SECTION A

Answer any THREE questions, using the AL(C) Answer Book.

Based on the information given below, sketch a labeled
1. (a) (i)
pressure-temperature diagram for carbon dioxide. Indicate on your
diagram the supercritical fluid region
triple point:
-56oC and 5.1 atm
critical point:
31oC and 72.9atm
solid carbon dioxide is denser than liquid carbon dioxide

(ii)

State ONE characteristic of a supercritical fluid.

High penetration power like gas and high density like liquid
High Mobility like gas and low viscosity like liquid
*Just state 1 characteristic each from gas and liquid

(iii)

Supercritical carbon dioxide finds a number of applications, e.g. as a

dry-cleaning solvent and as a decaffeinating solvent. State TWO
advantages of using supercritical carbon dioxide over using organic
solvents in such applications

2008-AL-CHEM 2-1

Low toxicity
Environmentally friendly
Stable to the coffee bean sample

(iv)

A student made the following assertion:

As carbon dioxide is a greenhouse gas, the extensive use of
supercritical carbon dioxide in industry will pose harm to our
environment.
Do you agree with the student? Explain.

No
The supercritical CO2 used is recycled

(7 marks)
1.

(b) Both Sodium and Chloride are elements of Period 3 of the Periodic Table.
(i)

At room temperature and atmospheric pressure, Na2O is a solid with a

very high melting point whereas Cl2O is a gas. Account for this
difference in property between Na2O and Cl2O.

(ii)

Na2O is ionic compound with strong ionic bonds (non-directional

electrostatic attraction between cations and anions)
Large amount of energy is required to overcome these forces
Cl2O is simple molecular structure with weak van der Waals forces
between molecules only
Relatively lower amount of energy can overcome these forces
So at r.t.p., Cl2O is a gas and Na2O is solid
Na2O2 is another oxide of sodium. Write the chemical equation for the
reaction of Na2O with water and that of Na2O2 with water.
Na2O + H2O 2NaOH
Na2O2 + 2 H2O 2 NaOH + H2O2

(iii)

Cl2O7 is another oxide of chlorine. Give the products formed when

Cl2O and Cl2O7 are treated separately with water.
Cl2O + H2O 2HOCl
Cl2O7 + H2O 2HClO4
(6 marks)

2008-AL-CHEM 2-2

1.

(c) The table below lists the standard enthalpy change of formation of four
compounds
HfO298/kJ mol-1

Compound
H2O(l)
HCl(g)
SiO2(s)
SiCl4(l)
(i)

-286
-92
-910
-640

State the meaning of the term standard enthalpy change of formation

of a compound.
Enthalpy change with the formation of 1 mole of substances from its
elements in their standard states under standard conditions

(ii)

SiCl4(l) undergoes hydrolysis to give SiO2(s)

(I) Write the chemical equation for the hydrolysis.
SiCl4 + 2H2O SiO2 + 4HCl
(II) Using the above data, calculate the standard enthalpy change for
the hydrolysis.
State ONE assumption made in your calculation

Hfo[SiCl4] + 2Hfo[H2O] + Ho = Hfo[SiO2] + 4Hfo[HCl]

(-640) + (-286*2) +Ho = (-910) + (-92*4)
Ho = -66kJ mol-1
Obey Hesss Law (Initial and final conditions are the same)
Hydrolysis gives HCl(g) (not aq)

2008-AL-CHEM 2-3

(III) Does the hydrolysis have a positive, negative or zero enthalpy

change? Explain.

2.

