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1. (a) Define the term standard electrode potential.

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(2)

(b) When a metal is placed in a solution of its ions, the electrical potential set up between the
metal and the solution cannot be measured without using a reference electrode. Explain
why this is so.

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(1)

(c) The following data will be required in this part of the question.


E /V

2+
Zn (aq) + 2e Zn(s) 0.76

2+
Fe (aq) + 2e Fe(s) 0.44
2+
Sn (aq) + 2e Sn(s) 0.14


O2(g) + 2H2O(1) + 4e 4OH (aq) +0.40

(i) Write an overall equation for the first stage in the rusting of iron.

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(2)

1

(ii) Calculate E for the reaction in (i) and show that it is feasible.

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(2)


(iii) Use the E values above to explain why zinc is used in preference to tin for
preventing corrosion of steel car bodies.

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(3)
(Total 10 marks)

2. Domestic bleaches contain sodium chlorate(I), NaOCl.

(a) Write the ionic equation to show the disproportionation of the chlorate(I) ion. Use
oxidation numbers to explain the meaning of the term disproportionation in this reaction.

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(3)

(b) Domestic bleaches are dilute solutions of sodium chlorate(I). The amount of ClO ions in
a sample can be found by reacting it with excess acidified potassium iodide solution.

+
ClO + 2I + 2H I2 + Cl + H2O

The iodine produced is then titrated with standard sodium thiosulphate solution.
3 3
10.0 cm of a domestic bleach was pipetted into a 250 cm volumetric flask and made
up to the mark with distilled water.
3
A 25.0 cm portion of the solution was added to excess acidified potassium iodide
solution in a conical flask.
3
This mixture was titrated with 0.100 mol dm sodium thiosulphate solution, using
starch indicator added near the end point.
3
The mean titre was 12.50 cm .

(i) Give the colour change you would see at the end point.

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(1)

3
(ii) The equation for the reaction between iodine and thiosulphate ions is

2 2
2S2O3 + I2 S4O6 + 2I

3
Calculate the amount (moles) of chlorate(I) ions in 1.00 dm of the original bleach.

(5)

3
(iii) Use the equation below to calculate the mass of chlorine available from 1.00 dm
of the original bleach. Give your answer to 3 significant figures.

+
ClO + Cl + 2H Cl2 + H2O

(1)
(c) Sodium thiosulphate can be used to remove the excess chlorine from bleached fabrics.

2 2 +
S2O3 + 4Cl2 + 5H2O 2SO4 + 10H + 8Cl

By considering the change in oxidation number of sulphur, explain whether chlorine or


iodine is the stronger oxidising agent when reacted with thiosulphate ions.

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(2)

(d) Starch-iodide paper can be used to test for chlorine. It contains starch and potassium
iodide.

Explain the reactions taking place when a piece of damp starch-iodide paper is put in a
gas jar of chlorine. State what you would see.

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(2)
(Total 14 marks)

5
3. This question is about the arene, naphthalene. The structure of naphthalene can be shown as

(a) What is the molecular formula of naphthalene?

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(1)

(b) The enthalpy change, H, for the addition of hydrogen to cyclohexene to form
1
cyclohexane is 120 kJ mol .

1
+ 2 H H = 1 2 0 k J

(i) Calculate the enthalpy change of the hydrogenation reaction shown below.

+ 2 5 H

1
H = ...................... kJ mol
(1)

(ii) Experimental work shows that H for the hydrogenation of naphthalene is


1
actually 333 kJ mol . What does this suggest about the stability and structure of
naphthalene?

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(2)
(iii) Would you expect naphthalene to decolorise bromine solution? Justify your
answer.

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(1)

(c) The Friedel-Crafts reaction enables an alkyl group to be attached to an arene ring.

(i) Suggest the reagent and catalyst you would need to make
C H 3( 2 C H )

from naphthalene.

Reagent ..............................................................................

Catalyst ..............................................................................
(2)

(ii) Name the type of reaction and its mechanism.

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(2)
(Total 9 marks)

4. This question concerns redox chemistry.

Consider the following data



E /V
3+ 2+
Fe (aq) + e Fe (aq) +0.77

Cl2(aq) + 2e 2Cl (aq) +1.36
+ 2+
MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O(l) +1.51

7
(a) (i) Use the data to explain why dilute hydrochloric acid is not used to
acidify solutions of potassium manganate(VII).

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(2)

(ii) Explain why titrations involving potassium manganate(VII) solution do not require
the addition of an indicator.

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(1)

(b) (i) The ionic equation for the oxidation of iron(II) ions by
manganate(VII) ions in acidic solution is

2+ + 2+ 3+
MnO4 (aq) + 5Fe (aq) + 8H (aq) Mn (aq) + 4H2O(l) + 5Fe (aq)

Explain, in terms of the half equations listed above, why the ratio of
manganate(VII) ions to iron(ii) ions is 1 : 5 in this reaction.

(1)
(ii) Patients suffering from iron deficiency are often prescribed tablets containing
hydrated iron(II) sulphate, FeSO4.7H2O.

Some tablets, of total mass 6.00 g, were dissolved in distilled water and made up to
3 3
200 cm in a volumetric flask. 25.0 cm portions of this solution were titrated
3
against a 0.0200 mol dm solution of acidified potassium manganate(VII). The
3
mean titre was 20.10 cm .

Calculate the percentage of hydrated iron(II) sulphate in the tablets.


1
[Molar mass FeSO4.7H2O = 278 g mol ]

(5)

(c) An important application of redox reactions is in car batteries. The electrolyte is aqueous
sulphuric acid and the standard electrode potentials involved are shown below.

E /V
2+
Pb (aq) + 2e Pb(s) 0.13
+ 2+
PbO2(s) + 4H (aq) + 2e Pb (aq) + 2H2O(l) +1.46

(i) Calculate the standard e.m.f. of the cell.

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(1)

9
(ii) A single cell in a car battery has an e.m.f. of 2.00 V. Suggest why this value is
different from the answer calculated in (i).

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(1)
(Total 11 marks)

5. The element iodine can be produced from the mineral Chile saltpetre, which contains sodium
iodate, NaIO3. The iodate ions are converted to iodine in a two-step process.

Ionic equations for the reactions are shown below.


Step 1 IO3 (aq) + 3HSO3(aq) I (aq) + 3HSO4 (aq)

+
Step 2 IO3 (aq) + 5I (aq) + 6H (aq) 3I2(aq) + 3H2O(l)

(a) (i) Describe a test you could carry out to confirm the presence of iodide
ions in a solution. Indicate the result of the test.

Test ...................................................................................................................

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Result ................................................................................................................

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(2)
(ii) Identify the TWO elements in Step 1 which show a change of oxidation number
during the reaction.

Give their initial and final oxidation numbers.

First element ........................................ Second element


...................................

Initial oxidation number ...................... Initial oxidation


number .....................

Final oxidation number ....................... Final oxidation


number ......................
(3)


(iii) The equation for Step 1 shows that 1 mole of iodate ions, IO3 , reacts with 3 moles
of hydrogensulphite ions, HSO3. Show that your answers to (ii) agree with this
ratio.
(1)

(b) An experiment was carried out to determine the concentration of the iodine prepared in
Step 2

3
A 10.0 cm portion of the iodine solution was titrated with sodium thiosulphate solution
3
of concentration 0.0100 mol dm . The volume of sodium thiosulphate solution added at
3
the end-point was 24.0 cm .

The equation for the reaction is

I2(aq) + 2Na2S2O3(aq) 2NaI(aq) + Na2S4O6(aq)

3
(i) What piece of apparatus would you use to measure out the 10.0 cm portion?

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(1)

(ii) Suggest a suitable indicator to show the end-point of this titration. State the colour
change you would see.

Indicator .................................................................................................................

From .........................................................to ........................................................


(2)

11
(iii) Calculate the number of moles of sodium thiosulphate used in the titration.

(1)

(iv) Calculate the number of moles of iodine which reacted with the sodium
thiosulphate solution.

(1)

3
(v) Calculate the concentration, in mol dm , of the iodine solution.

(1)
(Total 12 marks)
3
6. Air is drawn through 10.0 cm of an aqueous solution of vanadium(II) chloride of concentration
3
0.100 mol dm . The colour of the solution slowly changes as oxidation takes place.

The air-oxidised solution is titrated with a solution of acidified potassium manganate(VII) of


3 3
concentration 0.0200 mol dm . The end point is found to be 20.0 cm .

(i) Draw a diagram of suitable apparatus for carrying out the air-oxidation of the
vanadium(II) chloride solution.

(1)

(ii) Complete the half equation for acidified manganate(VII) ions acting as an oxidising
agent.

+ 2+
MnO4 (aq) + ..............H (aq) + 5e (aq) Mn (aq) + ..............H2O(1)
(1)

13
(iii) Calculate the number of moles of manganate(VII) ions used in the titration, and hence the
number of moles of electrons removed by the manganate(VII) ions.
3
Calculate the number of moles of vanadium(II) ions in the 10 cm of solution used. Find
the oxidation number of vanadium in the air-oxidised solution given that vanadium(V)
ions are formed in the titration.

(4)

(iv) Suggest ONE reason why acidified potassium manganate(VII) is a useful oxidising agent
in redox titrations.

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(1)
(Total 7 marks)
7. Brass is a widely-used alloy that contains copper and zinc. There are many varieties of brass
with different compositions.

In the volumetric analysis of the composition of brass, the first step is to react a weighed sample
of the alloy with nitric acid. This gives a greenish-blue solution.

(a) The following standard electrode potentials are needed for this question:

E /V
2+
Zn + 2e Zn 0.76
2+
Cu + 2e Cu + 0.34
+
NO3 + 2H + e NO2 + H2O + 0.81


(i) Use the half equations given above and the values of E to calculate the standard
electrode potential for the reaction between zinc and nitric acid and derive the
equation.

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(2)

(ii) Suggest why zinc does not produce hydrogen with nitric acid.

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(2)

15
(iii) If the greenish-blue solution is diluted with water it turns light blue and contains
hydrated copper(II) ions.

Name the light blue complex ion and draw its structure so as to show its shape.

Name .................................................................................................................

Structure:

(2)

(iv) If concentrated hydrochloric acid is added to a portion of the light blue solution it
turns green.

State the type of reaction that occurs and give an equation for the reaction.

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(2)

(b) The light blue solution from (a)(iii) is then neutralised, and reacted with an excess of
potassium iodide solution.

The following standard electrode potentials are needed:



E /V
2+ +
Cu + e Cu + 0.15

I2 + 2e 2I + 0.54

(i) Use these E values to explain why you would not expect the following reaction to
occur.

2+
2Cu (aq) + 4I (aq) 2CuI(s) + I2(aq)

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(1)

(ii) Explain why, in practice, the reaction in (i) does occur and iodine is liberated.

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(2)

(iii) When the precipitate formed in the reaction in (i) is filtered off and then dissolved
in concentrated aqueous ammonia, a colourless solution is produced.

Suggest the formula of the cation in this solution.

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(1)

(iv) If the colourless solution from (iii) is left to stand in air for some time, it turns blue.

State why this is so, naming the reactant responsible for the change.

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(2)

17
(c) In a determination of the composition of a sample of brass, 1.50 g of the alloy was treated
3
to give 250 cm of a neutral solution of copper(II) nitrate and zinc nitrate.

3
Excess potassium iodide solution was added to 25.0 cm portions of this solution, and the
3
liberated iodine titrated with 0.100 mol dm sodium thiosulphate solution. The mean titre
3
was 16.55 cm .

2+
2Cu (aq) + 4I (aq) 2CuI(s) + I2(aq)
2 2
2S2O3 (aq) + I2(aq) 2I (aq) + S4O6 (aq)

(i) State which indicator you would use for the titration and the colour change seen at
the end point.

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(2)

(ii) Explain why the indicator is not added until the reaction is nearly complete.

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(1)

(iii) Calculate the percentage of copper by mass in this brass.

(5)
(Total 22 marks)
8. (a) Give the electronic configuration of:

Cu : [Ar] ......................................................................................................................
+
Cu : [Ar] ......................................................................................................................
(1)

+
(b) (i) Explain why Cu ions are colourless.

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(2)

(ii) Copper(I) ions disproportionate in aqueous solution. Give the equation for the
reaction and use the standard electrode potentials given below to explain why the
reaction occurs.

E /V
2+ +
Cu (aq) + e Cu (aq) + 0.15
+
Cu (aq) + e Cu(s) + 0.52

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(2)

+
(iii) Explain why your answer to (ii) does not rule out the existence of Cu (aq) under
standard conditions.

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(1)

19
(c) (i) When a small amount of dilute ammonia solution is added to a
solution of copper(II) sulphate, a turquoise blue precipitate, F, is formed.

F has the composition Cu 49.4%, S 12.5%, O 37.4%, H 0.78% by mass. Calculate


its empirical formula.

(2)

(ii) When F is dissolved in dilute hydrochloric acid, the resulting blue solution gives a
white precipitate with barium chloride solution.

Suggest a formula for F, given that all the hydrogen is present in hydroxide ions.

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(2)

(iii) When excess concentrated ammonia is added to F, a deep blue solution is formed.
Give the formula of the ion responsible for this colour.

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(1)

(iv) What type of reaction is occurring in (iii)?

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(1)
(d) Copper metal can be used as a catalyst. When propan-1-ol vapour is passed over heated
copper, the following reaction occurs:

CH3CH2CH2OH CH3CH2CHO + H2

(i) Outline how, by the use of 2,4-dinitrophenylhydrazine and suitable tables of data,
you could show that the product is propanal.

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(4)

(ii) When propan-1-ol is oxidised with a solution of potassium dichromate(VI) in


dilute sulphuric acid care must be taken to avoid further oxidation of the aldehyde
product. How is this achieved?

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(1)

(iii) What is the further oxidation product of the aldehyde?

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(1)

(iv) Suggest why the oxidation of the alcohol by passing it over heated copper does not
lead to further oxidation of the aldehyde.

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(1)

21
(v) There are a few places on the surface of the metal where catalysis can occur.
These are called active sites.

Suggest why this leads to the rate of reaction being independent of the gas pressure
unless this pressure is extremely low.

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(1)
(Total 20 marks)

9. (a) (i) Complete the electronic configurations of:

Cr: [Ar].

Cu: [Ar]..
(1)

(ii) The electronic configurations of chromium and of copper are not readily
predictable from a consideration of the elements on either side of them in the first
transition series in the Periodic Table.

State how these electronic configurations differ from others in the first transition
series and explain why this difference arises.

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(2)
3+
(b) Chromium can form the ion [Cr(H2O)6] in aqueous solution.

(i) Draw the structure of this ion so as to clearly show its shape.

