The questions in this mock paper are adapted from the 2013 H2 Chemistry Preliminary Exams

of the following schools: MJC, NYJC, PJC, SAJC, SRJC and YJC.
Note: This document is intended only for the revision purposes of students in Raffles
Institution. Distribution of this document to unauthorized personnel is strictly prohibited.

H2 Chemistry

9647/2

Paper 2 Structured
2013

24 October

Additional Materials: Data Booklet

hours

Planning
The solubility of solid lead iodate(V), Pb(IO3)2, in water is low. When a sample of this salt is
mixed with water, a small amount dissolves and an equilibrium between the solid salt and its
aqueous ions is established.
Pb(IO3)2(s)

Pb2+(aq) + 2IO3-(aq)

Ksp = [Pb2+] [IO3-]2 mol3 dm-9

The concentration of iodate(V) ions present in the saturated solution is described as follows:

Iodine is liberated when excess potassium iodide, KI, is added to an acidified solution
containing iodate(V) ions.
IO3-(aq) + 5I-(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)

The liberated iodine can then be reacted with a standard solution of sodium thiosulfate.
2S2O32-(aq) + I2(aq) 2I-(aq) + S4O62-(aq)

You are to design a titrimetric experiment to determine the solubility product of lead iodate (V).
(a)

You are provided the following:

Solid lead iodate(V)

Solid potassium iodide
1 mol dm-3 hydrochloric acid
0.0200 mol dm-3 sodium thiosulfate
Starch indicator
Distilled water
And any other standard laboratory apparatus.

Describe, step-by-step (including quantities of reagents used), the procedure involved in

your experiment.
[4]
1

(b)

Suggest one possible error that may occur during the experiment.
[1]

(c)

Calculate the solubility product of lead iodate(V) given that 25.0 cm3 of the saturated
solution requires v cm3 of Na2S2O3.
[3]

1
(d)
A solution contains a mixture of chloride ions and iodide ions.
You are provided with the reagents HCl(aq), NH3(aq), AgNO3(aq), HNO3(aq) and distilled water
together with test tubes, a filter funnel and filter papers.
Devise a sequence of steps by which, using only the above materials, the two anions could be
separately obtained as precipitates.

Test
1

Expected Observations

Deduction

[4]

[Total: 12 marks]

2
(a)
Elements J, K, and L are consecutive elements in period 3 of the Periodic Table.

The first eight ionisation energies, I.E., of element K are as follows.

I.E. / kJ
mol1

1011

1907

2914

4963

6273

21267

25431

29872

(i)
With reference to the data given above, deduce the Group of the Periodic Table to which K is
likely to belong to.

(ii)
Predict, giving your reasoning, whether the first ionisation energy of element L will be higher or
lower than that of K.

[4]

(b)
(i)
Construct an energy level diagram for the formation of Ca 3(PO4)2 from its elements using
relevant data from the table below and other appropriate values in the Data Booklet. Hence
calculate the lattice energy of Ca3(PO4)2.

Enthalpy
Standard enthalpy change of formation of Ca3(PO4)2
Standard enthalpy change of atomisation of Ca
Standard enthalpy change of atomisation of P
P(g) + 4O(g) + 3e PO43-(g)

H / kJ mol-1
4132
+178
+315
2810

(ii)
Using your answers to (i) and other enthalpy change value if any, explain why Ca 3(PO4)2 is
insoluble in water.
5

[6]

2
(c)
Ammonia shows significant deviations from the ideal behaviour that is predicted by the kinetic
theory of gases.

State three important assumptions of ideal gas behaviour.

[2]

(d)
In a typical iodine clock reaction, solutions of hydrogen peroxide, sulfuric acid, potassium iodide,
starch and sodium thiosulfate are mixed. There are two reactions occurring in the reaction
mixture.

In the first reaction, iodide ions are oxidised slowly by acidified hydrogen peroxide to form
iodine.

H2O2(aq) + 2I(aq) + 2H+(aq) I2(aq) + 2H2O(l)

reaction I

In the second reaction, iodine is reduced back to iodide ions as they are generated.

2S2O32(aq) + I2(aq) S4O62(aq) + 2I(aq)

reaction II

When all the sodium thiosulfate present has reacted, iodine will appear in the solution producing
an immediate deep blue colour with starch indicator.

A series of experiments was carried out using different volumes of the five reagents, each
solution being made up to the same total volume with water. The following results were
obtained.

expt no.

1
2
3
4

volume of
0.10
mol dm-3
H2O2
/ cm3

volume of
0.100
mol dm-3
KI
/ cm3

18
6
6
12

12
12
18
12

volume of
0.100
mol dm-3
HCl
/ cm3
6
12
12
12

volume of
0.050
mol dm-3
Na2S2O3
/ cm3
2
2
2
2

volume of
starch
solution
/ cm3

3
3
3
3

volume of
water
/ cm3

59
65
59
59

time for
the
appearan
ce of
deep blue
colour
/s
23
70
47
35

(i)
Calculate the relative initial rate of reaction I for each of these experiments.