S = +ve since the stoichiometric ratio reactant:product increases

The disorderness of the system increases

For a feasible reaction G must be +ve
H need to be +ve according to G = H - TS

(7 marks)
(a) The gaseous reaction below takes place at 750 C in a closed container with a
fixed volume.
o

2H2(g) + 2NO(g) 2H2O(g) + N2(g)

(i)

Suggest an experimental method that can be used to follow the

concentration of N2(g) in the reaction mixture. Briefly explain the
principle of your suggested method

(ii)

Measure the pressure change of the system

No. of moles changes as reaction proceeds
Pressure change is proportional to no. of moles of N2 formed

The table below lists three sets of experimental data of the reaction at
750oC:
Experiment

1
2
3

Initial concentration / mol dm-3

H2(g)
NO(g)
0.010
0.005
0.010

0.0250
0.0250
0.0125

Initial rate for the

formation of N2(g) /
mol dm-3 s-1
0.500
0.250
0.125

Deduce the rate equation for the reaction, and calculate the rate
constant at 750oC.
0.5/0.25 = [0.01/0.005]x , x = 1, order w.r.t. [H2] = 1
0.5/0.125 = [0.025/0.0125]x , x = 2, order w.r.t. [NO] = 2
rate = k[NO(g)]2[H2(g)]
0.5 = k (0.025)2(0.01) , k = 8 x 104 mol-2 dm6 s-1

2008-AL-CHEM 2-4

(iii)

Is the reaction an elementary reaction? Explain.

2.

No
Very difficult for 4 molecules to simultaneously collide + react
The molecularity is different from the reaction order

(b) The reaction below is catalyzed by

Fe2+(aq)

ions but not by

Cr3+(aq)

(6 marks)
ions.

S2O82-(aq) + 2 I-(aq) 2 SO42-(aq) + I2(aq)

(i)

Outline an experimental method to show that the reaction is catalyzed

by Fe2+(aq) ions.

(ii)

Prepare a known volume of I-(aq) with S2O32-(aq) + starch indicator

Add a known volume of S2O32-(aq)
Measure the time for blue color to appear
Repeat the experiment with adding a few drops of Fe2+(aq)
Time for blue color to appear will reduce significantly

It is known that the catalytic reaction is a multi-step process. With

reference to the standard reduction potential given on page 15, deduce
possible steps for the catalytic reaction.
From the SRP:
S2O82- + 2e- 2SO42- Eo =+2.01V
Fe3+ + e- Fe2+ Eo = +0.77V
I2 + 2e- 2I- Eo = +0.54V
After calculation:
S2O82- + 2Fe2+ 2SO42- + 2Fe3+ Eo = +1.24V
2Fe3+ + 2I- 3Fe2+ + I2 Eo = +0.23 V

more +ve the reduction potential, higher tendency to reduce

I- I2 is energetically unfavoured (-ve Eo), but with the presence
of Fe2+, the catalyzed rxn has a +ve Eo

2008-AL-CHEM 2-5

Since the first step has +ve Eo as well, the activation energy of
catalyzed rxns is most likely to be lower than the uncatalyzed one
5

(iii)

Sketch, in the same diagram, the energy profile of the reaction with
and without Fe2+(aq) ions.

(iv)

Suggest why Cr3+(aq) ions do not catalyse the reaction.

2Cr3+ + 2I- 2Cr2+ + I2 Eo = -0.95V
the first step has a negative Eo
energetically unfavorable will not catalyze this reaction

2.

(c)

(10 marks)
The following four substances all exist in the form of white powder:
Baking soda(NaHCO3), cornstarch, finely ground sugar, and plaster of
Paris (CaSO4.H2O)
Suggest how you would do experiments at home to distinguish the
four substances from one another. (You are not allowed to taste the
substances)
Baking Soda: add acid (HCl/vinegar) effervescence
Cornstarch: add small amt of iodine dark blue
Sugar: add sulphuric acid black solid
Plaster of Paris: add water release large amt of heat

2008-AL-CHEM 2-6

(a) (i)

(ii)

(4 marks)
Sketch the variation of pH when 25.0cm3 of 0.05mol dm Na2CO3(aq)
is titrated against 0.10mol dm-3 HCl(aq)
-3

