Answer two questions from Section A, one question from Section B, two questions from

Section C and one other question.

SECTION A

1 (a) By reference to relevant E data in the Data Booklet, explain how the halogen/halide electrode
potentials relate to the relative reactivity of the halogens as oxidising agents. [2]
(b) Use data from the Data Booklet to construct redox equations, and calculate the standard cell
potentials, for the reactions between
(i) Acidified H2O2 (aq) and KI (aq),
(ii) Cl2 (aq) + SO2 (aq). [4]
(c) Use data from the Data Booklet to predict the likely product of the reaction between I 2 (aq) and tin
metal, writing a balanced equation for the reaction. [2]
(d) (i) Write a chemical equation representing the lattice energy of AgBr.
(ii) Use the following data to calculate a value for the lattice energy of AgBr (s).
First ionisation energy of silver = +731 kj mol–1
Electron affinity of bromine = –325 kj mol–1
Enthalpy change of atomisation of silver = +285 kj mol–1
Enthalpy change of atomisation of bromine = +112 kj mol–1
Enthalpy change of formation of AgBr (s) = –100 kj mol–1
(iii) How might the lattice energy of AgCl compare to that of AgBr? Explain your answer. [4]

2 (a) What do you understand by the term order of reaction? [2]

(b) Cyanohydrins can be made by reacting ketones with an acidified solution of sodium cyanide.
(CH3)2C=O + H+ + CN– → (CH3)2 C (OH) CN
In a series of experiments, the reaction was carried out with different concentrations of the three reagents,
and the following relative initial rates were obtained.

(i) Use the data in the table to deduce the order of the reaction with respect to propanone, hydrogen ions,
and cyanide ions.’
(ii) Hence write a rate equation for this reaction.
Two different mechanisms have been suggested for this reaction
Mechanism A: (CH3)2C=O + H+ → (CH3)2COH+
(CH3)2COH+ + CN– → (CH3)2 C (OH) CN
Mechanism B: (CH3)2C=O + CN– → (CH3)2 C (O–) CN
(CH3)2C (O–) CN + H+ → (CH3)2 C (OH) CN
(iii) Which mechanism is consistent with the rate equation you deduced in (ii), and which step in this
mechanism is the slower (rate determining) step? Explain your answer. [7]
(c) Copper can be recovered from low-grade ores by ‘leaching’ the ore with dilute H 2SO4, which converts
the copper compounds in the ore into CuSO4 (aq). The concentration of copper in the leach solution can
be estimated by adding an excess of aqueous potassium iodide, and titrating the iodine produced with
standard Na2S2O3 (aq).
 2Cu2+ + 4I– 2CuI + I2
I2 + 2S2O32– 2I– + S4O62–
When an excess of KI (aq) was added to a 50.0 cm3 sample of leach solution, and the resulting mixture
titrated, 19.5 cm3 of 0.0200 mol dm–3 Na2S2O3 (aq) were required to discharge the iodine colour. Calculate
the [Cu2+ (aq)], and hence the percentage by mass of copper, in the leach solution. [3]

3 (a) In ethylamine, the alkyl group donates electrons to the N, making lone pair more available and in
phenyl amine, the lone pair is delocalized over the ring, so is less available. Describe how the basicities of
ammonia, ethylamine and phenyl amine differ.

[2]
(b) Describe how the use of aqueous silver nitrate and aqueous ammonia can distinguish between aqueous
solutions containing chloride, bromide or iodide ions. [3]
(c) Silver bromide is sparingly soluble in water.
AgBr(s) Ag+ (aq) + Br– (aq) Ksp = 5 × 10–13 mol2
–6
dm
(i) Calculate [Ag+(aq)] in a saturated aqueous solution of AgBr.
(ii) State and explain whether AgBr will be less or more soluble in 0.1 mol dm –3 KBr than it is in pure
water. [2]
(d) Silver ions form complexes with ammonia and with amines.
Ag+ (aq) + 2RNH2 (aq) [Ag (RNH2)2]+ (aq)
(i) Write an expression for the Kc for this reaction, and state its units. Kc has the numerical value of 1.7 ×
107 when R = H.
(ii) Using your expression for Kc calculate the [NH3 (aq)] needed to change the [Ag+ (aq)] in a 0.10 mol
dm–3 solution of silver nitrate to the value that you calculated in (c) (i).
(iii) Explain whether you would expect the Kc for the reaction where R = C 2H5 to be greater or less than
that for the reaction where R = H. [5]

SECTION B
4 Radium was discovered in the ore pitchblende by Marie and Pierre Curie in 1898, and the metal was
first isolated by them in 1910. The metal was obtained by first reacting the radium present in the
pitchblende to form insoluble radium sulfate which was converted into aqueous radium bromide. This
solution was then electrolysed using a mercury cathode and a carbon anode.
(a) Radium has chemical reactions that are typical of Group II metals and forms ionic compounds.
(i) What is the characteristic feature of the electronic configurations of all Group II metals?
(ii) Radium sulfate is extremely insoluble. From your knowledge of the simple salts of
Group II metals, suggest another very insoluble radium salt. [1]
(b) (i) Describe what you would see when magnesium reacts with
Cold water,
Steam.
(ii) Write an equation for the reaction with steam. [5]
(c) Radium reacts vigorously when added to water.
(i) State two observations that could be made during this reaction.
(ii) Suggest the approximate pH of the resulting solution.
(iii) Will the reaction be more or less vigorous than the reaction of barium with water? Explain your
answer. [4]
(d) Describe and explain qualitatively the trend in the solubilities of the sulfates of the Group II elements.
[2]

