than benzylamine.

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 (b) (i) 2–methyl–1,3–butadiene, also called isoprene, is a colourless, volatile liquid
hydrocarbon obtained in processing petroleum.

Draw the structures of the products A and B formed and suggest reagents and
conditions for reaction I shown in Fig. 3.1.

I IBr (2 mol) B
A
C5H12O4
isoprene

Fig. 3.1
[3]

Step I: KMnO4, NaOH(aq), cold

HO Br
HO OH Br I

HO I
A B

Isoprene can be synthesised from the product obtained via a substitution reaction between
compound C and a suitable halogen.

(ii) Suggest a suitable halogen and the condition for the substitution reaction. [1]

(Limited) Cl2 / Br2, uv light

(iii) Draw the structure of the two possible products formed via the substitution reaction of
C with the halogen and hence, determine the expected ratio in which they will be formed
assuming equal rate of substitution of H atom. [2]

X
X :

6 : 1

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 (c) Hydration of alkenes can be carried out by reacting alkenes with borane, BH 3 followed by
treatment with alkaline hydrogen peroxide, H2O2.

An example of such a reaction is shown in Fig. 3.2.

CH3 H H BH2 H OH
BH3 H2O2
C C CH3 C C H CH3 C C H
II NaOH/H2O
CH3 CH3 CH3 CH3 CH3 CH3
III

Fig. 3.2

Reaction II occurs via a mechanism similar to electrophilic addition and it involves the BH 3
acting as an electrophile.

(i) Explain what do you understand by the term electrophile. [1]

An electrophile is a cation or electrically neutral molecule which has an electron deficient

atom / is an electron–pair acceptor which is attracted to an electron–rich site.

(ii) It is suggested that the mechanism for reaction II goes through the formation of a
transition state as shown in Fig. 3.3.

H
H B
H H BH2
CH3 H
C C CH3 C C H

CH3 CH3 CH3

CH3

Fig. 3.3

Using information given in Table 3.2, complete Fig. 3.3. In your answer, indicate clearly
the polarity of the B–H bond in borane by drawing + and – on the appropriate atoms
and draw curly arrows for the movement of electrons.

Table 3.2

element electronegativity

boron 2.0

hydrogen 2.2
. [2]

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  
H
H B
H
H BH2
CH3 H
C C CH3 C C H

CH3 CH3 CH3

CH3

(iii) By determining the change in the oxidation number of the reactive carbon, suggest the
role of hydrogen peroxide in reaction III. [2]

O.N. of C bonded to –BH2 changes from –2 to 0.

H2O2 acts as an oxidising agent.

(iv) Two possible molecular arrangements of H2O2 exhibiting cis–trans isomerism despite
the absence of double bond to restrict rotation is shown in Fig 3.4.

H
x
x x x
O Ox O xO
x x
H H H
molecular arrangement 1 molecular arrangement 2

Fig 3.4

Using the principles of the Valence Shell Electron Pair Repulsion theory, explain the
shape of the H2O2 molecule and suggest which molecular arrangement, 1 or 2, would
result in a more stable molecule. [2]

The 4 electron pairs around each oxygen atom are arranged in a as far apart as possible
/ tetrahedral manner in order to minimise inter–electronic repulsion. Hence the shape is
bent about each O atom.

Molecular arrangement 2 is more stable than 1 as lone – pair repulsion > lone pair –
bond pair repulsion > bond pair – bond – pair repulsion / the lone pairs of electrons are
arranged away from one another which minimises repulsion.

(d) (i) Benzene rings are commonly found in many naturally occurring organic compounds.

Explain why benzene tends to undergo substitution reactions instead of addition

reactions like alkenes. [2]

Benzene does not undergo addition reactions as an addition reaction will require a pi
bond to be broken.

This leads to the loss of resonance stability in the product formed as the continuous 
electron cloud is disrupted

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 (ii) The position of substitution in the electrophilic substitution of arenes can be explained
based on the stability of the intermediate carbocation formed.

