CHEM 6821 Ext Award 1-12 11/2/03 9:51 am Page 1

General Certificate of Education

June 2003
Advanced Extension Award

CHEMISTRY

6821

Wednesday 25 June 2003 9.00 am to 12 noon

In addition to this paper you will require:

a calculator,
a 16-page answer book,
graph paper.

Time allowed: 3 hours

Instructions
Use blue or black ink or ball-point pen.
Write the information required on the front of your answer book. The
Examining Body for this paper is AQA. The Paper Reference is 6821.
Answer all questions.
All working must be shown.
Graph paper must be fastened securely inside the answer book.
Do all rough work in the answer book. Cross through any work you do
not want marked.
Information
The maximum mark for this paper is 160.
Mark allocations are shown in brackets.
You are expected to use a calculator where appropriate.
A Periodic Table is provided on page 2 of this paper.
Advice
You are advised to spend about 30 minutes on Section A, 2 hours on
Section B and 30 minutes on Section C.

Copyright 2003 AQA and its licensors. All rights reserved.

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This Periodic Table may be useful in answering some of the questions in the examination.

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4
SECTION A
You are advised to spend about 30 minutes on this section.

Total for this question: 15 marks

The following passage gives information about the manufacture and reactions of epoxyethane.
Read this passage and answer the questions which follow.
O
Epoxyethane, H2C CH2 , is a simple cyclic compound.
It is manufactured on a large scale by the direct oxidation of ethene with air or oxygen in the
presence of a silver catalyst deposited on a porous support.
Most reactions of epoxyethane involve ring opening and are very exothermic.
Epoxyethane undergoes addition reactions with many compounds containing hydrogen
covalently bonded to an electronegative atom.
Compounds which react with epoxyethane include
H2O, NH3, RNH2, RCOOH and ROH
where R represents an alkyl group.
Commercially, the hydrolysis of epoxyethane to ethane-1,2-diol is an important example of this
type of reaction. An equation for this reaction is shown below.
O
H2O + H2C CH2

HOCH2CH2OH

Acids catalyse this reaction by initially protonating the epoxyethane.

Epoxyethane can also add to compounds with C=O double bonds. Carbon dioxide forms the
cyclic product
H2C C H2
O

C
||
O
1, 3-dioxolan-2-one
When 1, 3-dioxolan-2-one is treated with water, carbon dioxide is formed.
Grignard reagents have the general formula RMgX, where R is an alkyl group and X is a halogen.
Grignard reagents react with epoxyethane in a 1:1 mol ratio to form compounds with the general
formula RCH2CH2OMgX.
Primary alcohols can be produced by the hydrolysis of RCH2CH2OMgX.

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(a)

The hydrolysis of epoxyethane is an exothermic reaction. List the bonds broken and formed
in this reaction and suggest why the reaction is exothermic.
(4 marks)

(b)

Outline a mechanism for the acid-catalysed reaction between one molecule of epoxyethane
and one molecule of ethanol.
(4 marks)

(c)

Deduce the structure of the compound formed when epoxyethane reacts with methanoic
acid.
(1 mark)

(d)

Deduce the structure of the product X formed when epoxyethane reacts with propanone
and predict the compounds formed when X reacts with water.
Deduce the number of peaks in the proton n.m.r. spectrum of X.
(4 marks)

(e)

A compound Y is produced by the reaction of the Grignard reagent CH3CH2MgCl with

epoxyethane. Identify compound Y and the organic compound obtained when compound
Y is hydrolysed by water.
(2 marks)

TURN OVER FOR THE NEXT QUESTION

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6
SECTION B
Answer all three questions in this section.
You are advised to spend about 40 minutes on each question.
Each question carries 40 marks.

Total for this question: 40 marks

(a)

Compound W reacts slowly with water according to the following equation. The reaction is
catalysed by hydrogen ions and eventually goes to completion.
W(aq) + H2O(l) X(aq) + Y(aq) + H+(aq)
Starting with a 0.10 mol dm3 solution of W, the concentration of compound X was
determined at various times at a constant temperature T. The results of this experiment are
shown in the following table.

Concentration of X / mol dm3

0.005

0.010

0.020

0.030

0.040

Time / s

14

25

41

54

68

0.050

0.060

0.070

0.080

0.090

84

104

130

201

380

Concentration of X / mol dm3

Time / s

(b)

(i)

Using these data draw, on the graph paper provided, a graph of concentration against
time. A line should be drawn to pass through all the points.
(3 marks)

(ii)

From your graph determine values for the initial rate of reaction and the maximum
rate of reaction. Show how you determined these values.
Suggest why the values of reaction rate that you have calculated are different from
each other and account for the shape of the curve that you have drawn.
Suggest why your value for the initial rate of reaction is likely to be less accurate than
the maximum rate value.
(10 marks)

The initial rate of the reaction in part (a) was measured for a different series of three
experiments, all at the same temperature, T. A little dilute hydrochloric acid was added in
each case and the initial pH was recorded. The results from these experiments are shown in
the table below.
Initial concentration of W / mol dm3