(1)

(ii) How are the bonds between the water ligands and the metal ion formed?

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(1)

(iii) Write an equation to show what happens initially when a solution containing
3+
hydroxide ions is added to a solution of [Cr(H2O)6] ions.

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(2)

(iv) State what you would see as dilute sodium hydroxide is gradually added to a
3+
solution of [Cr(H2O)6] until it is in excess.

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(2)

23
(v) What property of chromium(III) hydroxide is shown by the reaction in part (iv)?

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(1)

(c) (i) A 1.00 g sample of a metal alloy that contains chromium was
3
converted into 250 cm of an acidified solution of potassium dichromate(VI).

3
25.0 cm of this solution was added to an excess of potassium iodide solution.

2 + 3+
Cr2O7 + 6I + 14H 2Cr + 3I2 + 7H2O

3
The iodine liberated was titrated with 0.100 mol dm sodium thiosulphate
solution.
2 2
I2 + 2S2O3 2I + S4O6

The mean (average) titre was 37.2 cm3.

Calculate the amount (moles) of iodine liberated and hence the percentage, by
mass, of chromium in the alloy.

(5)

(ii) In titrations involving iodine, starch is usually added near the end-point to make
the colour change clearer, although in many cases it is not really necessary.

Suggest why starch is necessary in the titration in (i).

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(1)
(Total 16 marks)
2+
10. A firm claims that their iron tablets contain 10 mg of Fe per tablet. A chemist wishes to check
this by titration using potassium manganate(VII) and dilute sulfuric acid.

2+ 3+
Fe (aq) Fe (aq) + e

+ 2+
MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O(l)

(a) Why is the acid necessary?

.....................................................................................................................................

.....................................................................................................................................
(1)

2+
(b) How many moles of Fe react with one mole of MnO4 ?

.....................................................................................................................................
(1)

2+
(c) Each tablet contains 10 mg of Fe .
2+
(i) How many moles of Fe are in one tablet?

(1)

25
3
(ii) Use your answer to (i) to calculate the volume of 0.010 mol dm potassium
manganate(VII) solution that would be needed to react with one tablet.

(2)

(iii) Is this a suitable volume to verify the integrity of the firms claim? How would you
alter the experiment to obtain a more suitable volume?

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(1)
2+
(d) The recommended consumption of Fe per day is 14 mg. The tolerable upper level of
2+
consumption of Fe per day is 45 mg.

The 10 mg iron tablets produced by a pharmaceutical company contain between 9 and


2+
11 mg of Fe .

Discuss whether or not this range of iron content is acceptable.

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(2)
(Total 8 marks)

27
1. This question is about Group 7 of the Periodic Table - the halogens.
The standard electrode potentials for these elements are given below.

Electrode reaction E /V

1
2
F2 + e F +2.87

1
2
Cl2 + e Cl +1.36

1
2
Br2 + e Br +1.07

1
2
I2 + e I +0.54

(a) (i) Define the term standard electrode potential.

......................................................................................................................

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......................................................................................................................
(2)

(ii) State which element or ion in the table above is the strongest oxidising agent.

......................................................................................................................
(1)

(b) The standard electrode potentials for chromium(III) changing to chromium(II) and for
chromium(VI) changing to chromium(III) are given below.

Cr3+ + e Cr2+ E = 0.41V

1
2
Cr2 O72+ 7H+ + 3e Cr3+ + 7
2
H2O E = +1.33V

1
(i) On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III).

......................................................................................................................
(1)

(ii) On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III) but not to chromium(VI).

......................................................................................................................
(1)

(iii) Chromium(II) in aqueous solution is sky blue while aqueous chromium(III)


solution is dark green. Describe how you would show that your prediction in part
(ii) actually worked in practice.

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(2)

2. (a) The electronic configuration of a cobalt atom can be written as [Ar]3d74s2.


Give the electronic configuratin of the Co3+ ion.

......
(1)

2
(b) (i) By reference to the standard electrode potentials given below, suggest a reducing
agent which might reduce aqueous Co3+ ions to cobalt metal. Give your reasoning.

E /V
Zn2+(aq) + 2e Zn(s) 0.76
Fe2+(aq) + 2e Fe(s) 0.44
Co2+(aq) + 2e Co(s) 0.28
Sn2+(aq) + 2e Sn(s) 0.14
O2(g) + 2H+(aq) + 2e H2O2(aq) +0.68

Co3+(aq) + e Co2+(aq) +1.82

Suitable reducing agent ....

Reasoning .....

.......
(3)

(ii) Suggest two factors that might prevent a reducing agent from being as effective as
the electrode potentials might seem to suggest.

.......

.......

.......

.......
(2)

(c) (i) Write the formula of the hexaaquacobalt(II) ion.

.......
(1)

3
(ii) Give an equation, involving the hexaaquacobalt(II)ion, to illustrate the process
of ligand exchange.

.......
(2)
(Total 9 marks)

3. The concentration of iron(II) ions in a solution can be found by titration with standard
potassium manganate(VII) solution. In the reaction iron(II) ions are oxidised to iron(III)
ions.

If a solution contains both iron(II) and iron(III) ions, the concentration of each ion can be
found by:

titrating samples of the original solution with standard potassium manganate(VII) solution

reacting samples of the original solution with zinc and dilute sulphuric acid and then titrating
with the same potassium manganate(VII) solution.

The following standard electrode potentials are required:

E/V

Zn2+ + 2e Zn 0.76

Fe2+ + 2e Fe 0.44

Fe3+ + e Fe2+ + 0.77

MnO4 + 8H+ + 5e Mn2+ + 4H2O + 1.51

(a) (i) Use suitable E values to show that both iron(II) and iron(III) ions in solution
should react with zinc to give iron metal.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(ii) In practice the reaction produces only iron(II) ions and no iron metal.

2Fe3+ + Zn 2Fe2+ + Zn2+

4
Suggest a reason for this.

.....................................................................................................................................

.....................................................................................................................................
(1)

(b) (i) Derive the ionic equation for the reaction between iron(II) ions and
manganate(VII), MnO4, ions.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(ii) State what you would see as iron(II) ions in solution are titrated with potassium
manganate(VII). How would you detect the endpoint of the titration?

.....................................................................................................................................

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.....................................................................................................................................

.....................................................................................................................................
(3)

5
(c) A solution containing both iron(II) and iron(III) ions was titrated with 0.0200 mol dm3
potassium manganate(VII) solution, 18.20 cm3 being required.

Another portion of the same volume of the same solution was reacted with zinc, and then
titrated with the same potassium manganate(VII) solution; 25.30 cm3 was required.
What mass of zinc had reacted?

(5)

6
(d) (i) Explain, including an equation, why aqueous solutions of hexaaqua ions such as
[Fe(H2O)6]2+ are acidic.

.....................................................................................................................................

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.....................................................................................................................................

.....................................................................................................................................
(3)

(ii) Suggest with reasons which of 0.1 mol dm3 aqueous solutions of [Fe(H2O)6]2+ and
[Fe(H2O)6]3+ would be the more acidic.

.....................................................................................................................................

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(3)
(Total 20 marks)

4. (a) (i) Define the term standard electrode potential, making clear the meaning of
standard in this context.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

7
(ii) Explain the need for a standard reference electrode in electrochemical
measurements.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(1)

(b) The following data will be required in this part of the question.

E/V
+ 2+
MnO4 + 8H + 5e Mn + 4H2O +1.52
O2 + 2H+ + 2e H2O2 +0.68
H2O2 + 2H+ + 2e 2H2O +1.77

(i) Derive the equation for the reaction between hydrogen peroxide and
manganate(VII) ions in acidic solution and use E values to show that the reaction
is feasible.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(ii) If a sample of hydrogen peroxide was titrated with potassium manganate(VII)


solution, what would you see during the reaction, and then at the endpoint?

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

8
(iii) Derive the equation for the disproportionation of hydrogen peroxide and explain, in
terms of oxidation states, why it is a disproportionation reaction.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)
(Total 12 marks)

5. (a) (i) Give the electronic configuration of:

Fe [Ar].....................................................................................................

Fe2+ [Ar].....................................................................................................
(2)

(ii) Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6]2+, so as to clearly show
its shape.

(1)

(iii) Give the equation for the complete reaction of sodium hydroxide solution with a
solution of hexaaquairon(II) ions.

............................................................................................................................
(1)

9
(iv) State what you would see if the product mixture in (iii) is left to stand in air.

............................................................................................................................

............................................................................................................................
(1)

(v) Give the equation for a reaction in which iron metal is used as a catalyst.

............................................................................................................................
(1)

(b) Consider the half reaction

Fe2+ + 2e Fe E = 0.44 V

(i) Define the term standard electrode potential with reference to this electrode.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

10
(ii) Explain, with the aid of an equation, why the value of E suggests that iron will
react with an aqueous solution of an acid to give Fe2+ ions and hydrogen gas.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.

............................................................................................................................

............................................................................................................................
(1)

(c) Use the following standard electrode potentials to explain why iron(III) iodide does not
exist in aqueous solution.

Fe3+ + e Fe2+ E = +0.77 V

I2 + 2e 2I E = +0.54 V

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(2)
(Total 15 marks)

11
6. (a) Define the term standard electrode potential.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(b) When a metal is placed in a solution of its ions, the electrical potential set up between the
metal and the solution cannot be measured without using a reference electrode. Explain
why this is so.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(1)

(c) The following data will be required in this part of the question.

E/V

Zn2+(aq) + 2e Zn(s) 0.76

Fe2+(aq) + 2e Fe(s) 0.44

Sn2+(aq) + 2e Sn(s) 0.14

O2(g) + 2H2O(1) + 4e 4OH(aq) +0.40

(i) Write an overall equation for the first stage in the rusting of iron.

...........................................................................................................................

...........................................................................................................................
(2)

12
(ii) Calculate E for the reaction in (i) and show that it is feasible.

...........................................................................................................................

...........................................................................................................................
(2)

(iii) Use the E values above to explain why zinc is used in preference to tin for
preventing corrosion of steel car bodies.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)
(Total 10 marks)

7. (a) The elements from scandium to zinc belong to the d-block. Some, but not all, of these
elements are transition elements.

(i) What is meant by the term transition element?

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Which of the elements, from scandium to zinc inclusive, are in the d-block but are
not transition elements?

...........................................................................................................................
(1)

(b) (i) Complete the electronic configurations of the Fe2+ and Mn2+ ions below.

Fe2+ [Ar] ..............................................................................................................

Mn2+ [Ar] .............................................................................................................


(1)

13
(ii) Suggest why Fe2+ ions are readily oxidised to Fe3+ ions, but Mn2+ ions are not
readily oxidised to Mn3+ ions.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(c) Draw a diagram to show the three-dimensional structure of the [Fe(CN)6]4 complex ion.

(2)

(d) A solution of potassium manganate(VII), KMnO4, can be standardised by titration with


arsenic(III) oxide, As2O3. In this reaction, 5 mol of arsenic(III) oxide are oxidised to
arsenic(V) oxide, As2O5, by 4 mol of manganate(VII) ions, MnO4.

Calculate the final oxidation number of the manganese.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(4)

14
(e) Ammonium vanadate(V), NH4VO3, reacts with dilute sulphuric acid to form a solution
containing yellow VO2+ ions.

(i) Write an ionic equation for the reaction of the anion in NH4VO3 with dilute
sulphuric acid.

...........................................................................................................................
(1)

(ii) Is the reaction in (i) a redox reaction? Justify your answer.

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Addition of zinc to the solution containing VO2+ ions causes the colour to change
from yellow to green then to blue, followed by green again and finally violet.
State the formulae of the ions responsible for each of these colours.

The first green colour ...............................................................................

The second green colour ...............................................................................

The violet colour ................................................................................


(3)
(Total 16 marks)

15
8. Domestic bleaches contain sodium chlorate(I), NaOCl.

(a) Write the ionic equation to show the disproportionation of the chlorate(I) ion. Use
oxidation numbers to explain the meaning of the term disproportionation in this reaction.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(b) Domestic bleaches are dilute solutions of sodium chlorate(I). The amount of ClO ions in
a sample can be found by reacting it with excess acidified potassium iodide solution.

ClO + 2I + 2H+ I2 + Cl + H2O

The iodine produced is then titrated with standard sodium thiosulphate solution.

10.0 cm3 of a domestic bleach was pipetted into a 250 cm3 volumetric flask and made
up to the mark with distilled water.
A 25.0 cm3 portion of the solution was added to excess acidified potassium iodide
solution in a conical flask.
This mixture was titrated with 0.100 mol dm3 sodium thiosulphate solution, using
starch indicator added near the end point.
The mean titre was 12.50 cm3.

(i) Give the colour change you would see at the end point.

...........................................................................................................................

...........................................................................................................................
(1)

16
(ii) The equation for the reaction between iodine and thiosulphate ions is

2S2O32 + I2 S4O62 + 2I

Calculate the amount (moles) of chlorate(I) ions in 1.00 dm3 of the original bleach.

(5)

(iii) Use the equation below to calculate the mass of chlorine available from 1.00 dm3
of the original bleach. Give your answer to 3 significant figures.

ClO + Cl + 2H+ Cl2 + H2O

(1)

17
(c) Sodium thiosulphate can be used to remove the excess chlorine from bleached fabrics.

S2O32 + 4Cl2 + 5H2O 2SO42 + 10H+ + 8Cl

By considering the change in oxidation number of sulphur, explain whether chlorine or


iodine is the stronger oxidising agent when reacted with thiosulphate ions.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(d) Starch-iodide paper can be used to test for chlorine. It contains starch and potassium
iodide.

Explain the reactions taking place when a piece of damp starch-iodide paper is put in a
gas jar of chlorine. State what you would see.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)
(Total 14 marks)

18
9. This question concerns redox chemistry.

Consider the following data

E / V
Fe3+(aq) + e Fe2+(aq) +0.77
Cl2(aq) + 2e 2Cl(aq) +1.36
MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l) +1.51

(a) (i) Use the data to explain why dilute hydrochloric acid is not used to acidify solutions
of potassium manganate(VII).

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Explain why titrations involving potassium manganate(VII) solution do not require
the addition of an indicator.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

19
(b) (i) The ionic equation for the oxidation of iron(II) ions by manganate(VII) ions in
acidic solution is

MnO4 (aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)

Explain, in terms of the half equations listed above, why the ratio of
manganate(VII) ions to iron(ii) ions is 1 : 5 in this reaction.

(1)

20
(ii) Patients suffering from iron deficiency are often prescribed tablets containing
hydrated iron(II) sulphate, FeSO4.7H2O.