A solid sample was known to contain Na2CO3(s), NaHCO3(s) and other

water-soluble inert substances. 2.382g of the sample was dissolved in
deionised water and made up to 250.0cm3. 25.00cm3 of the solution
was withdrawn and titrated against 0.0980 mol dm-3 HCl(aq) using
phenolphthalein as an indicator. When 13.40cm3 of the HCl(aq) was
added, the solution instantaneously turned from pink to colourless. A
few drops of methyl orange indicator were then added to the resulting
solution and the titration was continued. Addition of a further
23.65cm3 of the HCl(aq) caused the solution to turn orange.
Calculate the percentage by mass of Na2CO3(s) and that of NaHCO3(s)
in the solid sample.
No. of moles of CO32- ion in 250.0cm3 = 0.098 (13.40/1000)(10)
= 0.013 mol
mass of Na2CO3 in sample = 0.013 (106) = 1.38g
% by mass of Na2CO3 in sample = 1.38/2.382 x 100 ~ 58.0%
No. of moles of HCO3- in 250.0cm3 = 0.098(23.65-13.40/1000)(10)
= 0.01mol
mass of NaHCO3 in sample = 0.01(84) = 0.84g
% by mass of NaHCO3 in sample = 0.84/2.382 x 100 = 35.2%

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(b) (i)

(7 marks)
Mercury(I) chloride, Hg2Cl2(s), is sparingly soluble in water, and gives
Hg22+(aq) and Cl-(aq) ions
The solubility products Ksp of Hg2Cl2(s) is 2.4 x 10-18 mol3 dm-9 at
298K. Calculate, at 298K, the solubility of Hg2Cl2(s)
(I) in pure water, and
Let x be the solubility of Hg2Cl2(s) in pure water
Ksp = [Hg22+(aq)][Cl-(aq)]2
= x(2x)2
2.4 x 10-18 = 4x3
x = 8.43 x 10-7 mol dm-3
(II) in 0.10 mol dm-3 KCl(aq)
Let y be the solubility of Hg2Cl2(s) in 0.1M KCl(aq)
Ksp = y(0.1 + 2y)2
= y x 0.01
y = 2.4 x 10-16 mol dm-3

(ii)

Calomel electrode is commonly used as a reference electrode in e.m.f.

measurements. Its half reaction is as follows:
Hg2Cl2(s) + 2 e-

2 Hg(l) + 2 Cl-(aq)

When saturated KCl(aq) is used in a calomel electrode, the reduction

potential is +0.244 V at 298 K. Explain the effect on the reduction
potential if 0.10 mol dm-3 KCl(aq) is used in the electrode instead.
As the [Cl-(aq)] decrease, the eqm shifts to RHS
Applying Nernst equation, reduction potential will be more positive
(iii)

Suggest TWO advantages of using a calomel electrode over using a

standard hydrogen electrode as a reference electrode in e.m.f.
measurements.
H2(g) is flammable
Standard hydrogen electrode is difficult to set as the pressure needs to
be kept at 1 atm

2008-AL-CHEM 2-8

(8 marks)
(c) Account for each of the following:
(i)

Zn2+(aq) is colourless but Ni2+(aq) is coloured.

Zn2+ has 3d10 full filled 3d subshell configuration
Ni2+ has 3d8 partially filled 3d subshell configuration
Ni2+ can absorb EM radiation in the visible light region and undergoes
d-d transition, so it is colored
Not possible for Zn2+

(ii)

The degree of dissociation of HF(aq) increases significantly as

concentration increases.
HF forms 2 different compounds in dilute & conc. solution separately
In dilute solutions:
H3O+ + F- [H2O-HF]
In conc. solutions
HF + F- HF2As more HF2- forms, [F-] decrease and shifts the 1st eqm to LHS
Degree of dissociation of HF increases
(5 marks)

2008-AL-CHEM 2-9

4.

Iodine reacts reversibly with I-(aq) to give brown I3-(aq) according to

following equation:

(a)

I2(aq) + I-(aq)

I3-(aq)

(1)

An experiment, based on the partition of I2 between an organic solvent

and water, was carried out to determine the equilibrium constant Kc
for reaction (1):
A solution of iodine in 0.810 mol dm-3 KI(aq) was shaken with CHCl3(l)
in a separating funnel until equilibrium was attained at 298K. The
liquid mixture was then allowed to settle into two layers. The iodine in
each layer was titrated against standard Na2S2O3(aq). The concentration
of iodine in the organic layer was determined to be 1.680 mol dm-3
and that of total iodine in the aqueous layer, both I2(aq) and I3-(aq), to be
0.735 mol dm-3.
(i)

State ONE safety precaution when shaking the liquid mixture in the
separating funnel.