Initial pH

Initial reaction rate / mol dm3 s1

Expt 1

0.040

3.00

8.8 105

Expt 2

0.020

3.00

2.2 105

Expt 3

0.020

2.82

3.3 105

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(i)

Use these data to determine a rate equation for the reaction of W with water.
Calculate the value, at temperature T, of the rate constant and give its units.
(5 marks)

(ii)

Using your value of the rate constant, calculate the initial rate of reaction of W with
water for a solution of W that has an initial concentration of 0.10 mol dm3 and is
maintained at a pH of 2.90 by using a buffer solution. With the aid of this initial rate
value, sketch on your graph from part (a)(i) a second curve to show how the
concentration of X would vary with time in this buffered solution at temperature T.
Suggest reasons for any differences and any similarities between the two curves.
(If you have been unable to calculate the initial reaction rate you may assume a value
of 8.5 104 mol dm3 s1 but this is not the correct value.)
(7 marks)

(c)

Buffer solutions involving carbon dioxide and hydrogencarbonate ions are important in
biochemistry.
When carbon dioxide dissolves in water, all of the carbon dioxide may be considered to form
the weak acid H2CO3 that dissociates as shown in the following equation.
H2CO3(aq)

H+(aq) + HCO3 (aq)

The dissociation constant, Ka, for this acid has a value of 4.0 107 mol dm3 at 298 K.
(i)

Calculate the pH of a saturated aqueous solution of carbon dioxide that contains

134 cm3 of carbon dioxide gas (measured at 100 kPa and 298 K) dissolved in 200 cm3 of
water.
(The gas constant, R = 8.31 J K1 mol1; the volume of one mole of carbon dioxide gas
at 298 K and 100 kPa is 24.8 dm3)
(6 marks)

(ii)

Human blood is maintained at a pH of 7.4 by organic buffers. Calculate the ratio of

concentrations of HCO3 ions to H2CO3 that would be present in blood at a pH of 7.4
and a temperature of 298 K. Use your answer to suggest what happens to dissolved
carbon dioxide in blood.
(3 marks)

(iii) At higher pH values, hydrogencarbonate ions dissociate as shown below.

HCO3 (aq)

H+(aq) + CO23 (aq)

The dissociation constant, Ka, for this acid has a value of 4.8 1011 mol dm3 at 298 K.
Calculate the mass of solid sodium hydroxide that must be added to 1.0 dm3 of a
0.20 mol dm3 solution of sodium hydrogencarbonate at 298 K in order to produce a
buffer solution with a pH of 10.0.
(6 marks)

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Total for this question: 40 marks

(a)

Consider the following reaction scheme and answer the questions below.

white
precipitate

dil HNO3/

aqueous
copper(II) salt
AgNO3(aq)
A

dilute
aqueous
NH3
precipitate
dissolves

excess
NaCl

yellow/green
solution
containing
complex
B

dilute
aqueous
NH3

precipitate
filtered off

solid white
copper salt
C
dilute
aqueous
NH3

pale blue
precipitate
E
excess
dilute
aqueous
NH3

reduction with
SO2

air

colourless
solution
containing a
linear
complex
copper cation
D

dark blue
solution
F
(i)

Suggest identities for species A to F above and give the shape of complex B.
(7 marks)

(ii)

Write a half-equation (ion-electron equation) for the oxidation of aqueous SO2 to SO24 .
Write an equation for the reaction of aqueous SO2 with complex B.
(2 marks)

(iii) Explain the role of air in the conversion of D into F and, by considering the electron
arrangement of the copper in D, explain why the complex ion D is not coloured.
(3 marks)
(b)

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A reaction in which one of the elements in a substance is both oxidised and reduced at the
same time is called a disproportionation reaction. Chlorine forms several oxides, one of
which is chlorine dioxide, ClO2.
(i)

Chlorine dioxide may be produced from potassium chlorate(V) in a two-step process.

In the first step, potassium chlorate(V) reacts with concentrated sulphuric acid to form
compound J which has the composition H, 1.18%; Cl, 42.01%; O, 56.81% by mass and
an Mr of 84.5.
In the second step, J disproportionates to form chlorine dioxide, together with
chloric(VII) acid, HClO4.
Deduce the formula of compound J and, hence, write equations for the two reactions
involved in the production of chlorine dioxide.
(5 marks)

(ii)

When chlorine dioxide reacts with Fe2+(aq) ions under acidic conditions, or with H2S,
it is converted into Cl(aq) ions. In the reaction with Fe2+(aq) ions, the solution turns
yellow/brown. In the reaction with aqueous hydrogen sulphide, a pale yellow
precipitate of sulphur is formed. Write equations to represent these two reactions.
(4 marks)

CHEM 6821 Ext Award 1-12 11/2/03 9:51 am Page 9

(iii)