Some tablets, of total mass 6.00 g, were dissolved in distilled water and made up to
200 cm3 in a volumetric flask. 25.0 cm3 portions of this solution were titrated
against a 0.0200 mol dm3 solution of acidified potassium manganate(VII). The
mean titre was 20.10 cm3.

Calculate the percentage of hydrated iron(II) sulphate in the tablets.

[Molar mass FeSO4.7H2O = 278 g mol1]

(5)

(c) An important application of redox reactions is in car batteries. The electrolyte is aqueous
sulphuric acid and the standard electrode potentials involved are shown below.

E / V
Pb2+(aq) + 2e Pb(s) 0.13
PbO2(s) + 4H+(aq) + 2e Pb2+(aq) + 2H2O(l) +1.46

(i) Calculate the standard e.m.f. of the cell.

...........................................................................................................................

...........................................................................................................................
(1)

21
(ii) A single cell in a car battery has an e.m.f. of 2.00 V. Suggest why this value is
different from the answer calculated in (i).

...........................................................................................................................

...........................................................................................................................
(1)
(Total 11 marks)

10. Brass is a widely-used alloy that contains copper and zinc. There are many varieties of brass
with different compositions.

In the volumetric analysis of the composition of brass, the first step is to react a weighed sample
of the alloy with nitric acid. This gives a greenish-blue solution.

(a) The following standard electrode potentials are needed for this question:

E/V
Zn2+ + 2e Zn 0.76
Cu2+ + 2e Cu + 0.34
NO3 + 2H+ + e NO2 + H2O + 0.81

(i) Use the half equations given above and the values of E to calculate the standard
electrode potential for the reaction between zinc and nitric acid and derive the
equation.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Suggest why zinc does not produce hydrogen with nitric acid.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

22
(iii) If the greenish-blue solution is diluted with water it turns light blue and contains
hydrated copper(II) ions.

Name the light blue complex ion and draw its structure so as to show its shape.

Name .................................................................................................................

Structure:

(2)

(iv) If concentrated hydrochloric acid is added to a portion of the light blue solution it
turns green.

State the type of reaction that occurs and give an equation for the reaction.

...........................................................................................................................

...........................................................................................................................
(2)

(b) The light blue solution from (a)(iii) is then neutralised, and reacted with an excess of
potassium iodide solution.

The following standard electrode potentials are needed:

E/V
2+ +
Cu + e Cu + 0.15
I2 + 2e 2I + 0.54

23
(i) Use these E values to explain why you would not expect the following reaction to
occur.

2Cu2+(aq) + 4I (aq) 2CuI(s) + I2(aq)

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Explain why, in practice, the reaction in (i) does occur and iodine is liberated.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) When the precipitate formed in the reaction in (i) is filtered off and then dissolved
in concentrated aqueous ammonia, a colourless solution is produced.

Suggest the formula of the cation in this solution.

...........................................................................................................................
(1)

(iv) If the colourless solution from (iii) is left to stand in air for some time, it turns blue.

State why this is so, naming the reactant responsible for the change.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

24
(c) In a determination of the composition of a sample of brass, 1.50 g of the alloy was treated
to give 250 cm3 of a neutral solution of copper(II) nitrate and zinc nitrate.

Excess potassium iodide solution was added to 25.0 cm3 portions of this solution, and the
liberated iodine titrated with 0.100 mol dm3 sodium thiosulphate solution. The mean titre
was 16.55 cm3.

2Cu2+(aq) + 4I (aq) 2CuI(s) + I2(aq)


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

(i) State which indicator you would use for the titration and the colour change seen at
the end point.

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Explain why the indicator is not added until the reaction is nearly complete.

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Calculate the percentage of copper by mass in this brass.

(5)
(Total 22 marks)

25
11. (a) Define the term standard electrode potential, making clear the meaning of standard.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(b) Explain why a reference electrode is needed whenever a standard electrode potential is
measured.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(1)

(c) Hydrogen peroxide decomposes in a disproportionation reaction.

(i) Explain the meaning of disproportionation.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

26
(ii) Use the following information to derive the equation for the disproportionation of
hydrogen peroxide.

Calculate Ecell and explain whether the reaction is thermodynamically feasible.

O2 + 2H+ + 2e H2O2 E = + 0.68 V


H2O2 + 2H+ + 2e 2H2O E = + 1.77 V

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(iii) Explain why your answer to (ii) does not necessarily show that hydrogen peroxide
will disproportionate under standard conditions.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)
(Total 9 marks)

27
12. (a) The conversion of butan-2-ol to 2-bromobutane can be performed as outlined below:

Butan-2-ol is heated with a mixture of 50 % aqueous sulphuric acid and sodium


bromide for 45 minutes.
The crude 2-bromobutane is distilled off.
The crude 2-bromobutane is shaken with pure water, which removes the sulphuric
acid and some of the butan-2-ol that contaminates the product.
The organic layer is separated and then shaken with concentrated hydrochloric acid to
remove residual butan-2-ol.
The organic layer is then shaken with dilute sodium carbonate solution.
Anhydrous calcium chloride is added to the organic layer and allowed to stand for
some hours.
The organic layer is then redistilled in a dry apparatus.

(i) Explain, in terms of kinetic factors, why the mixture is heated for a significant
amount of time.

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Why is sulphuric acid necessary in the reaction mixture?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) Suggest why butan-2-ol, which is only partially miscible with water, is much more
soluble in concentrated hydrochloric acid.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

28
(iv) Why is the organic layer shaken with dilute sodium carbonate solution?

...........................................................................................................................

...........................................................................................................................
(1)

(v) What is the purpose of the anhydrous calcium chloride?

...........................................................................................................................
(1)

(vi) How would you heat the mixture safely? Explain your choice of method.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

29
(b) Both 2-bromobutane and butan-2-ol are chiral molecules.

If one optical isomer of 2-bromobutane is used to make butan-2-ol by reaction with


aqueous hydroxide ions, the product mixture is not optically active.

The mechanism for the reaction is either SN1 or SN2; these are given below

SN1 CH2CH3 CH2CH3

+
H3 C C Br H3C C + :Br

H H

CH2CH3 CH2CH3

+
H3 C C + :OH H3C C OH

H H


SN2 HO: CH2CH3 CH2CH3

H3 C C Br HO C Br

H3C H
H

CH2CH3


HO C H + :Br

CH3

30
Explain which one of these mechanisms is consistent with the lack of optical activity in
the product mixture.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(c) The oxidation of butan-2-ol with hot potassium dichromate(VI) in acidic solution
produces butanone, CH3COCH2CH3.

(i) What would you see as the reaction proceeds?

...........................................................................................................................
(1)

(ii) The dichromate(VI) ion is reduced under these conditions to chromium(III) ions.

The half-equation for the oxidation of butan-2-ol to butanone is

CH3CH(OH)CH2CH3 CH3COCH2CH3 + 2H+ + 2e

Write the ionic half-equation for the reduction of dichromate(VI) ions, and hence
derive the overall equation for the oxidation of butan-2-ol.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

31
(iii) The IR spectra of butan-2-ol and of the organic product from its oxidation with
dichromate(VI) ions are given below.

Spectrum of butan-2-ol

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500

Wavenumber/cm 1

Spectrum of the organic product from the oxidation of butan-2-ol

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500

Wavenumber/cm 1

Bond Wavenumber/cm1 Bond Wavenumber/cm1


CO (alcohols,
CH (alkanes) 28503000 10001300
esters)
OH (hydrogen-
CH (alkenes) 30003100 32303550
bonded alcohols)
C=O (aldehydes, 16801750 OH (hydrogen- 25003300
ketones, carboxylic bonded carboxylic
acids) acids)

32
What evidence is there from the spectra that the reaction in part (ii) has occurred?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(d) When potassium dichromate(VI) is dissolved in water, the following equilibrium is set up

Cr2O72(aq) + H2O(l) 2CrO42(aq) + 2H+(aq)

(i) If a solution of barium ions is then added to this solution, solid barium chromate,
BaCrO4, is precipitated; it is sparingly soluble in water, so the equilibrium given
below also exists in the solution

Ba2+(aq) + CrO42(aq) BaCrO4(s)

Explain what happens to the pH when the barium ions are added.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

33
(ii) If a solution of lead(II) ions is added instead of barium ions, solid PbCrO4 is
precipitated. This is almost completely insoluble in water so all chromate(VI) ions
are removed from solution

Pb2+(aq) + CrO42(aq) PbCrO4(s)

State how the pH of this solution differs from your answer in part (i).

...........................................................................................................................

...........................................................................................................................
(1)
(Total 20 marks)

13. In a standard hydrogen electrode

A the hydrogen gas is at one atmosphere pressure

B a solution of 1 mol dm3 sulfuric acid is used

C a temperature of 273 K is maintained

D a piece of shiny platinum foil is used


(Total 1 mark)

14. For a redox reaction to be thermodynamically feasible, Ecell must be

A positive

B negative

C greater than +0.3 V

D more negative than 0.3 V


(Total 1 mark)

34
15. The standard electrode potential for the electrode system based on the equation below is
+1.51 V.

MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l)

Which of the following statements about the electrode system is correct?

A the electrode potential at pH 5 is +1.51 V.

B Mn2+(aq) is acting as an oxidising agent.

C changing the concentration of Mn2+(aq) would cause a change in the electrode potential.

D the electrode used in this half-cell is made of manganese.


(Total 1 mark)

16. Which of the following is always proportional to Ecell for a chemical reaction?

A Hr

B Ssystem

C Ssurroundings

D Stotal
(Total 1 mark)

17. Methanol can be vigorously oxidised with an acidified solution containing dichromate(VI) ions,
Cr2O72, to form methanoic acid and chromic(III) ions.

(a) What are the oxidation numbers of carbon in methanol and methanoic acid?

Methanol Methanoic acid

A 1 +1

B 2 +2

C +1 1

D +2 2
(1)

35
(b) How many moles of methanol react with one mole of dichromate(VI) ion, Cr2O72?

A 1

C 1

D 3
(1)
(Total 2 marks)

18. (a) (i) Give the electron configuration of:

Fe [Ar] .........................................................................................................

Fe2+ [Ar] .........................................................................................................


(1)

(ii) Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6]2+, clearly showing its
shape.

(1)

(iii) Give the equation for the complete reaction of hydroxide ions with a solution of
hexaaquairon(II) ions.

(1)

36
(iv) State what you would see if the product mixture in (iii) is left to stand in air.

...........................................................................................................................

...........................................................................................................................
(1)

(b) Consider the equation for the half reaction

Fe2+ + 2e Fe E = 0.44 V

(i) Define the term standard electrode potential with reference to this electrode.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(ii) Explain why the value of E suggests that the iron will react with an aqueous
solution of an acid to give Fe2+ ions and hydrogen gas.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

37
(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.

...........................................................................................................................

...........................................................................................................................
(1)
(Total 10 marks)

38
1. This question is about nickel compounds.

(a) Hydrated nickel(II) salts are green in colour. Give the electron configuration of a
nickel(II) ion and hence state why the ion is coloured.

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................
(2)

(b) (i) Which is the only nickel compound, in Table 5.3 in the Book of Data, in which the
nickel atom does not have an oxidation number of +2?

............................................................................................................................
(1)

(ii) What is the oxidation number of nickel in this compound?

............................................................................................................................
(1)

(c) Nickel(II) chloride solution contains the ion Ni(H2O)62+(aq). On adding ammonia
solution, the colour changes to blue or purple as different complexes are formed.

(i) Write the equation, including state symbols, for the displacement of one water
molecule by an ammonia molecule.

(1)

(ii) Would you expect Ssystem for this reaction to be positive, negative or close to
zero? Justify your answer.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(2)

St Michael's Catholic Grammar School 1


(d) The complexes formed when ammonia solution is added to nickel(II) chloride solution
have the formula [Ni(H2O)x(NH3)6x]Cl2. An experiment was carried out to determine the
value of x in one of them.

A sample of 5.000 g of this complex was dissolved in water and reacted with excess
silver nitrate. 6.133 g of silver chloride was produced.

(i) Write the ionic equation, including state symbols, for the formation of silver
chloride.

(1)

(ii) Calculate the number of moles of silver chloride produced.

Each mole of the complex contains two moles of chloride ions. Calculate the
number of moles of the complex present in the 5.000 g sample.

Hence calculate the mass of one mole of the complex.

(3)

St Michael's Catholic Grammar School 2


(iii) Use your answer in (ii) to calculate the value of x and hence the formula of this
complex ion.

(1)

(iv) Draw TWO possible structures for this complex ion.

(2)
(Total 14 marks)

2. This question is about the element chromium and its compounds.

(a) (i) State the full electronic configuration of a chromium atom in the ground state,
using the s,p,d notation.

(1)

St Michael's Catholic Grammar School 3


(ii) Apart from differing numbers of electrons, how does the ground state electronic
configuration of chromium differ from those of the two adjacent elements in the
Periodic Table, vanadium and manganese? Suggest the reason for this difference.

................................................................................................................................

................................................................................................................................

................................................................................................................................

................................................................................................................................
(2)

(b) Compounds containing the chromium(II) ion, Cr2+, are unstable in aqueous solution
because they are readily oxidised by oxygen in the air.
State the appropriate electrode potentials and half-cells, and use them to explain why this
oxidation takes place.

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................
(3)

(c) A useful method of stabilising an unstable oxidation state is to form a complex. You may
have prepared chromium(II) ethanoate, Cr2(CH3CO2)4(H2O)2, where the Cr2+ ion is
stabilised in this way. [Details can be found on pages 464465 of your Students Book.]

St Michael's Catholic Grammar School 4


(i) Explain how water acts as a monodentate ligand in this complex.

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................
(2)

(ii) What type of ligand is the ethanoate ion in this complex?

...............................................................................................................................
(1)

(iii) Deduce the number of hydrogen peaks in the NMR spectrum of the complex from
the structural formula Cr2(CH3CO2)4(H2O)2. Justify your answer.

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................
(2)

(iv) Suggest TWO characteristic absorptions in the infra-red spectrum of the complex.

You should state the bond associated with each absorption and give the
corresponding absorption value in wavenumbers.

................................................................................................................................

................................................................................................................................

................................................................................................................................

................................................................................................................................
(2)

St Michael's Catholic Grammar School 5


(d) (i) When first introduced, breathalysers used acidified sodium dichromate(VI) crystals
to detect ethanol on the breath. Using oxidation numbers, or otherwise, balance the
equation for the reaction.

C2H6O + Na2Cr2O7 + H2SO4 C2H4O + Cr2(SO4)3 + H2O + Na2SO4

(2)

(ii) State the colour change you would expect to see if exhaled air containing an
excessive amount of ethanol reacted with the breathalyser chemicals.

................................................................................................................................
(1)

(iii) What hazard is associated with the use of sodium dichromate(VI)?