Fig. 3.5 shows the possible carbocation intermediates that can be formed from the
bromination of methylbenzene.
CH3 CH3 CH3
Br
H 2-position 3-position
Br

H
methylbenzene

4-position

CH3

H Br

Fig. 3.5

Use the information and your knowledge about the stability of carbocations to suggest
why the CH3 group directs incoming electrophiles to the 2– and 4–positions in
preference to the 3–position. [2]

Substitution at 2– and 4– position forms tertiary carbocations which are more stable
compared to the secondary carbocation formed at the 3–position.

The greater number of electron–donating alkyl groups attached to the positively

charged carbon in the tertiary carbocation help to disperse the positive charge
more, making the tertiary carbocation more stable than a secondary carbocation.

(iii) Suggest a synthesis of 2–bromobenzoic acid starting from methylbenzene according to

the scheme in Fig. 3.6.

CH3 CO2H
more than
one step

Br
3-bromobenzoic acid

Fig. 3.6 [3]

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 Section B
Answer one question from this section.

4 (a) Describe the reactions, if any, when separate samples of the oxides Na2O, Al2O3 and P4O10
are added to water. Write equations where appropriate and suggest the pH of any aqueous
solution formed. [4]

Na2O dissolves / is soluble in water to give a colourless solution of NaOH with pH 13.
NaO(s) + H2O(l)  2NaOH(aq)

Al2O3 is insoluble in water and hence pH remains at 7.

P4O10 hydrolyses / dissolves / is soluble in water / reacts with water to give a colourless
solution of H3PO4 with pH 2 (accept 1)
P4O10(s) + 6H2O(l)  4H3PO4(aq)

(b) Lithium metal reacts with bromoalkanes to give organolithium compounds.

R–Br + 2Li  R–Li + LiBr

– +
The carbon–lithium covalent bond in organolithium compounds is polarised C–Li. These
compounds are useful carbon–nucleophiles. They react with carbonyl compounds to give
lithium alkoxides, which form alcohols on treatment with dilute acid as shown in Fig 4.1.

R' R' R'

H+
R Li + C O C OLi C OH + Li+
R'' R R
R '' R ''

(R is alkyl; R’ and R” are either alkyl or H)

Fig 4.1

(i) Butan–2–ol, CH3CH2CH(OH)CH3 is formed when CH3CH2CHO reacts with CH3Li in a

similar two–step process.

Draw the mechanism for this reaction, assuming that CH3Li produces the methyl
anion, :CH3–, as the reacting species. In your answer, show any relevant charges, lone
pairs of electrons and movement of electrons. [2]

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 (nucleophilic addition)
H+
 O O Li+ OH
(slow) (fast)
CH3CH2 C H CH3CH2 C H
 C
CH3CH2 H CH3 CH3

+
CH3 Li
+ Li+

(ii) With reference to the mechanism you have described in (b)(i), explain why the
butan–2–ol formed does not rotate plane–polarised light. [1]

:CH3– nucleophile attacks the (trigonal) planar carbonyl carbon of CH3CH2CHO from
both sides of the plane with equal probability, producing an equimolar mixture of two
enantiomers (racemic mixture)

(iii) Deduce the structures of a suitable bromoalkane, RBr and a suitable carbonyl
compound, R’R’’CO, to synthesise each of the following isomeric alcohols.

 CH3CH2CH2CH(OH)CH3

 (CH3CH2)2CH(OH) [2]

product RBr R’R’’CO

CH3Br CH3CH2CH2CHO
CH3CH2CH2CH(OH)CH3
CH3CH2CH2Br CH3CHO

(CH3CH2)2CH(OH) CH3CH2Br CH3CH2CHO

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 (c) p–coumaric acid, C9H8O3 (Mr = 164.0), occurs in tomatoes, carrots and strawberries and is
thought to help prevent the development of stomach cancer. It is an aromatic compound with
two substituents occupying positions 1 and 4 of the benzene ring.

8.2 g of p–coumaric acid reacts with excess sodium metal to give 1.2 dm 3 of hydrogen gas
at room temperature and pressure conditions.