5 (a) The Group IV oxides CO2 and SiO2 differ widely in their physical properties. Describe these
differences and explain them in terms of their structure and bonding. [2]
(b) What are the properties of a ceramic material? Why is silicon (IV) oxide very suitable as a component
of ceramics? [2]
(c) Tin forms an oxide, A, that contains the metal in both oxidation states II and IV. The ormula of A can
be found by the following method.
• A sample of A was dissolved in H2SO4 (aq), producing solution B, which was a mixture of tin (II)
sulfate and tin(IV) sulfate.
• A 25.0 cm3 sample of solution B was titrated with 0.0200 mol dm–3 KMnO4. 13.5 cm3 of KMnO4 was
required to reach the end-point.
• Another 25.0 cm3 sample of solution B was stirred with an excess of powdered zinc. This converted all
the tin into tin (II). The excess of zinc powder was filtered off and the filtrate was titrated with 0.0200
mol dm-3 KMnO4, as before. This time 20.3 cm3 of KMnO4 was required to reach the end-point.
The equation for the reaction occurring during the titration is as follows.
2MnO4– + 16H+ + 5Sn2+ 2Mn2+ + 8H2O + 5Sn4+
(i) Write a balanced equation for the reaction between Zn and Sn 4+.
(ii) Use the Data Booklet to calculate the E o values for the reactions between
• Zn and Sn4+, ....................................................................................................
• MnO4– and Sn2+.. ................................................................................................
(iii) Use the results of the two titrations to calculate
• the number of moles of Sn2+ in the first titration sample,
• the number of moles of Sn2+ in the second titration sample.
(iv) Use the results of your calculation in (iii) to deduce the Sn2+/ Sn4+ ratio in the oxide
A, and hence suggest the formula of A. [8]

SECTION C
6 Astronomers using modern spectroscopic techniques of various types have found evidence of many
molecules, ions and free radicals in the dust clouds in Space. Many of the species concerned have also
been produced in laboratories on Earth. Two such species are the dicarbon monoxide molecule, C 2O, and
the amino free radical, NH2.
(a) (i) Dicarbon monoxide can be produced in a laboratory and analysis of it shows that the sequence of
atoms in this molecule is carbon-carbon-oxygen and there are no unpaired electrons, but one of the atoms
is only surrounded by six electrons. Draw a ‘dot-and-cross’ diagram of C 2O and suggest the shape of the
molecule.
(ii) What is meant by the term free radical ?
(iii) Explain why NH2 is described as a ‘free radical’. [4]
Two derivatives of ethene which have been detected in dust clouds in Space are acrylonitrile
(2-propenenitrile), CH2=CHCN, and vinyl alcohol (ethenol), CH2=CHOH.
(b) Like ethene, acrylonitrile can be polymerised. The resulting polymer can be used to make carbon
fibres.
(i) Draw the structural formula of the polymer made from acrylonitrile, showing two repeat units.
(ii) What type of polymerisation is this reaction? [2]
Vinyl alcohol cannot be polymerised in the same way as acrylonitrile because it will readily isomerise
into another common organic compound, Z.
(c) (i) Suggest the structural formula of the organic compound Z.
(ii) Suggest the structural formula of another isomer of vinyl alcohol which has a cyclic (ring) structure.
[2]
Acrolein (2-propenal), CH2=CHCHO, has also been found in Space.
(d) Give the structural formulae of the organic compounds formed when acrolein is reacted separately
with each of the following reagents.

[4]

7 (a) Compound G can be synthesised from benzene by the route shown below.

(i) Name the functional group formed in step 5.

(ii) Draw the structures of the intermediates H and J in the boxes above.
(iii) Suggest reagents and conditions for the following.
Step 2 ........................................................................................................................
Step 3 ........................................................................................................................
Step 4 ........................................................................................................................
Step 5 ........................................................................................................................
[6]
(b) In a reaction discovered just over 100 years ago by the German chemist Karl Fries, compound G is
converted into compound K when it is heated with AlCl3. Compound K is a structural isomer of G.

Compound K is a 1,4-disubstituted benzene derivative. It is insoluble in water, but dissolves in NaOH

(aq). It gives a white precipitate with Br 2 (aq), and a yellow precipitate with alkaline aqueous iodine.
(i) What is meant by the term structural isomerism?
(ii) Use the information given above to name two functional groups in compound K.
(iii) Suggest the structural formula of K, and draw it in the box above.
(iv) Suggest structures for the aromatic products of the following reactions.

[6]

8 Menthone, C10H18O, is a cyclic ketone that occurs in oil of peppermint.

menthone
(a) Use asterisks (*) on the formula above to identify any chiral centres in the molecule of menthone.

[2]
(b) Menthone can be reduced to menthol, which can be dehydrated to a mixture of two alkenes, L and M.

(i) Suggest reagents for

step 1, ......................................................................................................................
step 2. .......................................................................................................................
(ii) Suggest structures for L and M and draw them in the boxes above. [4]
(c) When heated with concentrated, acidified KMnO 4 (aq), one of the two alkenes L or M produces the
dicarboxylic acid N.

N
(i) Give the letter of the alkene that produced N by this reaction.
(ii) Suggest the structure of the product, P, of the reaction between the other alkene you have drawn and
hot concentrated acidified KMnO4.
(iii) Suggest one chemical test that would enable you to distinguish between N and P. [3]
(d) Chlorocyclohexane can be prepared by bubbling HCl (g) through a solution of cyclohexene.

Suggest the mechanism of this 2-stage reaction by means of a diagram. Include all whole or partial
charges, and represent the movements of electron pairs by curly arrows. [3]