................................................................................................................................

................................................................................................................................
(1)
(Total 17 marks)

3. The element iodine can be produced from the mineral Chile saltpetre, which contains sodium
iodate, NaIO3. The iodate ions are converted to iodine in a two-step process.

Ionic equations for the reactions are shown below.

Step 1 IO3(aq) + 3HSO3(aq) I(aq) + 3HSO4(aq)

Step 2 IO3(aq) + 5I(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)

St Michael's Catholic Grammar School 6


(a) (i) Describe a test you could carry out to confirm the presence of iodide ions in a
solution. Indicate the result of the test.

Test ...................................................................................................................

...........................................................................................................................

Result ................................................................................................................

...........................................................................................................................
(2)

(ii) Identify the TWO elements in Step 1 which show a change of oxidation number
during the reaction.

Give their initial and final oxidation numbers.

First element ........................................ Second element ...................................

Initial oxidation number ...................... Initial oxidation number .....................

Final oxidation number ....................... Final oxidation number ......................


(3)

(iii) The equation for Step 1 shows that 1 mole of iodate ions, IO3, reacts with 3 moles
of hydrogensulphite ions, HSO3. Show that your answers to (ii) agree with this
ratio.
(1)

(b) An experiment was carried out to determine the concentration of the iodine prepared in
Step 2

A 10.0 cm3 portion of the iodine solution was titrated with sodium thiosulphate solution
of concentration 0.0100 mol dm3. The volume of sodium thiosulphate solution added at
the end-point was 24.0 cm3.

The equation for the reaction is

I2(aq) + 2Na2S2O3(aq) 2NaI(aq) + Na2S4O6(aq)

(i) What piece of apparatus would you use to measure out the 10.0 cm3 portion?

...........................................................................................................................
(1)

St Michael's Catholic Grammar School 7


(ii) Suggest a suitable indicator to show the end-point of this titration. State the colour
change you would see.

Indicator .................................................................................................................

From .........................................................to ........................................................


(2)

(iii) Calculate the number of moles of sodium thiosulphate used in the titration.

(1)

(iv) Calculate the number of moles of iodine which reacted with the sodium
thiosulphate solution.

(1)

St Michael's Catholic Grammar School 8


(v) Calculate the concentration, in mol dm3, of the iodine solution.

(1)
(Total 12 marks)

4. Air is drawn through 10.0 cm3 of an aqueous solution of vanadium(II) chloride of concentration
0.100 mol dm3. The colour of the solution slowly changes as oxidation takes place.

The air-oxidised solution is titrated with a solution of acidified potassium manganate(VII) of


concentration 0.0200 mol dm3. The end point is found to be 20.0 cm3.

(i) Draw a diagram of suitable apparatus for carrying out the air-oxidation of the
vanadium(II) chloride solution.

(1)

(ii) Complete the half equation for acidified manganate(VII) ions acting as an oxidising
agent.

MnO4(aq) + ..............H+(aq) + 5e(aq) Mn2+(aq) + ..............H2O(1)


(1)

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(iii) Calculate the number of moles of manganate(VII) ions used in the titration, and hence the
number of moles of electrons removed by the manganate(VII) ions.

Calculate the number of moles of vanadium(II) ions in the 10 cm3 of solution used. Find
the oxidation number of vanadium in the air-oxidised solution given that vanadium(V)
ions are formed in the titration.

(4)

(iv) Suggest ONE reason why acidified potassium manganate(VII) is a useful oxidising agent
in redox titrations.

.....................................................................................................................................

.....................................................................................................................................
(1)
(Total 7 marks)

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5. Brass is a widely-used alloy that contains copper and zinc. There are many varieties of brass
with different compositions.

In the volumetric analysis of the composition of brass, the first step is to react a weighed sample
of the alloy with nitric acid. This gives a greenish-blue solution.

(a) The following standard electrode potentials are needed for this question:

E/V
Zn2+ + 2e Zn 0.76
Cu2+ + 2e Cu + 0.34
NO3 + 2H+ + e NO2 + H2O + 0.81

(i) Use the half equations given above and the values of E to calculate the standard
electrode potential for the reaction between zinc and nitric acid and derive the
equation.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Suggest why zinc does not produce hydrogen with nitric acid.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

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(iii) If the greenish-blue solution is diluted with water it turns light blue and contains
hydrated copper(II) ions.

Name the light blue complex ion and draw its structure so as to show its shape.

Name .................................................................................................................

Structure:

(2)

(iv) If concentrated hydrochloric acid is added to a portion of the light blue solution it
turns green.

State the type of reaction that occurs and give an equation for the reaction.

...........................................................................................................................

...........................................................................................................................
(2)

(b) The light blue solution from (a)(iii) is then neutralised, and reacted with an excess of
potassium iodide solution.

The following standard electrode potentials are needed:

E/V
2+ +
Cu + e Cu + 0.15
I2 + 2e 2I + 0.54

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(i) Use these E values to explain why you would not expect the following reaction to
occur.

2Cu2+(aq) + 4I (aq) 2CuI(s) + I2(aq)

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Explain why, in practice, the reaction in (i) does occur and iodine is liberated.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) When the precipitate formed in the reaction in (i) is filtered off and then dissolved
in concentrated aqueous ammonia, a colourless solution is produced.

Suggest the formula of the cation in this solution.

...........................................................................................................................
(1)

(iv) If the colourless solution from (iii) is left to stand in air for some time, it turns blue.

State why this is so, naming the reactant responsible for the change.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

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(c) In a determination of the composition of a sample of brass, 1.50 g of the alloy was treated
to give 250 cm3 of a neutral solution of copper(II) nitrate and zinc nitrate.

Excess potassium iodide solution was added to 25.0 cm3 portions of this solution, and the
liberated iodine titrated with 0.100 mol dm3 sodium thiosulphate solution. The mean titre
was 16.55 cm3.

2Cu2+(aq) + 4I (aq) 2CuI(s) + I2(aq)


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

(i) State which indicator you would use for the titration and the colour change seen at
the end point.

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Explain why the indicator is not added until the reaction is nearly complete.

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Calculate the percentage of copper by mass in this brass.

(5)
(Total 22 marks)

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6. (a) Give the electronic configuration of:

Cu : [Ar] ......................................................................................................................

Cu+: [Ar] ......................................................................................................................


(1)

(b) (i) Explain why Cu+ ions are colourless.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Copper(I) ions disproportionate in aqueous solution. Give the equation for the
reaction and use the standard electrode potentials given below to explain why the
reaction occurs.

E/V
Cu2+(aq) + e Cu+(aq) + 0.15
Cu+(aq) + e Cu(s) + 0.52

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) Explain why your answer to (ii) does not rule out the existence of Cu+(aq) under
standard conditions.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

St Michael's Catholic Grammar School 15


(c) (i) When a small amount of dilute ammonia solution is added to a solution of
copper(II) sulphate, a turquoise blue precipitate, F, is formed.

F has the composition Cu 49.4%, S 12.5%, O 37.4%, H 0.78% by mass. Calculate


its empirical formula.

(2)

(ii) When F is dissolved in dilute hydrochloric acid, the resulting blue solution gives a
white precipitate with barium chloride solution.

Suggest a formula for F, given that all the hydrogen is present in hydroxide ions.

...........................................................................................................................
(2)

(iii) When excess concentrated ammonia is added to F, a deep blue solution is formed.
Give the formula of the ion responsible for this colour.

...........................................................................................................................
(1)

(iv) What type of reaction is occurring in (iii)?

...........................................................................................................................
(1)

St Michael's Catholic Grammar School 16


(d) Copper metal can be used as a catalyst. When propan-1-ol vapour is passed over heated
copper, the following reaction occurs:

CH3CH2CH2OH CH3CH2CHO + H2

(i) Outline how, by the use of 2,4-dinitrophenylhydrazine and suitable tables of data,
you could show that the product is propanal.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(4)

(ii) When propan-1-ol is oxidised with a solution of potassium dichromate(VI) in


dilute sulphuric acid care must be taken to avoid further oxidation of the aldehyde
product. How is this achieved?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

(iii) What is the further oxidation product of the aldehyde?

...........................................................................................................................
(1)

(iv) Suggest why the oxidation of the alcohol by passing it over heated copper does not
lead to further oxidation of the aldehyde.

...........................................................................................................................

...........................................................................................................................
(1)

St Michael's Catholic Grammar School 17


(v) There are a few places on the surface of the metal where catalysis can occur.
These are called active sites.

Suggest why this leads to the rate of reaction being independent of the gas pressure
unless this pressure is extremely low.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)
(Total 20 marks)

7. (a) (i) Complete the electronic configurations of:

Cr: [Ar].

Cu: [Ar]..
(1)

(ii) The electronic configurations of chromium and of copper are not readily
predictable from a consideration of the elements on either side of them in the first
transition series in the Periodic Table.

State how these electronic configurations differ from others in the first transition
series and explain why this difference arises.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

St Michael's Catholic Grammar School 18


(b) Chromium can form the ion [Cr(H2O)6]3+ in aqueous solution.

(i) Draw the structure of this ion so as to clearly show its shape.

(1)

(ii) How are the bonds between the water ligands and the metal ion formed?

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Write an equation to show what happens initially when a solution containing
hydroxide ions is added to a solution of [Cr(H2O)6]3+ ions.

...........................................................................................................................

...........................................................................................................................
(2)

(iv) State what you would see as dilute sodium hydroxide is gradually added to a
solution of [Cr(H2O)6]3+ until it is in excess.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

St Michael's Catholic Grammar School 19


(v) What property of chromium(III) hydroxide is shown by the reaction in part (iv)?

...........................................................................................................................
(1)

(c) (i) A 1.00 g sample of a metal alloy that contains chromium was converted into
250 cm3 of an acidified solution of potassium dichromate(VI).

25.0 cm3 of this solution was added to an excess of potassium iodide solution.

Cr2O72 + 6I + 14H+ 2Cr3+ + 3I2 + 7H2O

The iodine liberated was titrated with 0.100 mol dm3 sodium thiosulphate
solution.

I2 + 2S2O32 2I + S4O62

The mean (average) titre was 37.2 cm3.

Calculate the amount (moles) of iodine liberated and hence the percentage, by
mass, of chromium in the alloy.

(5)

(ii) In titrations involving iodine, starch is usually added near the end-point to make the
colour change clearer, although in many cases it is not really necessary.

Suggest why starch is necessary in the titration in (i).

...........................................................................................................................

...........................................................................................................................
(1)
(Total 16 marks)

St Michael's Catholic Grammar School 20


8. Methanol can be vigorously oxidised with an acidified solution containing dichromate(VI) ions,
Cr2O72, to form methanoic acid and chromic(III) ions.

(a) What are the oxidation numbers of carbon in methanol and methanoic acid?

Methanol Methanoic acid

A 1 +1

B 2 +2

C +1 1

D +2 2
(1)

(b) How many moles of methanol react with one mole of dichromate(VI) ion, Cr2O72?

A 1

C 1

D 3
(1)
(Total 2 marks)

9. Which of the following will not act as a ligand in the formation of complexes?

A C6H5NH2

B CH3NH2

C NH4+

D NH3
(Total 1 mark)

St Michael's Catholic Grammar School 21


10. Which of the following ground state electron configurations corresponds to an element most
likely to form an oxide with catalytic properties?

A 1s2 2s2

B 1s2 2s2 2p6 3s2

C 1s2 2s2 2p6 3s2 3p2

D 1s2 2s2 2p6 3s2 3p6 3d5 4s2


(Total 1 mark)

11. Which chemical term best describes what happens, when butylamine is added to a solution of a
copper(II) salt?

A precipitation

B redox

C proton transfer

D complex formation
(Total 1 mark)

12. (a) (i) Give the electron configuration of:

Fe [Ar] .........................................................................................................

Fe2+ [Ar] .........................................................................................................


(1)

(ii) Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6]2+, clearly showing its
shape.

(1)

St Michael's Catholic Grammar School 22


(iii) Give the equation for the complete reaction of hydroxide ions with a solution of
hexaaquairon(II) ions.

(1)

(iv) State what you would see if the product mixture in (iii) is left to stand in air.

...........................................................................................................................

...........................................................................................................................
(1)

(b) Consider the equation for the half reaction

Fe2+ + 2e Fe E = 0.44 V

(i) Define the term standard electrode potential with reference to this electrode.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(ii) Explain why the value of E suggests that the iron will react with an aqueous
solution of an acid to give Fe2+ ions and hydrogen gas.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.

St Michael's Catholic Grammar School 23


...........................................................................................................................

...........................................................................................................................
(1)
(Total 10 marks)

St Michael's Catholic Grammar School 24


1. (a) Write the electronic structure of a manganese atom and a Mn2+ ion.

3d 4s

Mn [Ar]

Mn 2+ [Ar]

(2)

(b) Solutions of manganese(II) sulphate contain the hydrated manganese(II) ion.

(i) Write the formula of this ion.

......................................................................................................................
(1)

(ii) When aqueous ammonia is added to a solution of manganese(II) sulphate, a buff


coloured precipitate is obtained. Write an ionic equation for this reaction and state
the type of reaction taking place.

Equation .......................................................................................................

Type of reaction ............................................................................................


(3)

(iii) The precipitate produced slowly darkens on exposure to air. Suggest a reason for
this and state two characteristic properties of transition elements that are being
shown by manganese.

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................
(4)

1
(c) Potassium manganate(VII), KMnO4, reacts with sulphite ions, SO32, in acidic solution
according to the equation

2MnO4 + 5SO32 + 6H+ 2Mn2+ + 5SO42 + 3H2O

Sodium sulphite, Na2SO3, is slowly oxidised in air to sodium sulphate, Na2SO4, and
hence it is very difficult to keep it pure.

1.75 g of an impure sample of sodium sulphite was dissolved in water and made up to
250 cm3 with distilled water. 25.0 cm3 of this solution required 22.8 cm3 of 0.0216 mol
dm3 potassium manganate(VII) solution for complete oxidation.

(i) Calculate the change in oxidation number of sulphur in the reaction of sulphite ions
with manganate(VII) ions.

(1)

(ii) Calculate the amount (in moles) of manganate(VII) ions used in the titration.

(1)

(iii) Calculate the amount (in moles) of sodium sulphite present in 25.0 cm3 of the
solution.

(1)

2
(iv) Calculate the total mass of pure sodium sulphite in 250 cm3 of the solution.

(2)

(v) Calculate the percentage purity of the sample of sodium sulphite.

(1)
(Total 16 marks)

2. This question is about Group 7 of the Periodic Table - the halogens.


The standard electrode potentials for these elements are given below.