When solid NaHCO3 is added to p–coumaric acid, compound G is formed, together with
liberation of CO2.

p–coumaric acid reacts with aqueous bromine to give compound H, C9H7O4Br3.

(i) Deduce the structures of compounds G, H and p–Coumaric acid, explaining the
reactions described. [6]

8.2
n(p–coumaric acid) reacted with Na =
164.0
= 0.0500 mol
1.2
n(H2) evolved =
24
= 0.0500 mol

 Redox reaction occurs between p–coumaric acid and Na(s).

Since n(H2) : n(p–coumaric acid) is 1:1, there are two hydroxy groups in p–coumaric
acid. (each mole of –OH group liberates ½ mol of H2)

 One of the hydroxy groups is a carboxylic acid (only 3 O atoms) as CO2(g) is

liberated upon addition of NaHCO 3(s). Acid–base reaction occurs and G is the
carboxylate salt of p–coumaric acid.

 Presence of phenol and alkene because p–coumaric acid is 1,4–disubstituted so

only 2 Br atoms can substitute the H atoms on benzene ring via electrophilic
substitution. Hence the 3rd Br atom must have been added to a >C=C< together with
–OH group (aqueous Br2) via electrophilic addition.

OH OH OH
Br Br

+ CH CHCO2H
CH CHCO2 Na CH CHCO2H
OH Br
(accept w/o Na+) (accept minor product) (accept alternative with =CH2)

G H p–coumaric acid

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 (ii) p–coumaric acid consists of two stereoisomers. State the type of isomerism shown
here, and draw structures to illustrate your answer. [2]

cis–trans isomerism
HO HO

CO2H H
C C C C
H H H CO2H

cis trans

Compounds J and K are two isomers of p–coumaric and their structures are given below.

CO2H CO2H

COCH3 CH2CHO

J K

(iii) When these two compounds are heated separately under reflux with alkaline KMnO 4
followed by acidification, the same compound is formed in each case.

Suggest the structure of this compound. [1]

CO2H

CO2H

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 (iv) Describe how compounds J and K could be distinguished using a simple chemical test.
[2]

Add to separate test–tubes containing J and K, Tollens’ reagent and warm

K will give a silver mirror but J will not.

Fehling’s solution, warm

K will give a brick red precipitate but J will not.

K2Cr2O7, dilute H2SO4, heat (KMnO4 is not accepted)

K will turn orange K2Cr2O7 green but J will not.

I2(aq), NaOH(aq), warm

J will give yellow ppt but K will not

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 5 (a) The halogens react with hydrogen to form hydrogen halides which are colourless gases at
room temperature.

(i) With reference to the HCl molecule, explain the meaning of the term bond energy. [1]

Bond energy of H–Cl bond is the (average) amount of heat absorbed to break one mole
of H–Cl (covalent) bond in the gaseous state to form the gaseous H and Cl atoms.

Some bond energy values are given in the Table 5.1.

Table 5.1

Bond Bond Energy / kJ mol–1

H—H 436
P—P 200
Cl—Cl 244
P—H 320
H—Cl 431

(ii) The P—H bond energy is approximately the average of the H—H and P—P values.
However, the H—Cl bond energy is higher than the average of the H—H and Cl—Cl
values.

Explain why this is so. [1]

Cl is more electronegative than H. Hence the H–Cl bond is polar and the bond has ionic
character which results in extra bond strength due to the additional electrostatic forces
of attraction between the partial charges of the polar bond.

The electronegativity of P and H are similar, hence the bond energy of the P–H bond is
just the average of the H–H and P–H bond energies.

(iii) Explain how the thermal stabilities of the hydrogen halides vary down the group. [2]

Down the group, H–X bond strength decreases (as shown by bond energy data)
 Less energy required to break the weaker H–X bond.
 Thermal stabilities of HX decreases.

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 (b) Chlorine finds various uses as organochlorine compounds.

Chloroethanoyl chloride, ClCH2COCl, is used in the synthesis of the local anaesthetic,

lidocaine, from 2,6–dimethylphenylamine as shown below.