(ii)

Release the pressure built up as reaction proceeds

By invert it & open the tap from time to time

Calculate, in the aqueous layer,

(I) the concentration of I2(aq), and
[I2] in CHCl3 = 1.680 mol dm-3
[I2] in H2O = 1.680/130 = 0.01292 mol dm-3
(II) the concentration of I3-(aq).
Total [I2] in H2O = 0.735 mol dm-3
[I3-] in H2O = 0.735 0.0129 = 0.722 mol dm-3
(at 298 K, the partition coefficient of I2 between CHCl3(l) and H2O(l) is

2008-AL-CHEM 2-10

10

130, and I2 is more soluble in CHCl3(l) )

(iii)

Hence, calculate Kc of reaction (1) at 298 K.

[I-] in H2O = 0.810 0.722 = 0.088 mol dm-3
Kc = [I3-(aq)]/{[I2(aq)][I-(aq)]} = 0.722/(0.0129)(0.088)
= 636 mol-1 dm3
(7 marks)

(b)

Sketch the variation of the successive ionization enthalpies of sulphur

and briefly account for the variation.

Electronic configuration: 1s22s22p63s23p4

There are 3 shells for S
The farther the electron is from the nucleus, the smaller attraction it
will experience, hence less energy is required to overcome the
attractive force between nucleus and electron
Enormous amount of energy is required to break stable full-filled
configuration of shell, therefore fracture appears in ionization number
7 and 15
Successive IE increases as the effect of addition of protons outweighs
the screening effect, effective nuclear charge increases
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4.

(5 marks)
(c) Both diamond and graphite are allotropes of carbon. A unit cell of diamond
and a part of the structure of graphite are shown below:

(i)

Calculate the number of carbon atoms in one unit cell of diamond.

No. of C atoms = 8(1/8) + 6(1/2) + 4(1)
=8

(ii)

Diamond and graphite show a marked difference in electrical

conductivity. Account for their difference in electrical conductivity in
terms of bonding and structure.

Diamond: All C atoms are sp3 hybridized, no free electrons are

present to conduct electricity
It is a poor electrical conductor

Graphite: All C atoms are sp2 hybridized

The unhybridized electron in the pi orbitals sideway overlap to
give a delocalized electron cloud

These electrons move within the electron cloud within layers

So it is an electrical conductor

2008-AL-CHEM 2-12

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(iii)

Buckministerfullerene (C60) is another allotrope of carbon.

Suggest and explain how you would differentiate two samples of

black powder, one of buckministerfullerene and the other of graphite,
by
(I) a physical method, and
C60 is simple molecular (dissolve in organic solvent)
Graphite is covalent structure (not dissolve in organic solvent)
Pack the powder into a solid
Graphite conducts electricity while C60 does not

(II) a spectroscopic method

Mass Spectrometry
C60 gives a peak of mass-to-charge ratio 720 at the spectrum
As its molecular mass is 720

(8 marks)
2008-AL-CHEM 2-13

13

5.

END OF SECTION A
SECTION B
(a) Upon irradiation of visible light, 0.450 g of 2,4-dimethylpentane undergoes
monochloro-substitution to give 0.200 g of 1-chloro-2,4-dimethylpentane,
0.167 g of 2-chloro-2,4-dimethylpentane and 0.117 g of
3-chloro-2,4-dimethylpentane.
(i)
Draw the structure of 2,4-dimethylpentane.