Electrode reaction E /V

1
2
F2 + e F +2.87

1
2
Cl2 + e Cl +1.36

1
2
Br2 + e Br +1.07

1
2
I2 + e I +0.54

3
(a) (i) Define the term standard electrode potential.

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)

(ii) State which element or ion in the table above is the strongest oxidising agent.

......................................................................................................................
(1)

(b) The standard electrode potentials for chromium(III) changing to chromium(II) and for
chromium(VI) changing to chromium(III) are given below.

Cr3+ + e Cr2+ E = 0.41V

1
2
Cr2 O72+ 7H+ + 3e Cr3+ + 7
2
H2O E = +1.33V

(i) On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III).

......................................................................................................................
(1)

(ii) On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III) but not to chromium(VI).

......................................................................................................................
(1)

4
(iii) Chromium(II) in aqueous solution is sky blue while aqueous chromium(III)
solution is dark green. Describe how you would show that your prediction in part
(ii) actually worked in practice.

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)

3. (a) Complete the electronic structure of a scandium atom, a chromium atom and a Cr3+ ion.

3d 4s

Sc [Ar]

Cr [Ar]

Cr 3+ [Ar]

(3)

(b) Both scandium and chromium are d-block elements, but only chromium is a transition
element. Explain the meaning of these two terms.

....................................................................................................................................

....................................................................................................................................

....................................................................................................................................
(2)

5
(c) Cr3+ exists in aqueous solution as the green ion [Cr(H2O)6]3+.

(i) Complete the electrons in boxes diagram for the complex ion [Cr(H2O)6]3+.
Distinguish clearly the chromium electrons from those of the ligand.

3d 4s 4p

[Ar]

(2)

(ii) Draw the [Cr(H2O)6]3+ ion so as to clearly show its shape.

(1)

(iii) Explain the origin of the colour in [Cr(H2O)6]3+.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

(d) (i) State what you would see if aqueous sodium hydroxide was added drop by drop to
a solution of [Cr(H2O)6]3+ until the sodium hydroxide was in excess.

............................................................................................................................

............................................................................................................................
(2)

6
(ii) What type of reaction is occurring in (i)?

............................................................................................................................

............................................................................................................................
(1)
(Total 14 marks)

4. (a) The electronic configuration of a cobalt atom can be written as [Ar]3d74s2.


Give the electronic configuratin of the Co3+ ion.

......
(1)

(b) (i) By reference to the standard electrode potentials given below, suggest a reducing
agent which might reduce aqueous Co3+ ions to cobalt metal. Give your reasoning.

E /V
Zn2+(aq) + 2e Zn(s) 0.76
Fe2+(aq) + 2e Fe(s) 0.44
Co2+(aq) + 2e Co(s) 0.28
Sn2+(aq) + 2e Sn(s) 0.14
O2(g) + 2H+(aq) + 2e H2O2(aq) +0.68

Co3+(aq) + e Co2+(aq) +1.82

Suitable reducing agent ....

Reasoning .....

.......
(3)

7
(ii) Suggest two factors that might prevent a reducing agent from being as effective as
the electrode potentials might seem to suggest.

.......

.......

.......

.......
(2)

(c) (i) Write the formula of the hexaaquacobalt(II) ion.

.......
(1)

(ii) Give an equation, involving the hexaaquacobalt(II)ion, to illustrate the process


of ligand exchange.

.......
(2)
(Total 9 marks)

5. (a) State what is meant by the term transition element.

......

......
(1)

8
(b) Two reactions of chromium(III) chloride are outlined below

An aqueous solution of
chromium(III) chloride

NaOH(aq) Zn(s) + HCl(aq)

B, a green gelatinous precipitate C, a sky blue solution

(i) Give two features of chromium chemistry, illustrated in the above scheme, which
are typical of a transition element.

.......

.......

.......
(2)

(ii) Identify the chromium-containing species in solution C.

.......
(1)

(c) Evaporating cold aqueous chromium(III) chloride produces violet crystals. However
when hot aqueous chromium(III) chloride crystallises, green crystals result.

Both types of crystal have the same composition by mass: 19.5% chromium, 40.0%
chlorine and 40.5% water.

(i) Show that the empirical formula of these two salts is Cr(H2O)6Cl3.

(2)

9
(ii) The addition of excess aqueous silver nitrate to aqueous solutions of either of these
two salts produces a precipitate of silver chloride, AgCl.

Ag+(aq) + Cl(aq) AgCl(s)

Under these conditions all the chloride from the violet salt is precipitated but only
two-thirds of the chloride from the green salt.

Suggest formulae for the two salts given that water molecules may be either
ligands in the complex ion or simple water of crystallisation and that chloride ions
could be ligands in the complex ion or separate, simple ions.

(2)
(Total 8 mark)

6. (a) Complete the following electronic configurations.

(i) Cr:

3d 4s
[Ar]

(1)

(ii) Cr3+:

3d 4s
[Ar]

(1)

10
(b) Consider the following reaction scheme.

excess conc
[Cr(H2O)6]3+(aq) green precipitate
NH 3 (aq)
solution X
NH 3 (aq)

Step 1 Step 2

(i) Name the two types of bond present in the [Cr(H2O)6]3+ ion.

......................................................................................................................

......................................................................................................................
(2)

(ii) Name the type of reaction occurring in Step 1.

......................................................................................................................
(1)

(iii) Write a formula for the green precipitate.

......................................................................................................................
(1)

(iv) Name the type of reaction occurring in Step 2.

......................................................................................................................
(1)

(v) Give the formula of the chromium-containing species in solution X.

......................................................................................................................
(1)

11
(c) Explain the origin of the colour of transition metal aqua ions such as [Cr(H2O)6]3+.

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................
(3)
(Total 11 marks)

7. (a) Complete the electronic configurations for:

(i) a nickel atom;

1s2 ..............................................................................................................................
(1)

(ii) a Ni2+ ion.

1s2 ..............................................................................................................................
(1)

12
(b) Draw the ion hexaaqua nickel(II), [Ni(H2O)6]2+, so as to clearly show its shape. Label on
your diagram each type of bond present.

(3)

(c) If ammonia solution is added slowly to an aqueous solution containing nickel(II) ions, a
pale green precipitate initially forms. This dissolves to give a blue solution in excess
ammonia.

(i) Give the formula of the pale green precipitate.

.....................................................................................................................................
(1)

(ii) State the type of reaction occurring when ammonia solution is added as in (i) and
explain the formation of the precipitate.

.....................................................................................................................................

.....................................................................................................................................
(2)

13
(iii) Explain what occurs when excess ammonia is added.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)
(Total 10 marks)

(i) Give two features of chromium chemistry, illustrated in the above scheme, which
are typical of a transition element.

.......

.......

.......
(2)

(ii) Identify the chromium-containing species in solution C.

.......
(1)

14
(c) Evaporating cold aqueous chromium(III) chloride produces violet crystals. However
when hot aqueous chromium(III) chloride crystallises, green crystals result.

Both types of crystal have the same composition by mass: 19.5% chromium, 40.0%
chlorine and 40.5% water.

(i) Show that the empirical formula of these two salts is Cr(H2O)6Cl3.

(2)

(ii) The addition of excess aqueous silver nitrate to aqueous solutions of either of these
two salts produces a precipitate of silver chloride, AgCl.

Ag+(aq) + Cl(aq) AgCl(s)

Under these conditions all the chloride from the violet salt is precipitated but only
two-thirds of the chloride from the green salt.

Suggest formulae for the two salts given that water molecules may be either
ligands in the complex ion or simple water of crystallisation and that chloride ions
could be ligands in the complex ion or separate, simple ions.

(2)
(Total 8 mark)

15
8. The concentration of iron(II) ions in a solution can be found by titration with standard
potassium manganate(VII) solution. In the reaction iron(II) ions are oxidised to iron(III)
ions.

If a solution contains both iron(II) and iron(III) ions, the concentration of each ion can be
found by:

titrating samples of the original solution with standard potassium manganate(VII) solution

reacting samples of the original solution with zinc and dilute sulphuric acid and then titrating
with the same potassium manganate(VII) solution.

The following standard electrode potentials are required:

E/V

Zn2+ + 2e Zn 0.76

Fe2+ + 2e Fe 0.44

Fe3+ + e Fe2+ + 0.77

MnO4 + 8H+ + 5e Mn2+ + 4H2O + 1.51

(a) (i) Use suitable E values to show that both iron(II) and iron(III) ions in solution
should react with zinc to give iron metal.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

16
(ii) In practice the reaction produces only iron(II) ions and no iron metal.

2Fe3+ + Zn 2Fe2+ + Zn2+

Suggest a reason for this.

.....................................................................................................................................

.....................................................................................................................................
(1)

(b) (i) Derive the ionic equation for the reaction between iron(II) ions and
manganate(VII), MnO4, ions.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(ii) State what you would see as iron(II) ions in solution are titrated with potassium
manganate(VII). How would you detect the endpoint of the titration?

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

17
(c) A solution containing both iron(II) and iron(III) ions was titrated with 0.0200 mol dm3
potassium manganate(VII) solution, 18.20 cm3 being required.

Another portion of the same volume of the same solution was reacted with zinc, and then
titrated with the same potassium manganate(VII) solution; 25.30 cm3 was required.
What mass of zinc had reacted?

(5)

18
(d) (i) Explain, including an equation, why aqueous solutions of hexaaqua ions such as
[Fe(H2O)6]2+ are acidic.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(ii) Suggest with reasons which of 0.1 mol dm3 aqueous solutions of [Fe(H2O)6]2+ and
[Fe(H2O)6]3+ would be the more acidic.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)
(Total 20 marks)

9. (a) Complete the electronic configurations of

(i) a zinc atom:

1s2 ...............................................................................................................................
(1)

(ii) a Zn2+ ion:

1s2 ...............................................................................................................................
(1)

(b) State why zinc is classified as a d-block element but not as a transition element.

............................................................................................................................................

............................................................................................................................................

............................................................................................................................................
(2)

19
(c) Draw a 3-dimensional representation of the [Zn(H2O)6]2+ ion, including the bond angles.

Indicate on your diagram the types of bonding present.

(4)

(d) (i) State what you would see when ammonia solution is added to an aqueous solution
of zinc(II) ions, first in a small amount and then to excess.

.....................................................................................................................................

.....................................................................................................................................
(2)

20
(ii) Give equations for the reactions that occur in (d)(i)

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(e) (i) Explain why [Zn(H2O)6]2+ ions have no colour.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(ii) Why is zinc chromate(VI), ZnCrO4, bright yellow?

.....................................................................................................................................
(1)
(Total 16 marks)

10. (a) (i) Give the electronic configuration of:

Fe [Ar].....................................................................................................

Fe2+ [Ar].....................................................................................................
(2)

21
(ii) Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6]2+, so as to clearly show
its shape.

(1)

(iii) Give the equation for the complete reaction of sodium hydroxide solution with a
solution of hexaaquairon(II) ions.

............................................................................................................................
(1)

(iv) State what you would see if the product mixture in (iii) is left to stand in air.

............................................................................................................................

............................................................................................................................
(1)

(v) Give the equation for a reaction in which iron metal is used as a catalyst.

............................................................................................................................
(1)

22
(b) Consider the half reaction

Fe2+ + 2e Fe E = 0.44 V

(i) Define the term standard electrode potential with reference to this electrode.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

(ii) Explain, with the aid of an equation, why the value of E suggests that iron will
react with an aqueous solution of an acid to give Fe2+ ions and hydrogen gas.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.

............................................................................................................................

............................................................................................................................
(1)

23
(c) Use the following standard electrode potentials to explain why iron(III) iodide does not
exist in aqueous solution.

Fe3+ + e Fe2+ E = +0.77 V

I2 + 2e 2I E = +0.54 V

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(2)
(Total 15 marks)

11. (a) The elements from scandium to zinc belong to the d-block. Some, but not all, of these
elements are transition elements.

(i) What is meant by the term transition element?

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Which of the elements, from scandium to zinc inclusive, are in the d-block but are
not transition elements?

...........................................................................................................................
(1)

(b) (i) Complete the electronic configurations of the Fe2+ and Mn2+ ions below.

Fe2+ [Ar] ..............................................................................................................

Mn2+ [Ar] .............................................................................................................


(1)

24
(ii) Suggest why Fe2+ ions are readily oxidised to Fe3+ ions, but Mn2+ ions are not
readily oxidised to Mn3+ ions.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(c) Draw a diagram to show the three-dimensional structure of the [Fe(CN)6]4 complex ion.

(2)

(d) A solution of potassium manganate(VII), KMnO4, can be standardised by titration with


arsenic(III) oxide, As2O3. In this reaction, 5 mol of arsenic(III) oxide are oxidised to
arsenic(V) oxide, As2O5, by 4 mol of manganate(VII) ions, MnO4.

Calculate the final oxidation number of the manganese.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(4)

25
(e) Ammonium vanadate(V), NH4VO3, reacts with dilute sulphuric acid to form a solution
containing yellow VO2+ ions.

(i) Write an ionic equation for the reaction of the anion in NH4VO3 with dilute
sulphuric acid.

...........................................................................................................................
(1)

(ii) Is the reaction in (i) a redox reaction? Justify your answer.

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Addition of zinc to the solution containing VO2+ ions causes the colour to change
from yellow to green then to blue, followed by green again and finally violet.
State the formulae of the ions responsible for each of these colours.

The first green colour ...............................................................................

The second green colour ...............................................................................

The violet colour ................................................................................


(3)
(Total 16 marks)

26
12. Domestic bleaches contain sodium chlorate(I), NaOCl.

(a) Write the ionic equation to show the disproportionation of the chlorate(I) ion. Use
oxidation numbers to explain the meaning of the term disproportionation in this reaction.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(b) Domestic bleaches are dilute solutions of sodium chlorate(I). The amount of ClO ions in
a sample can be found by reacting it with excess acidified potassium iodide solution.

ClO + 2I + 2H+ I2 + Cl + H2O

The iodine produced is then titrated with standard sodium thiosulphate solution.

10.0 cm3 of a domestic bleach was pipetted into a 250 cm3 volumetric flask and made
up to the mark with distilled water.
A 25.0 cm3 portion of the solution was added to excess acidified potassium iodide
solution in a conical flask.
This mixture was titrated with 0.100 mol dm3 sodium thiosulphate solution, using
starch indicator added near the end point.
The mean titre was 12.50 cm3.

(i) Give the colour change you would see at the end point.

...........................................................................................................................

...........................................................................................................................
(1)

27
(ii) The equation for the reaction between iodine and thiosulphate ions is

2S2O32 + I2 S4O62 + 2I

Calculate the amount (moles) of chlorate(I) ions in 1.00 dm3 of the original bleach.