NH2 O
Cl H
Cl N
Cl
step I O

2,6-dimethylphenylamine compound A

step II

H
N
N
O

lidocaine
Fig. 5.1

(i) State the type of reaction that occur during step I. [1]

nucleophilic (acyl) substitution / condensation

(ii) A student suggested that compound B, an isomer of compound A, was produced in

Step I instead.
O
H
N
Cl

compound B

Explain clearly whether you agree with this suggestion. [2]

Disagree with the student suggestion.

Reason:
As both the chlorine and oxygen are highly electronegative, they attract the electrons
from the acyl carbon atom, making the acyl carbon atom more electron deficient.

 Hence the acyl carbon is more susceptible to nuclephilic attack by lone pair of electron
on nitrogen on 2,6–dimethylphenylamine nucleophile.

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 Step II proceeds by an SN2 mechanism.

(iii) Draw the structure of the transition state formed in the mechanism. [1]

NH

C O
+ –
HN C Cl
H
H

(iv) Suggest a reason which explains why step II did not proceed via S N1 mechanism.

If step II proceeds via SN1 mechanism, the carbocation formed would be

N CH2
C
O

This carbocation is unstable due to presence of electron–withdrawing O (or C=O) (which

would intensify the positive charge)/or, unstable because of absence of electron–
donating alkyl groups

(v) Suggest the skeletal formula of the product formed when lidocaine is reacted with
lithium aluminium hydride.

H
N
N

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 (c) Fig. 5.2 shows the reaction scheme involving chloroethanoyl chloride as a starting material.

O 2 steps
L mixture of products
Cl step III
Cl
Fig. 5.2

Compound L, C5H7O2N is neutral and has a pleasant fruity smell.

Compound M, C3H4O4 and N, C2H6O are two of the products formed in step II.

Effervescence is observed when solid sodium carbonate is added to compound M. One mole
of compound M is neutralised by two moles of potassium hydroxide.

Upon adding alkaline aqueous iodine to compound N, a yellow precipitate is obtained.

(i) Deduce the structures of compounds L, M and N and suggest the reagents and
conditions for step III. [4]

Observations Type of Deductions

reaction
1 Compound L, C5H7O2N , is L is likely an ester, amide or nitrile
neutral and has a pleasant L is not an amine
fruity smell
Hydrolysis M and N are carboxylic acid and alcohol

2 Effervescence observed with M Acid–base M is a carboxylic acid

C3H4O4 on adding solid sodium reaction
carbonate

3 One mol M reacts with 2 mol Acid–base M is a dibasic acid

KOH reaction

4 N C2H6O reacts with alkaline Oxidation Yellow ppt = CHI3

I2(aq) to give yellow ppt H
CH3 C
OH
Presence of

M = HO2CCH2CO2H
N = CH3CH2OH
O
NC CH2 C O CH2CH3
L=

Step III: Dilute H2SO4, heat under reflux

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 (ii) Hence, suggest the reagents and conditions for the 2–step synthetic route to form L
from chloroethanoyl chloride. [2]

(d) Chloroethanoyl chloride, ClCH2COCl, has four non–cyclic isomers. None of the isomers
contains O–Cl bond.

One of these isomers, compound P, exhibits different chemical properties from the other three.

(i) Draw the structures of all the four non–cyclic isomers of chloroethanoyl chloride and
identify which isomer is compound P.
[2]

Cl O
Cl CH C H

Cl H Cl Cl Cl H
C C C C C C
Cl OH H OH HO Cl

(ii) Describe a chemical test you would conduct to distinguish compound P from the other
three isomers. Include the observations expected for each isomer in your answers.
[2]
P is an aldehyde

(1) Add Tollen’s reagent to all 4 isomers and warm.

Silver (mirror) obtained for P, no silver (mirror) for the other 3 isomers

(2) Add 2,4–dinitrophenylhydrazine to all 4 isomers and warm.

Yellow/orange obtained for P, no ppt for the other 3 isomers

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