(ii)

(I)

the overall percentage yield for the monochlorinated products

formed, and

Total no. of moles of monochlorinated products

= (0.2 + 0.167 + 0.117) / 134.5
= 3.60 x 10-3 mol
No. of moles of 2,4-dimethylpentane = 0.45/100 = 4.5 x 10-3 mol
Overall percentage yield = 3.6 x 10-3 / 4.5 x 10-3 = 80%

(II) the mole ratio of the primary, secondary and tertiary

monochlorinated products formed. (Assign a value of 1.0 to the
monochlorinated product which has the lowest yield.)
No. of moles of:
1-chloro-2,4-dimethylpentane (1o) = 0.2/134.5 = 1.487 x 10-3
3-chloro-2,4-dimethylpentane (2o) = 0.117/134.5 = 0.870 x 10-3
2-chloro-2,4-dimethylpentane (3o) = 0.167/134.5 = 1.242 x 10-3
Mole ratio of 1o : 2o : 3o monochlorinated products
= 1.487 : 0.87 : 1.242
=1.71 : 1 : 1.43
~ 1.7 : 1 : 1.4

2008-AL-CHEM 2-14

14

(iii)

You are provided with the following bond dissociation enthalpy data:
Bond

Bond dissociation enthalpy / kJ mol-1

H-Cl

+432

Cl-Cl

+243

H-CH2CH3

+420

H-CH(CH3)2

+401

H-C(CH3)3

+390

Cl-CH2CH3

+338

Cl-CH(CH3)2

+339

Cl-C(CH3)3

+330

Estimate the respective enthalpy changes of the monochlorination of

primary, secondary and tertiary hydrogen atoms in
2,4-dimethylpentane.

General formula:
H + 432 + y = 243 + x
H = x - y - 189
substitute +420, +401, +390 into x respectively
substitute +338, +339, +330 into y respectively
primary: -107 kJ mol-1
secondary: -127 kJ mol-1
tertiary: -129 kJ mol-1

2008-AL-CHEM 2-15

15

(iv)

(I)

With reference to the structure of 2,4-dimethylpentane and the

information given above, suggest TWO factors that would affect
the yield of the monochlorinated products from
2,4-dimethylpentane.

Steric factor
Relative stability of alkyl radicals
Enthalpy change of different monochlorination reactions
Statistical factor
(II) Which of these factors is dominating in accounting for the higher
yield of 1-chloro-2,4-dimethylpentane? Explain.
Statistical factor
There are 12 primary H, 2 secondary H, 2 tertiary H in
2,4-dimethylpentane
Leads to higher probability of forming primary monochlorinated
product

(v)

Account for the following observation:

When a mixture of 2,4-dimethylpentane and chlorine is irradiated,
reaction starts immediately. However, the reaction does not stop
immediately when irradiation stops.
The reaction is undergoing free radical substitution mechanism
After irradiation, chlorine undergoes hemolytic cleavage to give 2
highly reactive Clfree radicals
Reaction proceeds immediately
When irradiation stops, the free radicals still remains in the reaction
mixture
The reaction will not stop until all radicals are reacted

2008-AL-CHEM 2-16

16

5.

(13 marks)
(b) Outline a synthetic route, with no more than five steps, to accomplish each of
the following transformations. For each step, give the reagent(s), conditions
and the structure of the organic product.
(i)

Step 1: KOH/EtOH, heat

A=

Step 2: Br2

B=

Step 3: excess NH3

(ii)

Hint:

Alkanols react with SOCl2 according to the equation:

ROH + SOCl2 > RCl + SO2 + HCl

Step 1: 1) O3/CCl4 2) Zn dust

A=

Step 2: LiAlH4

B=

Step 3: SOCl2
Step 4: heat

C=

2008-AL-CHEM 2-17

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6.

(7 marks)
(a) Figure 6.1 and Figure 6.2 below respectively show the mass spectrum and
infra-red spectrum of compound A (C4H8O2). Based on the information in the
figures, deduce ONE possible structure of A.

Figure 6.1: Mass spectrum of A

Figure 6.2: Infra-red spectrum of A

Strong absorption peak around 1750 cm-1 (C=O)
Strong absorption peak between 1000 to 1300 cm-1 (C-O)
NO broad absorption peak around 2500 to 3500 cm-1 (NO O-H, not acid)
=> ester / alkoxy carbonyl compounds
m/z 88 = peak of molecular ion
m/z 43 = CH3CO+ ion
m/z 29 = CH3CH2+ ion => CH3CO2CH2CH3
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18

(6 marks)
6.