(5)

(iii) Use the equation below to calculate the mass of chlorine available from 1.00 dm3
of the original bleach. Give your answer to 3 significant figures.

ClO + Cl + 2H+ Cl2 + H2O

(1)

28
(c) Sodium thiosulphate can be used to remove the excess chlorine from bleached fabrics.

S2O32 + 4Cl2 + 5H2O 2SO42 + 10H+ + 8Cl

By considering the change in oxidation number of sulphur, explain whether chlorine or


iodine is the stronger oxidising agent when reacted with thiosulphate ions.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(d) Starch-iodide paper can be used to test for chlorine. It contains starch and potassium
iodide.

Explain the reactions taking place when a piece of damp starch-iodide paper is put in a
gas jar of chlorine. State what you would see.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)
(Total 14 marks)

29
13. (a) Complete the following electronic configurations.

Ni

3d 4s

[ Ar ]

Ni2+

3d 4s

[ Ar ]
(2)

(b) Explain why nickel is classified as a transition metal.

.....................................................................................................................................

.....................................................................................................................................
(1)

(c) Consider the following reaction scheme.


a few drops
2+
of NH3(aq) pale green
Step 1: [Ni(H2O)6] (aq)
precipitate

excess
pale green NH3(aq)
Step 2: blue solution X
precipitate

(i) What types of bond are present in the [Ni(H2O)6]2+ ion?

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Write an equation for the formation of the pale green precipitate.

...........................................................................................................................
(1)

30
(iii) Explain why Step 1 is a deprotonation reaction.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iv) Name the type of reaction occurring in Step 2.

...........................................................................................................................
(1)

(v) Give an equation for the reaction in Step 2.

...........................................................................................................................

...........................................................................................................................
(2)

(d) Explain why the hexaaquanickel(II) ion, [Ni(H2O)6]2+, is coloured.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)
(Total 14 marks)

31
1. Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays
fatigue in muscles, thus allowing people to show great strength under stress.

Benzedrine is a pharmaceutical which stimulates the central nervous system in a similar manner
to adrenalin.

HO
H

CH 2 CH(CH 3 ) NH 2 HO CH(OH) CH 2 N CH 3

Benzedrine Adrenalin

(a) (i) On the structure for benzedrine mark with a (*) any asymmetric carbon atom that
causes chirality.
(1)

(ii) Suggest why adrenalin is more soluble in water than is benzedrine.

..........................................................................................................................

..........................................................................................................................

..........................................................................................................................
(2)

(b) Give the structural formulae of the organic products obtained when benzedrine reacts
with:

(i) an aqueous acid such as dilute hydrochloric acid;

(1)

(ii) ethanoyl chloride in the absence of a catalyst;

(1)

(iii) excess ethanoyl chloride in the presence of the catalyst anhydrous aluminium
chloride.

(2)

1
(d) It is possible to eliminate a molecule of water from adrenalin which for the purpose of
this question may be represented as RCH(OH)CH2NHCH3. Draw the structural
formulae of the two stereoisomers produced.

(2)

(e) The mass spectra of both benzedrine and adrenalin have a peak at a mass/charge ratio of
44. Draw the structure of the species which give these peaks.

(i) in benzedrine;

(1)

(ii) in adrenalin.

(1)
(Total 11 marks)

2. (a) Define:

(i) the standard enthalpy of formation of benzene, C6H6(l);

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)

(ii) the standard enthalpy of combustion of benzene, C6H6(l).

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)

2
(b) Calculate the standard enthalpy of formation of benzene, C6H6(l), using the following
enthalpy of combustion data:

Substance H c /kJ mol1

C6H6(l) 3273

H2(g) 286

C(s) 394

(3)

(c) If the standard enthalpy of formation is calculated from average bond enthalpy data
assuming that benzene has three C==C and three CC bonds, its value is found to be
+215 kJ mol1.
Explain, with reference to the structure and stability of benzene, why this value differs
from that calculated in (b). Use an enthalpy level diagram to illustrate your answer.

................................................................................................................................

................................................................................................................................

................................................................................................................................
(4)

3
(d) Benzene reacts with bromine when gently warmed in the presence of a catalyst of
anhydrous iron(III) bromide.

(i) The reaction is first order with respect to benzene and first order with respect to
bromine. Write the rate equation for the reaction.

......................................................................................................................
(1)

(ii) The mechanism of this reaction involves an attack by Br+ followed by loss of H+.

Step 1. H
Br + + Br

Step 2. H Br
+ Br
+H +

Deuterium, symbol D, is an isotope of hydrogen, and the CD bond is slightly


stronger than the CH bond. If step 2 were the rate-determining (slower) step,
suggest how the rate of this reaction would alter if deuterated benzene, C6D6, were
used instead of ordinary benzene, C6H6, and explain your answer.

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)
(Total 14 marks)

3. Benzene, C6H6, reacts with ethanoyl chloride, CH3COCl, by an electrophilic substitution


reaction in the presence of aluminium chloride as a catalyst.

(a) Identify the electrophile involved in this reaction and write an equation to show its
formation.

................................................................................................................................

................................................................................................................................
(2)

(b) Draw the mechanism for the electrophilic substitution of benzene by ethanoyl chloride.

4
(3)

(c) Suggest a reaction scheme, stating reagents and conditions, to convert the product of the
above reaction into

OH

C 6 H5 C COOH

CH 3
(5)
(Total 10 marks)

4. (a) Pure copper is needed for electrical applications. The purity of a sample of copper can be
found by reacting it with concentrated nitric acid, neutralising the resulting solution and
treating it with excess potassium iodide. Iodine is liberated and this can be titrated with
standard sodium thiosulphate solution. The reactions are:

Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(1)

2Cu2+(aq) + 4I(aq) 2CuI(s) + I2(aq)

A copper foil electrode from an electric cell weighs 1.74 g. It was made into 250 cm3 of a
solution of copper(II) ions. To 25.0 cm3 of this solution excess iodide ions were added,
and the mixture titrated with 0.100 mol dm3 sodium thiosulphate solution. On average
26.8 cm3 was required. Calculate the percentage purity of the copper foil.
(6)

5
(b) Copper(II) chloride is used as a catalyst in the reaction of benzenediazonium chloride in
the presence of hydrochloric acid to give chlorobenzene:

+
C6H5N 2 Cl C6H5Cl + N2

The catalytic effect of transition metals or their ions is often attributed to their having
several stable oxidation states. Explain why such states are possible in transition metals
and why they are important in catalysis.
(4)

(c) (i) State the reagents and conditions needed to make benzenediazonium chloride from
phenylamine.
(2)

(ii) Explain why the temperature needs to be carefully controlled in the reaction in part
(i).
(2)

(iii) Write the equation for the reaction of benzenediazonium chloride with phenol
using structural formulae. Give the conditions under which benzenediazonium
chloride reacts with phenol and state what you would see.
(5)

(d) Phenylamine is prepared from benzene. Give the reagents and conditions needed for each
of the steps in the conversion of benzene to phenylamine.
(6)
(Total 25 marks)

5. (a) Benzene, C6H6, reacts with ethanoyl chloride, CH3COCl, to give a compound of
molecular formula C8H8O.

(i) Identify another substance that must be present for this reaction to occur and state
the function of this substance in this reaction.

.......

.......
(2)

6
(ii) Give the mechanism for this reaction.

(4)

(b) Phenol, C6H5OH, reacts differently from benzene with ethanoyl chloride. State the type
of reaction that would occur between phenol and ethanoyl chloride and give the structure
of the organic product.

Type of reaction ..

Structure of the organic product

(2)

(c) A benzene ring containing two hydroxy groups, C6H4(OH)2, can exist as a range
of isomers.

(i) Draw the structure of each isomer.

(2)

7
(ii) A polymer can be formed by reacting one of these isomers with the di-acyl
chloride, ClCOCH2COCl.

Draw a diagram indicating clearly the structure of such a polymer.

(2)

(d) The compound 4-hydroxyazobenzene

N N OH

can be obtained from phenylamine and phenol in two steps. Identify the intermediate
formed and give the reagents and conditions for each step.

.........

.........

.........

.........

.........

.........
(4)
(Total 16 marks)

8
6. This question is about the reactions of methoxybenzene, which are summarised in the following
diagram.

(a) Draw the fully displayed formula for methoxybenzene.

(1)

(b) Three of the reactions in the diagram are electrophilic substitution reactions.

Explain what is meant by the term electrophilic substitution.

......................................................................................................................................

......................................................................................................................................

......................................................................................................................................

......................................................................................................................................
(2)

9
(c) Draw the structural formula for 2-nitromethoxybenzene formed when methoxybenzene
reacts with nitric acid.

(1)

(d) Give the molecular formulae of two of the products, A and B, formed when
methoxybenzene reacts with bromine in an inert solvent.

(2)

(e) (i) Suggest the name for the organic product, C, formed when methoxybenzene reacts
with concentrated sulphuric acid.

............................................................................................................................
(1)

(ii) Suggest ONE use for the class of chemicals to which C belongs.

............................................................................................................................
(1)

(f) (i) Name reactant D and catalyst E needed to make methoxycyclohexane from
methoxybenzene.

D ........................................................................................................................

E ........................................................................................................................
(2)

10
(ii) This reaction is not a substitution reaction.

Give TWO alternative names which do describe this type of reaction.

...........................................................................................................................

...........................................................................................................................
(2)

(g) Many arenes like methoxybenzene are made from benzene.

(i) What is the natural resource from which benzene is produced?

...........................................................................................................................
(1)

(ii) Suggest why methoxybenzene rather than benzene is used in schools and colleges.

...........................................................................................................................
(1)
(Total 14 marks)

7. (a) Benzene can be converted into nitrobenzene.

(i) Give the reagents for the reaction.

......................................................................................................................

......................................................................................................................
(2)

11
(ii) Write the mechanism for the reaction, including the formation of the species that
attacks the benzene molecule.

(4)

(iii) Name the type of mechanism involved in this reaction.

......................................................................................................................
(1)

(b) Further reaction produces trinitrobenzene. Draw the structural formulae of the three
isomeric trinitrobenzenes.

(3)

(c) Give the reagents and conditions required for the conversion of nitrobenzene into
phenylamine, C6H5NH2.

...............................................................................................................................

...............................................................................................................................
(2)

12
(d) (i) Draw the structural formula of the organic product of the reaction between
phenylamine and ethanoyl chloride, CH3COCl.

(1)

(ii) The organic product of the reaction in (d) (i) is a solid at room temperature.
An impure sample of the solid can be purified by recrystallisation.
Describe how this recrystallisation can be carried out.

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................
(6)
(Total 19 marks)

8. Alanine, 2-aminopropanoic acid, is the simplest chiral amino acid found in nature and is
optically active.

H O
H2N C C
CH3 O H

13
(a) (i) Explain the meaning of the term chiral.

.....................................................................................................................................

.....................................................................................................................................
(1)

(ii) How is optical activity detected experimentally?

.....................................................................................................................................

.....................................................................................................................................
(2)

(iii) If alanine is made from propanoic acid the product mixture does not show optical
activity. Explain why this is so.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

14
(b) Alanine reacts with both acids and bases. Give the structural formulae of the compounds
you would expect if alanine reacts with

hydrochloric acid

sodium hydroxide

(2)

(c) Alanine has a high melting temperature of 300 C, much higher than would be expected
for the structure given at the start of the question.

Draw the structure that is actually present in the solid, and explain why the melting
temperature is so high.

............................................................................................................................................

...........................................................................................................................................

............................................................................................................................................
(2)

15
(d) Polyamides are made from a diacid dichloride and a diamine; they are condensation
polymers.

(i) Explain the term condensation polymer.

.....................................................................................................................................

.....................................................................................................................................
(1)

(ii) Suggest the structural formula of a diacid dichloride and a diamine that could be
reacted to form a polyamide.

(2)

(iii) Draw sufficient of the polymer chain that would result from the reaction of the
compounds in (ii) to make the structure of the polymer clear.

(2)

16
(iv) Alanine could be converted to CH3CH(NH2)COCl which on its own could
polymerise to a polyamide. Draw the structure of the polymer chain showing three
alanine repeating units and all the bonds in the amide links.

(2)
(Total 16 marks)

9. (a) The enthalpy of hydrogenation of cyclohexene is 120 kJ mol1.

+ H2

(i) Predict the value of H for the reaction:

+ 2H2

.....................................................................................................................................
(1)

17
(ii) Suggest the value of H for the hydrogenation of the hypothetical molecule
1,3,5-cyclohexatriene:

+ 3H2

.....................................................................................................................................
(1)

(iii) The enthalpy of hydrogenation of benzene is 208 kJ mol1. Explain in terms of the
structure and bonding in benzene why this value is different from your answer to
(a)(ii).

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(b) Benzene, C6H6, reacts with bromine to form bromobenzene, C6H5Br, and hydrogen
bromide.

(i) Give the formula of the catalyst that is needed for the reaction.

.....................................................................................................................................
(1)

18
(ii) Give the mechanism for the reaction, making clear the role of the catalyst.

(4)

(iii) State the type of mechanism that is commonly found with reactions of benzene and
its derivatives.

.....................................................................................................................................
(1)
(Total 11 marks)

10. X and Y are isomers with the molecular formula C7H6O2.

19
(a) Complete the table with the observations you would make when separate samples of X
and Y are warmed gently in test-tubes with the following solutions.

Solution Observation with X Observation with Y

sodium carbonate

Bradys reagent
(2,4-dinitrophenylhydrazine)

potassium dichromate(VI) +
sulphuric acid

(6)

(b) Both X and Y can take part in reactions in which esters are formed.

(i) Complete the structural formula of the ester which forms when X reacts with
methanol.

(1)

(ii) Y reacts with ethanoyl chloride to form an ester.

Draw the displayed formula of ethanoyl chloride.

(1)

20
(iii) Complete the displayed formula of the ester which forms when Y reacts with
ethanoyl chloride.

(2)

(iv) When X forms an ester with methanol, a catalyst is needed for the reaction to
proceed at a reasonable speed when heated gently.

Name a suitable catalyst for the esterification reaction.

...........................................................................................................................
(1)

(v) Explain why ethanoyl chloride is reactive enough to form an ester with Y at a
reasonable speed without a catalyst and without heating.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(c) The benzene ring in Y reacts readily with bromine in a substitution reaction.

(i) Name the type of reagent which attacks a benzene ring in substitution reactions.

...........................................................................................................................
(1)

21
(ii) Give the formula of the species which attacks the benzene ring when it reacts with
bromine in a substitution reaction.

.............................................................................................................................
(1)

(iii) Suggest a structural formula for an organic product of the reaction of bromine with
Y.