(ii)
Given that the order of reaction with respect to hydrogen peroxide is found to be one, use the
results in (d)(i) to deduce the order of reaction with respect to I and H+ in reaction I. Explain
your reasoning.

(iii)
8

Hence write an overall rate equation for reaction I, stating the units of the rate constant.

2
(d)
(iv)
Suggest, with reasons, which of the following two mechanisms, A or B, fits the observed
kinetics data.

Mechanism A
2H+(aq) + 2I(aq) 2HI (aq)
2HI(aq) + H2O2 (aq) I2(aq) + 2H2O(l)

(fast)
(slow)

Mechanism B
H2O2 (aq) + I(aq) H2O(l) + OI(aq)
H+(aq) + OI(aq) HIO(aq)
HIO(aq) + I(aq) + H+(aq) I2(aq) + H2O(l)

(slow)
(fast)
(fast)

(v)
With the aid of a sketch of the Boltzmann distribution, explain how an increase in temperature
increases the rate of the reaction.

[10]

[Total: 22 marks]

3
Grignard reagents are very useful in organic synthesis reactions. This question concerns the
preparation and use of Grignard reagents. A Grignard reagent has the formula RMgX where X is
a halogen, and R is an alkyl or aryl group.

RX + Mg

RMgX
Grignard reagent

10

Grignard reagents readily react with carbonyl compounds to form their corresponding alcohols
as outlined in the general equations below.

step I

step II

(a)
State the type of reaction for steps I and II respectively.

[2]

(b)
Grignard reagents are formed readily by iodoalkanes. Using the above general reaction
scheme, the Grignard reagent, CH3CH2MgI is first generated from iodoethane. This is
subsequently reacted with pentan2one, converting it into a tertiary alcohol.
11

Draw the displayed formula of the final organic product formed in step II.

[1]

3
The experimental procedure below details the conversion of pentan2one to the alcohol
product, which involves the initial preparation of a Grignard reagent.
The Grignard reagent is highly reactive and has to be carefully prepared in an anhydrous
environment.

Procedure
1

1.50 g of magnesium turnings is added to a pear-shaped flask with an equimolar quantity of

iodoethane and 20 cm3 of diethylether.

A crystal of iodine is added to the mixture from step 1 to activate the magnesium, and this
mixture is refluxed.

The mixture is allowed to cool and 6.0 cm 3 of pentan2one is added dropwise. The mixture
is then gently heated under reflux.
12

Next, the mixture is cooled using an ice bath, and then 25 cm 3 of 4 mol dm3 hydrochloric
acid is slowly added.

The mixture from step 4 is added to a separating funnel. The aqueous layer is separated
and shaken successively with two 10 cm3 portions of diethylether, retaining the diethylether
extracts and combining them with the original diethylether layer.

The combined diethylether layer is washed successively with 20 cm3 of

(i)
water,
(ii)
saturated sodium hydrogencarbonate solution,
(iii)
1 mol dm3 aqueous sodium thiosulfate,
(iv)
saturated sodium chloride solution.

The diethylether layer is allowed to stand over anhydrous magnesium sulfate.

formula

molar
mass / g
mol1

density /
g cm3

iodoethane

C2H5I

156

1.93

diethylether

C2H5OC2H5

74

0.713

magnesium
turnings

Mg

24.3

1.74

pentan-2-one

C5H10O

86

0.814

substance

product
alcohol

0.823

solubility in
water
slightly
soluble
slightly
soluble
insoluble
slightly
soluble
slightly
soluble

boiling
point / C
72
35
1110
102
143

Table 2.1: Physical Properties of the reagents and the organic product

13

(c)
Suggest the role of the diethylether in step 1 of the procedure.

[1]

3
(d)
(i)
In step 2, the mixture is refluxed. Suggest why elevated temperatures and long periods of time
are required for reactions such as this.

(ii)
Show, with the use of calculation whether the Grignard reagent or pentan2one is in excess.
Assume that the reaction between magnesium and iodoethane in step 2 had 100 % yield.
14

[2]

(e)
In the diagram of the separating funnel below, draw the two layers that will be observed after
step 4. Indicate the relative position of the two layers.

15

[1]

(f)
In step 6, the water and the three aqueous solutions used to wash the diethylether layer are
intended to remove a particular impurity, either by dissolving or by chemical reaction followed by
dissolving.

Suggest the impurity removed in each step.

(i)
water

(ii)
saturated sodium hydrogencarbonate
16

(iii)
sodium thiosulfate

(iv)
saturated sodium chloride

[2]

17

(g)
After step 7, further separation and purification has to be carried out in order to collect the
alcohol product. Briefly describe how you would obtain a pure sample of the alcohol product.

[1]

[Total: 10 marks]

4
(a)
The gaseous hydrogen halides HCl, HBr and HI, may be prepared by reacting the corresponding
sodium salt with concentrated phosphoric (V) acid, H3PO4.

