1

SERANGOON JUNIOR COLLEGE

General Certificate of Education Advanced Level
Higher 2
CANDIDATE
NAME
CLASS

CHEMISTRY

9647/02

Mid-Year Examination
Paper 2 Structured Questions (SPA)

21 May 2015 (AM)

2 hours

Candidates answer on the Question Paper

Additional Materials:

Data Booklet

READ THESE INSTRUCTIONS FIRST

Write your name and class on all the work you hand in.
Write in dark blue or black pen on both sides of the paper.
You may use a soft pencil for any diagrams, graphs or rough work.
Do not use staples, paper clips, highlighters, glue or correction fluid.
Answer all questions.
A Data Booklet is provided.
You are advised to spend 30 minutes on question 1(P).
At the end of the examination, fasten all your work securely together.
The number of marks is given in the brackets [ ] at the end of each question or part questions.
For Examiners Use
P1
/ 40

For Examiners Use

1(P)
/ 12

P2

/ 72

/ 21

P3

/ 80

/ 5

/ 13

/ 21

TOTAL
P2

/ 72

GRAND
TOTAL
/ 192
%

GRADE

This document consists of 15 printed pages

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For
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2
1

Planning (P)
Hard water is water that has high mineral content. Hard water is formed when water percolates
through deposits of calcium and magnesium-containing minerals such as limestone, chalk and
dolomite. Hard drinking water can pose serious problems in industrial settings, where water
hardness is monitored to avoid costly breakdown in equipment that handles water.
The hardness of water can be quantified by instrumental analysis. The procedure is as
described below.
A sample of saturated calcium hydroxide solution is first prepared by reacting calcium metal
with water. The solids are then filtered. The filtrate must be clear as any solid such as Ca(OH)2
interferes with the determination of the saturation concentration of hydroxide ions.
The concentration of dissolved hydroxide will be determined by acid-base titration with
0.001 mol dm3 standardized HCl solution. The Ksp for Ca(OH)2 will be calculated from the
experimentally-determined saturation concentration of hydroxide ions.
(a)

Using the information given above:

(i)

Write a balanced equation for the preparation of the saturated calcium hydroxide
solution.
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(ii)

Suggest a suitable indicator for this titration.

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(iii) Calculate a value of the concentration of the hydroxide ions, given that the
approximate value of the Ksp for calcium hydroxide is 6.5 x 106 mol3 dm9.

(iv) Identify one potential safety hazard and state how you would minimise this risk.
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3
(b) Write a plan for the determination of hydroxide concentration in a saturated solution of
calcium hydroxide.
In your plan you should
give a full description of the procedure you would use to prepare the
saturated calcium hydroxide solution;
explain how you would store the freshly prepared
hydroxide solution to prevent the solution from degradation;

saturated

calcium

give a full description of the procedure you would use for the acid- base titration of
calcium hydroxide with hydrochloric acid.
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[6]
[Total: 12m]
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2 Crude oil, when cracked, gives a variety of organic compounds. It has various industrial uses,
from the petrol chemical industries to the pharmaceutical industries.
Two predominant cycloalkanes isolated from crude oil are 1,3-dimethylcyclopentane and
2-methylbicyclo[2.2.1]heptane.
(a)

(i)

The structure of 2-methylbicyclo[2.2.1]heptane is given below.

Identify the chiral carbons in the structure and hence calculate the number of
optical isomers present.

Number of optical isomers = ___________

(ii)

1,3-dimethylcyclopentane undergoes chlorination in the presence of sunlight to

form mono-chlorinated products in the ratio of 3:1. Draw the two possible
mono-chlorinated products.

[4]
(b) Long chain hydrocarbon undergoes thermal cracking to give short chain alkanes.
A mixture of propane and butane are used in portable gas stoves. This composition of the
fuel mixture can be determined through combustion.
Sample mass of compressed fuel = 5 g
% composition by mass

C3H8
x

C4H10
100 x

The contents of the gas canister was fully combusted in 15 dm3 of oxygen. The total
volume of the residual gas after combustion was 9.76 dm3. 1.50 dm3 of the gas remains
after it was passed through aqueous sodium hydroxide. These gaseous volumes were
measured at room temperature and pressure.
(i) Write two balanced chemical equations illustrating the complete combustion of the
gas mixture.

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For
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(ii) Calculate the volume of the gaseous product at the end of combustion.

(iii) Determine, in terms of x, the volume of the gaseous product produced when the
fuel mixture undergoes complete combustion respectively.

(iv) Based on the information given in the table, and your answer in (ii) and (iii),
determine the respective percentage composition in the gas canister.

[8]
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7
(c)

Hexamine, C6H12N4 is the main component of a solid fuel and its structure is given below.