(1)

(iv) Y reacts with bromine more readily than benzene does. Suggest a reason for this.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)
(Total 17 marks)

22
11. This question is about the reactions of benzene and some related compounds.

(a) (i) Name the reagent and conditions for Reaction 1.

Reagent ..................................................................................................................

Conditions...............................................................................................................
(2)

(ii) Give the formula of the attacking species in this reaction.

...............................................................................
(1)

(b) (i) Give the structural formula of the organic compound A formed in Reaction 2.

(1)

23
(ii) State the type of reaction and its mechanism in Reaction 2.

Type .......................................................................................................................

Mechanism ............................................................................................................
(2)

(iii) Phenol, C6H5OH, will react with bromine in a similar way to benzene, but no
catalyst is needed. Explain why phenol will react readily with bromine without a
catalyst.

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................
(2)

(c) (i) Give the name of product B.

...............................................................................................................................
(1)

(ii) Explain how aluminium chloride acts as a catalyst in Reaction 3. You may find it
helpful to use an equation in your answer.

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................

...............................................................................................................................
(2)

24
(d) (i) What condition is needed for chlorine to react with benzene in Reaction 4?

...............................................................................................................................
(1)

(ii) Give the systematic name of the product of Reaction 4.

...............................................................................................................................
(1)
(Total 13 marks)

12. (a) Give the structural formula of the organic product when phenol is reacted with:

(i) sodium hydroxide solution

(1)

(ii) aqueous bromine

(1)

25
(iii) ethanoyl chloride.

(1)

(b) An azo dye can be made from benzenediazonium chloride.

(i) State the reagents and conditions needed to make benzenediazonium chloride from
phenylamine.

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................

............................................................................................................................
(3)

26
(ii) Write an equation, using structural formulae, to show the reaction between
benzenediazonium ions and phenol to give the azo dye.

(2)

(iii) What condition is required for the reaction in (ii) above?

............................................................................................................................
(1)
(Total 9 marks)

13. The reaction sequence below shows a method that could be used to convert benzene into
benzoic acid.

27
(a) (i) Name the reagent and catalyst that could be used to convert benzene into A in
Step 1.

Reagent ......................................... Catalyst ..........................................................


(2)

(ii) Name the type of reaction in Step 1 and its mechanism.

Type ............................................... Mechanism ...................................................


(2)

(iii) Write an equation to show how the catalyst interacts with the reagent in Step 1 and
explain how this helps the reaction to take place.

Equation

Explanation ............................................................................................................

...............................................................................................................................

...............................................................................................................................
(2)

(b) (i) B has several isomers. Draw the structural formula of ONE of these isomers, and
give its systematic name.

Structural formula

Name ......................................................................................................................
(2)

28
(ii) Name the reagent and catalyst you would use to try to make your isomer from A.

Reagent .......................................... Catalyst ..........................................................


(2)

(c) (i) Name the type and mechanism of the reaction in Step 3.

Type ............................................... Mechanism ....................................................


(2)

(ii) By considering halogenoalkane B, suggest whether the reaction in Step 3 is first or


second order. Justify your answer. Draw formulae to show the mechanism that you
suggest.

................................................................................................................................

(2)

(d) What type of reaction is Step 4?

.......................................................................................................................................
(1)

29
(e) Suggest TWO reactions in which you would observe the same results when carried out
with either compound C or benzoic acid. Describe what you would see in each of the two
reactions.

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................

.......................................................................................................................................
(4)
(Total 19 marks)

14. (a) A liquid hydrocarbon, A, has the molecular formula C6H10.

A has a boiling point of 356.5 K.

On complete combustion, 4.1 g of A forms 7.2 dm3 of carbon dioxide, and 4.5 g of water.

[Molar volume of a gas is 24 dm3 under the conditions of the experiment.]

(i) Write the empirical formula of A and use the combustion data to show that the
empirical formula is correct.

Empirical formula of A .........................................................................................

(3)

30
(ii) A reacts with an excess of bromine water to form B, C6H10Br2. Suggest structural
formulae of A and B.

(2)

(iii) B reacts with ammonia to produce C, C6H14N2. Give the structural formula for C.

State appropriate conditions, and write the balanced equation, for this reaction.

(4)

(b) Compound C reacts with hexanedioyl dichloride to produce a polymer.


Draw the structure of part of the polymer to show TWO repeating units.
State the type of polymerisation involved in making this polymer.

(2)
(Total 11 marks)

31
15. (a) Equations for the hydrogenation of three compounds are given below, together with the
corresponding enthalpy changes.

H2 H = 120 kJ mol
1

2H2 H = 240 kJ mol


1

3H 2 H = 208 kJ mol
1

Explain, in terms of the bonding in benzene, why the enthalpy change of hydrogenation
of benzene is not 360 kJ mol1.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

32
(b) Benzene can be converted into phenylamine, C6H5NH2, in two stages. Give the reagents
needed for each step and identify the intermediate compound formed.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(4)

(c) Benzene, C6H6, reacts with bromoethane, CH3CH2Br, in the presence of a catalyst, to
form ethylbenzene, C6H5CH2CH3, and hydrogen bromide.

(i) Give the formula of a catalyst for this reaction.

...........................................................................................................................
(1)

33
(ii) Give the mechanism for the reaction between benzene and bromoethane, including
the formation of the species that reacts with the benzene molecule.

(4)

(iii) Name the type of mechanism involved in this reaction.

...........................................................................................................................
(1)
(Total 13 marks)

16. This question is about the arene, naphthalene. The structure of naphthalene can be shown as

(a) What is the molecular formula of naphthalene?

.....................................................................................................................................
(1)

34
(b) The enthalpy change, H, for the addition of hydrogen to cyclohexene to form
cyclohexane is 120 kJ mol1.

+ H2 H = 120 kJ mol 1

(i) Calculate the enthalpy change of the hydrogenation reaction shown below.

+ 5H2

H = ...................... kJ mol1
(1)

(ii) Experimental work shows that H for the hydrogenation of naphthalene is actually
333 kJ mol1. What does this suggest about the stability and structure of
naphthalene?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) Would you expect naphthalene to decolorise bromine solution? Justify your
answer.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

35
(c) The Friedel-Crafts reaction enables an alkyl group to be attached to an arene ring.

(i) Suggest the reagent and catalyst you would need to make
CH(CH 3 )2
from naphthalene.

Reagent ..............................................................................

Catalyst ..............................................................................
(2)

(ii) Name the type of reaction and its mechanism.

...........................................................................................................................
(2)
(Total 9 marks)

17. (a) (i) Describe the appearance of the organic product obtained when an aqueous solution
of bromine is added to aqueous phenol.

...........................................................................................................................
(1)

(ii) Give the equation for the reaction in (a)(i).

(2)

(iii) Phenol reacts with ethanoyl chloride to form an ester. Complete the structural
formula to show the ester produced in this reaction.

(1)

36
(iv) Suggest, in terms of the bonding in ethanoyl chloride, why the reaction in (a)(iii)
proceeds without the need for heat or a catalyst.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(b) Phenylamine, C6H5NH2, is formed by the reduction of nitrobenzene, C6H5NO2. Give the
reagents which are used.

.....................................................................................................................................

.....................................................................................................................................
(1)

(c) Phenylamine is used to prepare azo dyes.

(i) State the reagents needed to convert phenylamine into benzenediazonium


chloride.

...........................................................................................................................

...........................................................................................................................
(2)

(ii) The reaction in (c)(i) is carried out at a temperature maintained between 0 C and
5 C. Explain why this is so.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

37
(iii) Addition of benzenediazonium chloride solution to an alkaline solution of phenol
gives a precipitate of the brightly coloured dye, 4-hydroxyazobenzene. Give the
structural formula of 4-hydroxyazobenzene.

(1)

(iv) Describe how recrystallisation is used to purify a sample of the solid dye formed in
(c)(iii).

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(5)
(Total 17 marks)

38
18. Paracetamol can be manufactured from phenol using the reaction sequence below.

OH OH OH OH

Step 1 Step 2 Step 3

NO 2 NH 2 NHCOCH3
A B C Paracetamol

(a) Give reagents and conditions for Step 1.

.....................................................................................................................................

.....................................................................................................................................
(2)

(b) State the type of reaction that occurs in Step 2.

.....................................................................................................................................
(1)

(c) (i) Give the name of compound C.

...........................................................................................................................
(1)

(ii) Suggest a test and its results for the amino group in compound C.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

39
(d) (i) Write a balanced equation for the reaction occurring when paracetamol is boiled
with an aqueous solution of sodium hydroxide.

(2)

(ii) Would you expect paracetamol to react with sodium carbonate solution? Justify
your answer.

...........................................................................................................................

...........................................................................................................................
(1)

(e) (i) Suggest which types of intermolecular forces exist between paracetamol molecules.
For each type of force give an example of the parts of the molecules involved.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(4)

40
(ii) Suggest a reason why paracetamol is only sparingly soluble in water.

...........................................................................................................................

...........................................................................................................................
(1)

(f) Suggest which bond gives rise to the broadest absorption in the infrared spectrum of
paracetamol.
State the range of wavenumbers for this absorption.

...........................................................................................................................

...........................................................................................................................
(2)

(g) (i) Give the molecular formula of the ion with the highest molecular mass in the mass
spectrum of paracetamol.

...........................................................................................................................
(1)

(ii) Suggest the formulae of the ions responsible for the peaks at mass / charge ratios
43 and 93.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(h) Suggest ONE advantage of using paracetamol, rather than aspirin, as a pain reliever.

.....................................................................................................................................

.....................................................................................................................................
(1)
(Total 20 marks)

41
19. Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring ingredients
found in foods. Synthetic vanillin, which is identical to natural vanillin, can be manufactured
from methoxybenzene. One synthetic route is shown below:

SO 3 H OH OH
OCH 3 OCH 3 OCH3 OCH3

CHO

methoxybenzene 2-methoxybenzene 2-methoxyphenol vanillin


sulphonic acid

(a) (i) Name the reagent which converts methoxybenzene to 2-methoxybenzene sulphonic
acid.

...........................................................................................................................
(1)

(ii) Name the type of reaction which occurs and its mechanism.

...........................................................................................................................
(2)

(b) After the final stage, in which 2-methoxyphenol is converted to vanillin, the impure
product can be purified by recrystallisation. In this process the solid is dissolved in the
minimum volume of hot water. The mixture is then filtered whilst still hot. The filtrate is
cooled in an ice bath to produce crystals of vanillin. These can be removed by filtration
and dried.

(i) Why is the minimum volume of hot water used?

...........................................................................................................................

...........................................................................................................................
(1)

42
(ii) The impure vanillin may contain soluble and insoluble impurities. Describe how
each of these is removed during recrystallisation.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) How would you check the purity of the vanillin after recrystallisation, other than by
using an infrared spectrometer.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

43
(c) In order to establish whether or not vanillin had been formed, two infrared spectra were
obtained: a sample of pure 2-methoxyphenol and a sample of the product.

Study the spectra and data below.

Infrared Spectrum of 2-Methoxyphenol


100

80
Transmittance
/% 60

40

20

3000 2000 1000


1
Wavenumber/cm

Infrared Spectrum of Product

100

80
Transmittance
/%
60

40

3000 2000 1000


Wavenumber /cm 1

Wavenumber / cm1
C C Stretching Vibrations Arene 1600 1450
CH Stretching Vibrations Arene 3030
OH Stretching Vibrations Alcohols and phenols 3750 3200
C O Stretching Vibrations Aldehydes 1740 1720
Ketones 1700 1680
Carboxylic acids 1725 1680
Esters 1750 1735

44
Comment as to whether any vanillin is likely to have been formed during the process.
Support your answer with relevant evidence.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)
(Total 10 marks)

20. Phenylethanoic acid occurs naturally in honey as its ethyl ester: it is the main cause of the
honeys smell.

The acid has the structure CH 2 COOH

Phenylethanoic acid can be synthesised from benzene as follows:

CH3 CH2Cl
step 1 step 2
Cl2 , uv

step 3
KCN

step 4
CH 2COOH Compound A

(a) State the reagent and catalyst needed for step 1.

.....................................................................................................................................

.....................................................................................................................................
(2)

45
(b) (i) What type of reaction is step 2?

...........................................................................................................................
(1)

(ii) Suggest a mechanism for step 2. You should include the initiation step, the two
propagation steps and a termination step.
You may use Ph to represent the phenyl group, C6H5.

(4)

46
(iii) Draw an apparatus which would enable you to carry out step 2, in which chlorine
is bubbled through boiling methylbenzene, safely.
Do not show the uv light source.

(3)
(Total 10 marks)

47
21. Toluene is the non-systematic name of an arene widely used in industry. Its formula is
C6H5CH3. Some of its reactions are summarised in the following diagram.

CH3

Br

Reaction 3 Br2/FeBr3

CH3 CH3 CHO


Reaction 2 Reaction 4
MnO2

NO2 Toluene Benzaldehyde


Fuming
Reaction 1 Reaction 5
H2SO4

Compound A CO2H

Benzoic acid

(a) (i) Give the systematic name of toluene.

...........................................................................................................................
(1)

(ii) Draw a possible structural formula for compound A.

(1)

48
(b) (i) Name the TWO reagents needed for Reaction 2.

...........................................................................................................................

...........................................................................................................................
(2)

(ii) Give the formula of the attacking species in Reaction 2.

...........................................................................................................................
(1)

(c) (i) Give the reaction type and mechanism in Reaction 3.

Reaction Type

...........................................................................................................................

Mechanism

...........................................................................................................................
(2)

(ii) Suggest why Reactions 1, 2 and 3 all take place under milder conditions than
similar reactions involving benzene.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(d) What type of reaction does toluene undergo in Reaction 4?

.....................................................................................................................................
(1)

49
(e) Name the TWO reagents needed for Reaction 5.

.....................................................................................................................................

.....................................................................................................................................
(2)
(Total 12 marks)

22. (a) Glycine is an amino acid.

COOH

HCH

NH2

(i) Draw the full structural formula of the zwitterion of glycine, showing all bonds.

(1)

(ii) Explain how the zwitterion in glycine is formed.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

50
(iii) Use your answer to (i) to explain why glycine has a high melting temperature of
262 C.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(b) Suggest the formula of the organic product formed when glycine reacts, under suitable
conditions, with

(i) hydrogen ions, H+

(1)

(ii) hydroxide ions, OH

(1)

O
(iii) ethanoyl chloride, H 3 CC
Cl

(1)

51
(iv) methanol, CH3OH

(1)

(c) Glutamic acid is also an amino acid. The formula of glutamic acid is shown below.

H2 NCCOOH

CH2

CH2

COOH

Glutamic acid exists as two optical isomers whereas glycine does not.