Chlorine dioxide reacts with sodium peroxide, Na2O2, forming compound K (Mr = 90.5)
as the only solid product. Compound K contains only sodium, chlorine and oxygen,
and when dissolved in water does not produce a precipitate with aqueous silver
nitrate.
When a given mass of K was strongly heated for a considerable time, a
disproportionation reaction occurred and there was no change in the mass of the solid.
The resulting solid was dissolved in water and the solution formed then gave a
precipitate with aqueous silver nitrate. This solution required the addition of 15.8cm3
of 0.150 mol dm3 aqueous silver nitrate for complete precipitation of the Cl ions.
After the precipitate had been removed, the remaining solution was treated with SO2
to reduce all the remaining chlorine-containing species to Cl ions. A further addition
of 31.6 cm3 of 0.150 mol dm3 aqueous silver nitrate was required for complete
precipitation of these Cl ions.
Deduce the formula of K. Write equations to represent the formation of K and the
disproportionation reaction. Explain your deductions.
(6 marks)

(c)

A compound containing only barium and oxygen has 81.1% of barium by mass. When a
sample of this compound is added to ice-cold dilute sulphuric acid, a white solid is formed;
however, the reaction soon stops. Filtration of this mixture leaves a solution containing
hydrogen peroxide, H2O2, which decolourises acidified aqueous potassium manganate(VII)
and which causes an acidified aqueous solution of potassium iodide to turn brown.
(i)

Calculate the formula of the oxide of barium and write an equation for its reaction
with sulphuric acid. Suggest why the reaction soon stops.
(4 marks)

(ii)

Hydrogen peroxide reacts differently with potassium iodide and with potassium
manganate(VII).
For each reaction separately:

give the half-equation (ion-electron equation) for the reaction of hydrogen

peroxide and for the reaction of the other reactant,
state, and explain in terms of oxidation state changes, the role of the hydrogen
peroxide,
give an overall equation for the reaction.
(9 marks)

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10

Total for this question: 40 marks

(a)

(i)

Suggest why aqueous sodium hydroxide has no reaction with ring-substituted

aromatic halogen compounds such as C6H5Cl but reacts readily with haloalkanes such
as CH3Cl.

(ii)

Compound L contains 52.2% carbon, 3.7% hydrogen and 44.1% chlorine by mass.
When 1.00 g of L was heated with aqueous sodium hydroxide and the resulting
solution treated with an excess of dilute nitric acid followed by aqueous silver nitrate,
0.892 g of silver chloride was formed.
Deduce the empirical formula of L, which is also its molecular formula. Suggest three
possible structures for L. Name and outline a mechanism for the reaction of L with
aqueous sodium hydroxide.
(13 marks)

(b)

Consider the following information and answer the questions which follow.
Deuterium, D (2H), is an isotope of hydrogen and behaves identically to 1H in chemical
reactions. However, D gives no signal in the proton n.m.r. spectrum.
Hydrocarbons in which H is partially or totally replaced by D are said to be deuterated.
(i)

Compound P, C5H11OH, is a tertiary alcohol.

P reacts with an excess of hot, concentrated sulphuric acid to form alkenes Q and R.
The proton n.m.r. spectrum of Q has four peaks with areas in the ratio 3:3:2:2.
Compound Q reacts with DBr to form compounds S and T.
When heated with concentrated ethanolic potassium hydroxide, S forms only Q, but T
forms Q and three other products U, V and W. U gives a proton n.m.r. spectrum
which contains four peaks with areas in the ratio 3:2:2:2.
Deduce and label the structures of P, Q, R, S, T, U, V and W. Give the number of
peaks and the ratio of the peak areas in the proton n.m.r. spectra of R, V and W.
Explain your choice of Q and U and suggest why S is a minor product in the reaction
of Q with DBr. You are not required to write mechanisms or equations.
(14 marks)

(ii)

(c)

Another alcohol, CH2=CHCH2OH, reacts with D2 in the presence of a nickel catalyst

to form compound X. Dehydration of X forms alkenes Y and Z, each of which reacts
with D2 to form a different deuterated propane. Identify X, Y and Z and the
deuterated propanes.
(5 marks)

A compound has the molecular formula C3H5Cl3 and was formed during the reaction of
propane with an excess of chlorine.
Draw the structural isomers of C3H5Cl3 and identify any which show optical isomerism.
Given that chlorine exists as a mixture of the isotopes 35Cl (75%) and 37Cl (25%), deduce
the number of molecular ion peaks in the mass spectrum of C3H5Cl3. Give the m/z value
and the relative abundances of each peak.
(8 marks)

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11
SECTION C
Answer EITHER Question 5(a) OR Question 5(b).
You are advised to spend about 30 minutes on this section.

EITHER

(a)

There are trends in the bonding and properties of the chlorides formed
by the elements in a Period and down a Group in the Periodic Table.
Discuss the factors that influence these trends. Illustrate your answer
by reference to three appropriate chlorides formed by elements in one
Period and also to the chlorides formed by the elements in a single
Group in the Periodic Table.
(25 marks)

OR

(b)

Characteristic properties shown by transition elements and their

compounds include:

the existence of more than one oxidation state in their compounds,

the formation of coloured compounds,
the formation of complexes,
the ability to behave as catalysts.

Explain why each of these properties is shown by transition elements

but not usually by non-transition elements.
Illustrate, by giving an example in each case, how non-transition
elements can display each of the above properties.
(25 marks)

END OF QUESTIONS

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