Hexamine
( Mr of hexamine is 140.2 and Hc = - 4200 kJ mol-1 )
The percentage of hexamine in solid fuel is a trade secret so the exact composition is
unknown. However, it can be determined via calorimetry.
During a camping trip, 4.0 g of solid fuel tablet was used to boil 250 cm3 of water in a pot.
The water had an initial temperature of 30oC. This process was 93% efficient. Calculate
the amount of hexamine combusted and hence determine the percentage mass of
hexamine in the solid fuel tablet.
[3]

(d) (i)

Compound B, an isomer of hexamine, is derived from compound A by reacting with

hydrazine, N2H4.
Draw the Lewis structure of hydrazine, and use the VSEPR theory to predict its
shape and the H-N-H bond angle.

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8
(ii)

Compound A, C6H8O2, has a cyclic structure which does not rotate plane polarised
light. It gave various observations when reacted with different chemical reagents.
No.
1

Chemical reagent
Acidified potassium manganate(VII)

Observation(s)
Solution remains purple.

Phosphorus pentachloride

Solution remains colourless.

Sodium borohydride in ethanol

Diol formed.

Neutral iron(III) chloride

No purple complex formed.

Draw the structural formula of compounds A and B.

B
[6]
[Total: 21 m]

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9
3.

7,8-dihydrovomifoliol gives a fruity aroma in wine.

Complete the reaction scheme below with appropriate structural formula or reagents and
conditions.
Reagents & Conditions :

OH
O

OH
O

OH
+

KMnO4(aq), H , heat

Reagents & Conditions :

H2 (g), Pt, rtp

OH

CH3
CH3

OH

HO

OH
CH3

K2Cr2O7(aq), H ,
distillation

OH

[Total: 5m]
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10
4

The following chemical tests are conducted on compounds C, D and E which are halides
and oxides from Period 3.
Test Procedure
1
Aqueous silver nitrate was
dropwise to a solution of C.

Results
added White precipitate was formed.

Subsequently, aqueous ammonia was White precipitate dissolved in excess

added in excess.
ammonia.
2

The pH of a solution of C was tested pH of solution was approximately 3.

using Universal Indicator paper.

3(a)

Excess dilute hydrochloric acid was White solid D dissolved in dilute

added to D.
hydrochloric acid to form a colourless
solution.

3(b)

Excess dilute sodium hydroxide was White solid D dissolved in dilute

added to D.
sodium hydroxide to form a colourless
solution.

Excess cold water was added to E dissolved to form a colourless

0.010 mol of E. The solution obtained solution that turned blue litmus paper
was tested with litmus paper.
red.
Aqueous silver nitrate was carefully 0.050 mol of aqueous silver nitrate
added to this solution.
was
required
for
complete
precipitation.

(a)

Identify compounds C, D and E.

C:
D:
E:
[3]

(b) Write balanced chemical equations for Tests 3(a) and 3(b).
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[2]

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11
(c)

With the aid of equations, explain the following:

(i)

the observations in Test 1.

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(ii)

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the pH value obtained in Test 2.

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[3]

(iii) the results in Test 4.

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[2]
[Total: 13m]

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12
5

Procaine and Lidocaine were amongst the first injectable local anesthesia to reduce pain
in dental and medical procedures.
Both compounds can be synthesized differently using a reflux setup as shown below.

To synthesize procaine, an equimolar of 3 mol dm-3 of carboxylic acid and alcohol was
refluxed at 80 oC using the set-up below.
RCOOH (l)
(a)

ROH (l)

Procaine (l) +

H2O (l)

H < 0

(i)

Write an expression for the equilibrium constant, Kc.

(ii)

Given Kc is 3.35, determine the percentage conversion of the reactants.

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(iii)

The experiment was repeated using the same initial concentrations of carboxylic
acid and alcohol at 120 oC.
State and explain how this would affect the yield of procaine and the value of Kc.
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[7]

(b)

Chemical structures of Procaine and Lidocaine are given below.

CH3

CH3
CH3

CH3
CH3 O

O
H2N
1

N
2

CH3

Procaine

(i)

Lidocaine

Suggest why is N1 in procaine more basic than N2 in lidocaine.

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(ii)

Describe a chemical test to differentiate the two compounds.

Your chosen test must involve preliminary breakage of chemical bonds.
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[6]

(c)

Organic synthesis is a special branch of chemical synthesis and is concerned with the
construction of organic compounds via organic reactions.
The various methods to chemically synthesise lidocaine and procaine are explored in
the next section.
(i)

2Cl
Cl

The compound above is the starting material to synthesize lidocaine.

State which Cl atom is more reactive and explain your reasoning.
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15
(ii)

Lidocaine can be made via the following synthetic route :

O

2
Cl
Cl

Cl

N
H3C

CH3

G reflux

Lidocaine

Give suitable intermediates of the compounds F and G in the boxes.

(iii)

Procaine can be synthesised in three steps.

NO 2
Raney Nickel*

Procaine

3 steps
COOH

4-nitrobenzoic acid

Suggest a synthetic pathway that ensures high yield of Procaine and in your
chosen route, provide an alternative reducing agent to Raney nickel.
*Note : Raney Nickel is a reducing agent used to convert nitro groups to amino groups .

[8]
[Total : 21 m]

END OF PAPER

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