(b) Consider the reaction between compound B and water in mole ratio of 1:1 as
shown below:

(i)

Given the structure of D.

(ii)

Suggest why the reaction gives D as the major product.

The attacked double bond is tri-substituted, it gives a tertiary (most
stable) carbocation upon electrophilic attack
While the other double bond only gives secondary carbocation

is more stable than

Since the first carbocation is stabilized by dispersion of positive
charge by resonance
(iii)

Give the structure of the major organic product(s) if B and water are
allowed to react in mole ratio of 1:2.

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19

(4 marks)
(c) Ibuprofen, an over-the counter analgesic drug, can be synthesized from
compound E in three steps as shown below:

(i)

For each of Steps 1,2 and 3, suggest the reagent(s) used and the
reaction condition.
Step 1: NH2OH Step 2: heat OR dehydrating agent Step 3: H3O+/heat

(ii)

Suggest a chemical test to distinguish ibuprofen from E.

Any tests for aldehyde/carboxylic acid
Fehlings/ Tollens/ acidified K2Cr2O7
alkali which gives effervescence

(5 marks)
(d) Morphine, a potent analgesic drug, is obtained from the latex extracted from
opium poppy.

(i)

Given that the pKa of the phenolic hydroxyl group of morphine is 9.8
and that of its ammonium salt is 7.9, outline how morphine can be
obtained from the latex extracted from opium poppy.
Add HCl(aq) to latex to convert morphine to its ammonium salt
Add CCl4 to extract non-ionic organic compounds
Obtain the ammonium salt in aqueous layer by crystallization

(ii)

Both morphine and its ammonium salt sublime upon heating. Suggest
why it is necessary to add quicklime, CaO(s), to morphine before it is
disposed of by incineration.
Quicklime is a strong base, it reacts with morphine to form its calcium
phenoxide, which is non-volatile and will not sublime

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20

(5 marks)
7.

(a) Deduce the structure of isomeric compounds F and G, with formula C6H12,
that have the following characteristics:
Compound

Characteristics

It has a pair of enantiomers.

It loses its chiral centre after hydrogenation over Pt.

It reacts with Br2 to give a single compound.

It reacts with HBr to give a single achiral compound.

F is an alkene (undergoes hydrogenation under Pt)

F gives achiral 3-methylpentane upon hydrogenation

Structure:

Enantiomers:
G is an alkene (undergoes addition)
As it gives a single achiral compound only, each double bond C
should have same substitutents

Structure:

Achiral product:

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(6 marks)
(b) (i)

The following reaction gives an organic intermediate J which by

elimination of water gives product K.

(I)

Give the structure of J and that of K.

J:

K:

(II) Outline a mechanism for the formation of J.

(ii)

Polyimines, with a highly conjugated backbone, belong to a type of

conducting polymer which has a wide variety of applications, such as
in electronics and optoelectronics. A part of the structure of a
polyimine L is shown below:

(I)

Draw the structure of the repeating unit of L.

(II) Draw the structure of the monomer(s) of L.

(III) Suggest TWO reasons why the formation of L from its

monomer(s) is an example of green chemistry.
No toxic products are formed (only L and water)
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22

High atom economy

(9 marks)
7.

(c) Compounds M, N, P, Q and R are all colourless liquids. Without the aid of
instrumental analysis, suggest how you would differentiate the five
compounds from one another.
CH3CH2OH CH3COCH3 (CH3)3COH CH3(CH2)3NH2
CH3(CH2)7OH
M

Add acidified K2Cr2O7 to M and P, M is more readily oxidized

OR
Add conc.HCl/ZnCl2(Lucas test), P reacts more rapidly to give a cloudly
mixture
Add 2,4-DNP to N and an orange ppt is formed
Q gives a foul fishy smell
R is the only compound insoluble in water
(5 marks)
END OF PAPER

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