18

When sodium halide NaX was used, a sample of gaseous HX was collected in a gas jar. A hot
glass rod was placed in the sample of HX and orange fumes was observed immediately. When
aqueous NaOH was added, the orange colour disappeared.

(i)
Suggest the identity of NaX.

(ii)
Explain why concentrated phosphoric (V) acid rather than concentrated sulfuric acid is used to
prepare samples of HX from the corresponding sodium salt.

19

(iii)
The hydrogen halides can be thermally decomposed under suitable conditions. By quoting
appropriate data from the Data Booklet, explain the trend in the thermal stability of the hydrogen
halides.

[4]

(b)
Chlorine is manufactured commercially by the electrolysis of brine (concentrated sodium
chloride) using the diaphragm cell.
product A

product B

brine

product C
titanium electrode

steel electrode
diaphragm
20

(i)
Give half equations for the two electrode processes that occur.

(ii)
Calculate the current that needs to be passed through the diaphragm cell in order to produce
1.00 tonne of chlorine gas per day. (1 tonne = 1000 kg)

The diaphragm is made of a porous mixture of asbestos and polymers, designed to prevent the
products of the electrolytic cell from mixing with each other.
21

(iii)
Write a balanced equation for the reaction that will occur if A is allowed to mix with B. Describe
a potential safety hazard of this reaction.

(iv)
Write a balanced equation for the reaction that will occur if product A is allowed to mix with
product C at room temperature.

[7]

[Total: 11 marks]
5
(a)
Ascorbic acid is an antioxidant commonly found in fruits, better known as vitamin C. Its structure
is as shown below.
22

OH
O

HO

H
OHA

OHB

ascorbic acid
(Mr = 176.0)

When ascorbic acid dissociates in aqueous solution, the proton labelled HA is released to form
the ascorbate ion.

Values of the acid dissociation constant, Ka, for ascorbic acid and other organic acids are given
below.

acid
Ascorbic acid
Acetic acid
Formic acid

formula
given above
CH3COOH
HCOOH

Ka / mol dm3
7.9 105
1.8 105
1.8 104

Kordels Acid Free C is a health supplement that provides vitamin C in the form of the non-acidic
calcium ascorbate. This is suitable for consumption by people with sensitive stomachs who are
unable to tolerate vitamin C in its original acidic form.

23

(i)
Write an equation to show how non-acidic vitamin C is effective in controlling acidity levels in the
stomach.

(ii)
Calculate the pH of a solution of ascorbic acid and calcium ascorbate at its optimal buffering
capacity.

(iii)
Given that the mass of ascorbic acid used to create the buffer solution in (a)(ii) is 5.00 g, find
the change in pH when 0.01 g of calcium hydroxide is added to the buffer solution.

[5]
24

5
(b)
The Beckmann rearrangement reaction is one useful method of preparing amides by heating an
oxime with concentrated sulfuric acid. An example for the synthesis of N-methylethanamide is
shown below.

OH

NH
O

The reaction is thought to proceed via the following stages.

25

OH

H
H+

N
H

II

H+

III

(i)
Name the type of reaction occurring in step I.

(ii)
State the oxidation number of nitrogen in compound A.

26

NH
H+ O

IV

(iii)
Outline the mechanism occurring in the step IV, showing clearly the movement of lone pairs of
electrons with the use of curly arrows.

[3]

(c)
Aminocaproic acid is commonly used to treat excessive postoperative bleeding. The Beckmann
rearrangement can be used as the second step in the synthesis of aminocaproic acid from
cyclohexanone.

NH2OH

OH

conc. H2SO4
heat

II

III

C
Titrate with NaOH
until pH = pI

27

H3N

aminocaproic acid

(i)
Suggest the type of reaction occurring in step I.

(ii)
State the reagents and conditions used in step III.

28

CO2-

(iii)
Draw the structures of compounds B and C.

[4]

[Total: 12 marks]

6
(a)
Malic acid, HO2CCH2CH(OH)CO2H, was first isolated from apple juice by Carl Wilhelm Scheele
in 1785, and is now commonly added to food products to produce a tartness in various food
products like candy and beverages.

29

Malic acid is produced industrially by reacting malic anhydride with water in a two-step reaction
scheme as shown.

O +H O
2

I
malic anhydride

+ H2O
OH

HO
X

II

OH
OH

HO
O
malic acid

(i)
The intermediate product, X, obtained from step I exist only in the cis-isomeric form. Suggest
why this is so.

30

(ii)
Describe a simple chemical test to distinguish between X and malic acid, stating the expected
observations of each compound.

[3]

(b)
Melatonin can undergo a series of reactions to obtain compound X.

OCH3

NH2

Br

Br
O
NHCH2COBr

Compound X

Explain the different reactivities of the three bromine atoms in compound X.

31

[2]

[Total: 5 marks]

FOR EXAMINERS USE

~~~~END OF PAPER 2 ~~~~

32

Q1

/ 12

Q2

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Q3

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Q4

/ 11

Q5

/ 12

Q6

/5

Total

/ 72