(i) Why is glutamic acid chiral?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

(ii) How can the two optical isomers of glutamic acid be distinguished from each
other?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

52
(d) A section of the polymer nylon-6,6 is shown below

O O O O

C(CH2)4CNH(CH2)6NHC(CH2)4CNH(CH2)6NH

Give the formulae of TWO monomers which could react together, under suitable
conditions, to form nylon-6,6.

(2)
(Total 13 marks)

23. The reaction scheme below shows a synthesis of the antiseptic, Dettol, from benzene.

reagent W 2 moles of reagent X


Benzene A B
C6H6 C6H6SO3 catalyst Y C8H10SO3

OH

reagent Z Cl2(g)
B C
C8H10SO3 C8H10O
H3 C CH3
Cl
Dettol
Study this reaction scheme carefully before answering any of the questions below.

53
(a) (i) Give the structural formula of A.

(1)

(ii) Name reagent W.

...........................................................................................................................
(1)

(iii) State the type of reaction and the mechanism for the conversion of benzene into A.

...........................................................................................................................
(1)

(iv) Give the formula of the species which attacks benzene to form A.

...........................................................................................................................
(1)

(b) (i) Suggest the structural formula of B. You may find it helpful to study the formula
for Dettol, as well as your answer to (a)(i), when answering this question.

(1)

(ii) Give the formulae for reagent X and catalyst Y.

Reagent X ........................................... Catalyst Y ...........................................


(2)

54
(iii) What gaseous inorganic compound will also be produced during the formation of
B?

...........................................................................................................................
(1)

(c) (i) Give the systematic name for Dettol.

...........................................................................................................................
(1)

(ii) Suggest why Dettol does not mix well with water.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)
(Total 10 marks)

24. (a) Benzene reacts with 2-bromopropane in a Friedel-Crafts reaction to give


2-phenylpropane, C6H5CH(CH3)2, usually known as cumene.

CH3
CH
CH3
+ CH3CHBrCH3 + HBr

cumene

Cumene is used to manufacture phenol and propanone.

(i) Identify a suitable catalyst for the reaction between benzene and 2-bromopropane.

...........................................................................................................................
(1)

55
(ii) Give the mechanism for the reaction, including the formation of the electrophile.

(4)

(b) If benzene and 1-bromopropane, CH3CH2CH2Br, are reacted under similar conditions to
those in part (a), the product is still cumene although 1-phenylpropane C6H5CH2CH2CH3
might have been the expected product.

CH3
CH
CH3
+ CH3CH2CH2Br + HBr

cumene

56
(i) Draw the structure of the carbocation which would initially be formed.

(1)

(ii) Suggest, in terms of relative stabilities of carbocations, what happens to the


carbocation in (i) which results in cumene as the product of the reaction rather than
1-phenylpropane.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(c) Phenol reacts with the benzenediazonium cation, C6H5N2+, in alkaline conditions to give
an azo dye.

(i) State the reagents needed to convert phenylamine into a solution containing
C6H5N2+ ions.

...........................................................................................................................
(2)

(ii) Explain why the temperature of the reaction in (c)(i) needs to be kept between 0 C
and 10 C.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

57
(iii) Give the structural formula of the product from the reaction between
benzenediazonium chloride and phenol.

(2)

(d) (i) How would you show that propanone is a carbonyl compound and is a ketone, not
an aldehyde?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(ii) A characteristic reaction of the carbonyl group, C O, is nucleophilic addition.


The C C double bond reacts by electrophilic addition.

Suggest the reason for the difference.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

58
(iii) Give the mechanism for the nucleophilic addition reaction between propanone and
hydrogen cyanide in the presence of a catalyst of cyanide ions, CN.

(3)
(Total 22 marks)

25. (a) The conversion of butan-2-ol to 2-bromobutane can be performed as outlined below:

Butan-2-ol is heated with a mixture of 50 % aqueous sulphuric acid and sodium


bromide for 45 minutes.
The crude 2-bromobutane is distilled off.
The crude 2-bromobutane is shaken with pure water, which removes the sulphuric
acid and some of the butan-2-ol that contaminates the product.
The organic layer is separated and then shaken with concentrated hydrochloric acid to
remove residual butan-2-ol.
The organic layer is then shaken with dilute sodium carbonate solution.
Anhydrous calcium chloride is added to the organic layer and allowed to stand for
some hours.
The organic layer is then redistilled in a dry apparatus.

59
(i) Explain, in terms of kinetic factors, why the mixture is heated for a significant
amount of time.

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Why is sulphuric acid necessary in the reaction mixture?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iii) Suggest why butan-2-ol, which is only partially miscible with water, is much more
soluble in concentrated hydrochloric acid.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(iv) Why is the organic layer shaken with dilute sodium carbonate solution?

...........................................................................................................................

...........................................................................................................................
(1)

(v) What is the purpose of the anhydrous calcium chloride?

...........................................................................................................................
(1)

60
(vi) How would you heat the mixture safely? Explain your choice of method.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

61
(b) Both 2-bromobutane and butan-2-ol are chiral molecules.

If one optical isomer of 2-bromobutane is used to make butan-2-ol by reaction with


aqueous hydroxide ions, the product mixture is not optically active.

The mechanism for the reaction is either SN1 or SN2; these are given below

SN1 CH2CH3 CH2CH3

+
H3 C C Br H3C C + :Br

H H

CH2CH3 CH2CH3

+
H3 C C + :OH H3C C OH

H H


SN2 HO: CH2CH3 CH2CH3

H3 C C Br HO C Br

H3C H
H

CH2CH3


HO C H + :Br

CH3

62
Explain which one of these mechanisms is consistent with the lack of optical activity in
the product mixture.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

(c) The oxidation of butan-2-ol with hot potassium dichromate(VI) in acidic solution
produces butanone, CH3COCH2CH3.

(i) What would you see as the reaction proceeds?

...........................................................................................................................
(1)

(ii) The dichromate(VI) ion is reduced under these conditions to chromium(III) ions.

The half-equation for the oxidation of butan-2-ol to butanone is

CH3CH(OH)CH2CH3 CH3COCH2CH3 + 2H+ + 2e

Write the ionic half-equation for the reduction of dichromate(VI) ions, and hence
derive the overall equation for the oxidation of butan-2-ol.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

63
(iii) The IR spectra of butan-2-ol and of the organic product from its oxidation with
dichromate(VI) ions are given below.

Spectrum of butan-2-ol

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500

Wavenumber/cm 1

Spectrum of the organic product from the oxidation of butan-2-ol

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500

Wavenumber/cm 1

Bond Wavenumber/cm1 Bond Wavenumber/cm1


CO (alcohols,
CH (alkanes) 28503000 10001300
esters)
OH (hydrogen-
CH (alkenes) 30003100 32303550
bonded alcohols)
C=O (aldehydes, 16801750 OH (hydrogen- 25003300
ketones, carboxylic bonded carboxylic
acids) acids)

64
What evidence is there from the spectra that the reaction in part (ii) has occurred?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(d) When potassium dichromate(VI) is dissolved in water, the following equilibrium is set up

Cr2O72(aq) + H2O(l) 2CrO42(aq) + 2H+(aq)

(i) If a solution of barium ions is then added to this solution, solid barium chromate,
BaCrO4, is precipitated; it is sparingly soluble in water, so the equilibrium given
below also exists in the solution

Ba2+(aq) + CrO42(aq) BaCrO4(s)

Explain what happens to the pH when the barium ions are added.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

65
(ii) If a solution of lead(II) ions is added instead of barium ions, solid PbCrO4 is
precipitated. This is almost completely insoluble in water so all chromate(VI) ions
are removed from solution

Pb2+(aq) + CrO42(aq) PbCrO4(s)

State how the pH of this solution differs from your answer in part (i).

...........................................................................................................................

...........................................................................................................................
(1)
(Total 20 marks)

26. An important industrial compound, S, has the formula

C 12 H25 SO 3 Na+

(a) (i) Name the reagents and give the conditions where necessary for the two steps
needed to make

SO 3 Na+ from benzene.

Step 1 Reagent ..................................................................................................

Conditions .................................................................................................

Step 2 Reagent ..................................................................................................


(3)

(ii) Name the type of reaction in each step.

Step 1 ................................................................................................................

Step 2 ................................................................................................................
(2)

66
(b) (i) What is the specific name given to the reaction when an alkyl group is introduced
into the benzene ring by electrophilic substitution?

...........................................................................................................................
(1)

(ii) Give the molecular formula of the reagent and of the catalyst needed to make

C12 H 25 from benzene.

Reagent .............................................................................................................

Catalyst .............................................................................................................
(2)
(Total 8 marks)

27. The drug ibuprofen can be synthesised from benzene by the route shown below.

CH3 CH3 CH3 CH3

HCCH3 HCCH3 HCCH3 HCCH3

CH2 CH2 CH2 CH2


CO/Pd
Step A Step B Step C catalyst

C O HCOH HCCO2H

CH3 CH3 CH3


Ibuprofen

(a) Name the type and mechanism of the reaction in Step A, and suggest a suitable reagent
and catalyst.

Type and mechanism ..................................................................................................

Name of the reagent for Step A ..................................................................................

Catalyst .......................................................................................................................
(3)

67
(b) Step C is a reduction.

Give ONE reason why lithium tetrahydridoaluminate, LiAlH4, is preferred to hydrogen as


a reducing agent in this reaction.

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(2)

(c) A sample of the final product was analysed by combustion. 1.00 g was burnt in oxygen. It
produced 2.78 g carbon dioxide and 0.786 g water.

State the molecular formula of ibuprofen and show that these results are consistent with
it.

(4)

68
(d) Ibuprofen can be analysed by instrumental methods. The infrared spectra of ibuprofen
and two other drugs, aspirin and paracetamol, not necessarily in that order, are shown
opposite.

CH3

HCCH3

CH2

Ibuprofen has the formula

HCCO2H

CH3

CO2H
O
OC
Aspirin has the formula CH3

OH

Paracetamol has the formula


CH3
HNC
O

(i) Explain, referring to the structure of each molecule, why infrared spectroscopy is
not a good technique to distinguish aspirin from ibuprofen.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

69
(ii) Deduce which of X, Y or Z is the infrared spectrum of paracetamol, giving a piece
of evidence from the spectrum you select.

Spectrum X
100

Transmittance (%)

50

0
4000 3000 2000 1500 1000
Wavenumber / cm1
Spectrum Y
100
Transmittance (%)

50

0
4000 3000 2000 1500 1000
Wavenumber / cm1
Spectrum Z
100
Transmittance (%)

50

0
4000 3000 2000 1500 1000
Wavenumber / cm1

70
...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(1)

(iii) Ibuprofen and aspirin can be distinguished using their mass spectra.

A line at mass/charge ratio 57 occurs only in the mass spectrum of ibuprofen.


Give the formula of the ion which produces this line.

...........................................................................................................................

Suggest the mass/charge ratio of one line which occurs in the mass spectrum of
aspirin but not ibuprofen, and the formula of the species which produces it.

...........................................................................................................................

...........................................................................................................................
(3)
(Total 14 marks)

28. X, Y, and Z are three different compounds from the list below. X and Y react together to form
an ester. X and Z also react to give the same ester as X and Y, but less readily.

Compound Y could be

A propanoyl chloride

B propanoic acid

C propan-1-ol

D propanal
(Total 1 mark)

71
29. Which of the following isomers of C4H10O has a chiral centre?

A Butan-1-ol

B Butan-2-ol

C 2-methylpropan-1-ol

D 2-methylpropan-2-ol
(Total 1 mark)

30. When the colourless liquid chlorobenzene is shaken with bromine water, the chlorobenzene
becomes a yellow orange colour. What is the interpretation of this?

A an addition compound of chlorobenzene and bromine has formed.

B the chlorine atom has been replaced by a bromine atom.

C a hydrogen atom has been replaced by a bromine atom.

D the bromine is more soluble in chlorobenzene than in water.


(Total 1 mark)

31. What class of organic compound has a characteristic smell and gives a solution in water with a
pH of about 10?

A arene

B amine

C aldehyde

D carboxylic acid
(Total 1 mark)

72
32. The substance of formula (OCH2CH2OOCC6H4COOCH2CH2OOCC6H4CO)n is a

A polyester

B natural oil or fat

C detergent

D protein
(Total 1 mark)

33. The optical isomers of alanine, CH3CH(COOH)NH2

A have different melting points

B rotate the plane of plane polarised light in opposite directions

C react at different rates with ethanoyl chloride, CH3COCl

D both occur naturally in protein molecules


(Total 1 mark)

34. The rate equation for the reaction between aqueous sodium hydroxide and
2-chloro-2-methylpropane is

Rate = k[2-chloro-2-methylpropane]

The first step in the mechanism of this substitution reaction is

A nucleophilic attack by OH ions on the carbon atom in the CCl bond

B electrophilic attack by OH ions on the carbon atom in the CCl bond

C the breaking of the CCl bond to form a carbocation

D the simultaneous making of a OC bond as the CCl bond breaks


(Total 1 mark)

73
35. When hydrogen cyanide, HCN, is added to ethanal, CH3CHO, the resulting solution has no
effect on the plane of polarisation of plane polarised light.

This is because

A ethanal is not chiral

B the product is not chiral

C the intermediate is planar

D the product is a racemic mixture


(Total 1 mark)

36. This question is about the following organic compounds:

A Benzene, C6H6

B Glycine, NH2CH2COOH

C Propene, CH3CHCH2

D Propanone, CH3COCH3

Select, from AD, the compound which would

(a) be a solid at room temperature

D
(1)

74
(b) give a salt by reaction with sodium hydroxide

D
(1)

(c) give a sulfonic acid by reaction with fuming sulfuric acid

D
(1)

(d) form a precipitate when reacted with 2,4-dinitrophenylhydrazine

D
(1)
(Total 4 marks)

37. (a) (i) Write the equation for the reaction between cyclohexene, , and bromine.

(1)

75
(ii) Draw out the mechanism for this reaction.

(3)

(b) (i) Write the equation for the reaction between benzene, , and bromine in the

presence of a catalyst of anhydrous iron(III) bromide, FeBr3.

...........................................................................................................................
(1)

(ii) Draw out the mechanism for this reaction. Include an equation for the formation of
the species that attacks the benzene ring.

(4)

76
(iii) Write an equation to show how the catalyst is regenerated.

...........................................................................................................................
(1)

(c) Comment critically on:

(i) the differences and similarities of the first steps involving the organic compounds
in both reactions.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(ii) why the two intermediates formed in these first steps then react differently?

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(3)

(d) State the number of peaks in the proton nmr spectrum of the product of the reaction
between cyclohexene and bromine.

.....................................................................................................................................
(1)
(Total 17 marks)

77